Posts Tagged ‘Nexam Chemical’

What Is thermoplastic polymers and in what ways are Nexam Chemical improving the properties of the materials? One methodology will be described in this blog post.

A multitude of our popular plastics are defined as thermoplastics which means that upon recycling , their molecular properties does not change as the plastic is melted and reused (according to definition and in theory). Examples are PE, PP, PTFE (Teflon), ABS and polyamide (nylon).

A very easily digested full pedagogic description is available here:

https://sciencing.com/thermoplastic-polymer-5552849.html

Another example of a thermoplastic is PET (polyethyleneterephtalate) which is used in composite sandwich constructions and light weight construction materials. The company Armacell is active in this business with sustainability in focus (recycling of PET bottles):

https://local.armacell.com/en/armaform-pet-foam-cores/

CESI has already highlighted that according to the Q2 Nexam Chemical interim report, Armacell will use Nexam proprietary technology in the next generation PET foam:

“The delivery agreement that we signed with Armacell last quarter is about to, with some delay, find its practical form. Armacell will use NEXAMITE® in its ArmaFORM® PET-foam to achieve increased efficiency” Source link. Statement found on page 2.

The explanation to the repeated CESI highlight is the following finding: A new Nexam patent application was published a few days ago (November 22, 2017). The described invention relates to a process for increasing the melt strength of a thermoplastic polyester and to mitigate degradation of the polyester during melting.

The common (?) degradation issues of PET is pedagogically described in this open access article by Venkatachalam et. al.:

“The main degradations that can occur include thermal degradation, oxidative degradation and hydrolytic degradation. Radiation induced or photo degradation leading to free radical reactions and enzymatic catalysed reactions leading to logical degradation are also possible. In addition to these there can be chemical degradation reaction of polyester initiated by specific chemicals like glycol, ammonia or amines or other such reagents. Besides these there can be weathering ageing which could be the combined effect of exposure to temperature, moisture, chemical, UV and visible light and other conditions such as exposure to grease, oil. Polyester can also undergo stress induced degradation reactions when subjected to mechanical stress. The degradation of polyester can lead to several changes in the articles made out of the polymer. These changes include discoloration, chain scissions resulting in reduced molecular weight, formation of acetaldehyde and cross-links or gel formation and fish-eye formation in films.
The thermal and thermo oxidative results in poor processibility and performance
characteristics in the products. Discoloration is due to the formation of various
chromophoric systems following prolonged thermal treatment at elevated temperatures.
This becomes a problem when the optical requirements of the polymer are very high, such as in packaging applications.”

Let´s look at some quotes from the following new Nexam patent application…

EP3246349 PROCESS FOR INCREASING THE MELT STRENGTH OF A THERMOPLASTIC POLYMER

Publication Date:22.11.2017

Applicant: Nexam Chemical AB

Source link here (most easily digested if downloaded)

“However, especially thermoplastic polyesters, but also to some extent aliphatic polyamides, suffer from having a narrow processing window, thereby typically requiring specialized processing equipment. This is related to the melt rheology of thermoplastic polyesters. Thermoplastic polyesters typically have low melt viscosity, low melt strength, and low melt elasticity.”

[CESI: see blue font below for “rheology” explanations]

“[0012] By using PETA, rather than pyromellitic dianhydride (PMDA) commonly used in the art, the melt strength of thermoplastic polyesters could be considerably increased. By use of the same combination, i.e. PET A and a bisoxazoline, also the melt strength of polyamides, e.g. aliphatic polyamides, and thermoplastic polyurethanes, could be improved.

[0013] Further and importantly, the rate of the thermomechanical degradation seen in melt mixing of thermoplastic polyesters was considerably decreased compared to PBO/PMDA-systems, as can be seen from Fig. 1. For applications with longer residence times, such as residence times exceeding 10 minutes, this is a clear advantage, as the thermomechanical degradation is quite rapid for PBO/PMDA-systems. A typical example of an application with longer residence time is extrusion foaming of PET. polyesters was considerably decreased compared to PBO/PMDA-systems, as can be seen from Fig. 1.

CESI:  Nexam specify a large number of polyester polymer substrates and additives:

“According to an embodiment, the thermoplastic polymer is thus a polyester. The polyester is typically an aliphatic polyester or a semi aromatic polyester. The polyester may be selected from the group consisting of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), 30 polyglycolic acid (PGA), polylactic acid (PLA), polycaprolactone (PCL), and polyethylene naphthale (PEN). Specifically, the polyester employed may be a semi aromatic polyester. Examples of aliphatic polyesters include polylactic acid (PLA), polyglycolic acid (PGA), polycaprolactone (PCL), polyethylene adipate (PEA), and polyhydroxyalkanoate (PHA), e.g. poly-3-hydroxyvalerate (PHV), poly-4-hydroxybutyrate (P4HB), and poly-3-hydroxy propionate (P3HP). Examples of semi aromatic polyesters include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene 35 terephthalate (PPT), polybutylene terephthalate (PBT), and polytrimethylene terephthalate (PTT). Further, the semiaromatic polyester may be a co-polymer of PET, PBT, or PEN.

Thus, also a nucleating agent, such as talc, kaolin, silica gel, orTi02, a flame retardant, such as a halogenated, charforming (like phosphorus-containing) or water-releasing compound, a plasticizer, a lubricant, such as an ester of a fatty acid, an impact modifier, insulation modifier, a pigment, a filler, an antioxidant, a UV-stabilizer and/or a color improver may be added to the thermoplastic polymer and melt mixed therewith.”

Fig 2 visualizes (see graph in link here) that…

At high frequencies> 100 rad/s (i.e. at high shear rate) the differences between the different formulations is relatively small, whereas at low frequencies <1 rad/s (i.e. at low shear rate) the complex viscosity of the PETA-PBO formulation is approximately at least one order of magnitude higher than the comparative examples. Further, the cross-over point, which was determined from the frequency sweep analysis, was significantly lower for Example 1 as compared to the Comparative Examples 1-4. Determination of cross-over point is a method used to evaluate the melt strength (ref J. Frankland, Plastics Technology Online 2013-05-28). Thus, the  melt strength of the PETA-PBO formulation is superior compared to that of the comparative examples. Further, this confirms that pressure in the extruder may be used as a semi-quantitative measure of the melt strength, as the shear rate in the current experiments is about 6 rad/s in the extruder

The claim comprehends a number of polymides: PA6, PA 11, PA 12, PA46, PA41 0, 50 PA66, PA61 0, PA612, PA 1010, PA 1012, and PA 1212.

[CESI: Again, a polyamide is equivalent to nylon: https://en.wikipedia.org/wiki/Nylon]

And interestingly, the following article are stated in the final section of the patent application as a “document considered to be relevant”:

https://www.ptonline.com/articles/additives-multi-purpose-modifiers-pump-up-properties-of-virgin-recycled-plastics

Furthermore, the Armacell patent EP 2 163 577 A1 is exemplified.

In the ptonline link attached above,  a very interesting picture demonstrating the (potential) impact of Nexam technology is found (Nexam treated polymer vs untreated)

About Rheology- the science of deformation and flow of materials

Explanation of the unit rad/s found in the Nexam Chemical melt strength comparison plot:

  • Wikipedia (“shear rate unit” search): The SI unitof measurement for shear rate is s−1, expressed as “reciprocal seconds” or “inverse seconds
  • Wikipedia (“rad/s” search): In physics, the angular velocity of an object is the rate of change of its angular displacementwith respect to time. The SI unit of angular velocity is radians per second.

CESI Conclusion: It´s simply the frequency/velocity of the flow expressed in a more complicated way. Thus, it should directly correlate to the speed of the extrusion (the continuous manufacturing of plastics)

The link below describes fundamentals of Rheology in a pedagogic way: http://www.polydynamics.com/Rheology.pdf

CESI Learnings:

  • The higher the shear rate, the easier it is to force polymers to flow through dies and process equipment.”
  • When a force is acting tangentially on a surface, the corresponding stress is referred to as shear stress. Normal stress (=normal pressure) = when a force is perpendicular to a surface
  • Viscosity = Shear stress / shear rate (= a higher shear rate equals a lower viscosity)
  • Shear rate = Velocity / h (hight in the case of flow through 2 planes)
  • With careful rheological measurements, it is possible to determine whether, or under what conditions, a material will be processable. Blend ratios, or additive quantities necessary to facilitate processing can be determined. Many problems can be avoided by a thorough rheological characterization, before the material is introduced into the extruder hopper
  • With careful rheological measurements, it is possible to determine whether, or under what conditions, a material will be processable. Blend ratios, or additive quantities necessary to facilitate processing can be determined. Many problems can be avoided by a thorough rheological characterization, before the material is introduced into the extruder hopper

CESI rheology conclusion: So, rheology tells us that increased velocity (flow speed) will generally be beneficial for polymer processing up to the point shark skin (surface mattness) and melt fractures occurs as described in the article above.

In this patent application, Nexam demonstrate how melt strength can dramatically be increased even during slower speed (frequences,velocities, rad/s) and slow speed seems crucial for PET foam production and most importantly: The improvement is substantial – a full magnitude at < 1 rad/s (see page 14 here). The X axis unit “rad/s” was explained above (= frequency/ velocity/speed of the extrusion)

Thus, it seems that Nexam has solved/improved the melt strength in the “difficult slow extrusion PET foam case” by adding to Nexam product molecules that in fact result in a synergy effect As the key is to keep a high melt strength for an extended period of time as described here in the Nexam patent application quote:

[0058] Whereas system comprising PMDA or combinations of PMDA and PBO also are effective in reacting with PET to increase the melt strength (measured as increased pressured in the extruder), these systems are prone to quite rapidly cause degradation. For longer residence time, such as the ones typically used in e.g. foaming application, the final melt strength is thus significantly lower (cf. Fig. 1 and Table 4). However, as can be seen from Fig. 1 and Table 4, systems comprising combinations of PETA and PBO, may provide increased melt strength also for longer residence times as the melt strength declines far less rapidly. As can be seen in Fig. 1 for the PMDA, PMDA+PBO and PBO formulations, 20 the pressure reaches its maximum value in < 10 minutes and after that, it decreases with increasing time. For the PETA+PBO, on the other hand, the maximum pressure is obtained after> 10 minutes. Also, for the PETA+PBO formulation the pressure at the end of the experiment is significantly higher than for the comparative examples

The opposite easy case is the following scenario described at page 3 here: http://www.polydynamics.com/Rheology.pdf

“One remarkable property of polymeric liquids is their shear-thinning behavior (also known as pseudo-plastic behavior). If we increase the rate of shearing (i.e., extrude faster through a die), the viscosity becomes smaller [….] This reduction of viscosity is due to molecular alignments and disentanglements of the long polymer chains. As one author said in a recent article: “polymers love shear.” The higher the shear rate, the easier it is to force polymers to flow through dies and process equipment.”

Best regards, CESI

(Not skilled in the art of polymer chemistry but with an ambition to continuously gain learnings…)

The author, Cutting Edge Science Invest, is a Nexam Chemical share holder. Cutting Edge Science Invest can not guarantee, or take into  accountability, the content of truth and accuracy of the information in this article/post.Thus, Cutting Edge Science Invest requires that a possible reader gather complimentary information if any type of investment in the company described above is considered. Cutting Edge Science Invest provides personally biased information and at best also “general information and opinions”. The article/post does not contain professional investment advice. 

After a long period of humble and neutral statements, the Nexam Chemical CEO currently sings in major key. With cash ~100 Million SEK, the songs seems trustworthy:

Disclaimer: Presentation in Swedish. See recent interim reports for hard facts. 

 

The recent audiocasts also contain a lot of interesting information:

https://tv.streamfabriken.com/nexam-chemical-q3-2017

https://tv.streamfabriken.com/nexam-chemicals-q2-2017

Not only within its own internal patent portfolio, but also within the public external patent application landscape, Nexam Chemical seems healthy:

Slide1

Despite continued delays from Armacell (commented above)…

02/22/2017

 

…substantial scientific leaps within the research pipeline (with subsequent external funding) has been taken by the CEO Anders Spetz during the year:

05/15/2017

 

This press release is conceptually very interesting as graphene is predicted to become the next industry “wonder material” [Source link]

Furthermore, within the presumable future Nylon business area that…

09/21/2017

 

…vibrates well with the sheer CESI speculation that Nylon crosslinking using Nexam proprietary molecules eventually will be a reality (in industrial scale). Within the Nylon area, BASF is still presumably a Nexam partner due to (CESI speculation again):

  • The patent application previously commented here [Source link]
  • The Statement from Nexam in the original press release announcing the exclusivity agreement termination: “The collaboration will however continue between the parties and test material based on BASF’s polyamide 66 and Nexam Chemical’s additives will be tested in components by e.g. the automotive industry” )

 

Very interestingly, Nexam also attracted interest from the electronics industry:

10/17/2017

Nexam Chemical will early next year start supplying material to a new Japanese customer within the focus area high performance polymers, and thereby opening a new high performance segment – solutions for semiconductors.

The customer, a leading Japanese manufacturer of semiconductor materials, has for a long time collaborated with Nexam Chemical to produce materials that meet the high standards of semiconductor encapsulation materials. Semiconductors are included in the components of most of the electronics we currently have around us, e.g. mobile phones, computers etc. As components become smaller, the demand on heat resistance have increased. Nexam Chemical has materials that fit well for these requests.

”So far we have been focused on high temperature composites in the high performance area. We now have a first customer within semiconductors and we see opportunities for interesting projects together with several players, which in in the long run can lead to business. Initially it is about smaller volumes, but with a potential to develop further. This is a new exciting area where Nexam Chemical’s technology can create value for the material manufacturers” says Anders Spetz CEO at Nexam Chemical.

“The interest from the companies developing semiconductors is mainly based on that Nexam Chemical´s material and products enable curing at lower temperatures. The polymeric materials included in the semiconductors are cured in a later stage of the manufacturing process and therefore needs to be done at a lower temperature so that other parts are undamaged. As the industry moves towards smaller and smaller components, the temperature in the components are often higher during usage. Therefore, temperature-resistant materials like polyimide are needed. However, polyimide must normally be cured at fairly high temperatures, but with the help of NEXIMID®, the temperature can be reduced with up to 100 degrees Celsius. A significant difference” says Masaki Shimada at Kadotoku, Nexam Chemical´s distributor in Japan.

Another proof of principle of valuable product molecules is the announcement that Maverick has placed a first decent size order. Maverick is a producer of high temperature polyimide resins for the aerospace industry

0/26/2017

Nexam Chemical has received an order from Maverick with a value amounting to approximately SEK 5.3 million for NEXIMID®. The order will delivered according to call-off from the customer during 2018.

NEXMID® can be used to manufacture polyimide resin, which is an essential component in temperature resistant composites. Composites containing NEXIMID® is used in environments where extensive material stress and high temperature put extreme requirements on the material. The application area is mainly within advanced aircraft, space and other areas where the performance requirements on the materials are the highest.

“The order from Maverick is a confirmation that our solution add high value and that we have a strong offer within the high performance area. We are happy to see an increase in the order volume, which is promising for the future and we continuously work with the customer to provide new solutions that can generate additional value to their growing business”, says Anders Spetz, CEO.

Most importantly, new evidence that Nexam product molecules are viable is the following important press release. Despite the initial small order, this order should be defined as a proof of concept order:

11/07/2017

Diab, a global leader within core materials for various types of demanding composite constructions has placed its first major order of NEXAMITE®-based masterbatch. The order value amounts to approximately SEK 600 thousand and delivery will take place during the fourth quarter.

 

The launch of high performance PET-foam has started, with NEXAMITE®-technology forming an essential part. The PET-foam contains Nexam Chemical’s property enhancing additive NEXAMITE®, delivered in masterbatch formulation. Using NEXAMITE® in masterbatch formulation simplifies customers production process and secures a consistent product quality in the customers existing production equipment.

“I am very pleased that we now see the results from our development cooperation with Diab. It is a commercial breakthrough order for Nexam Chemical within the area PET-foam and I am convinced that we together with Diab has developed really strong products, relevant for solar and wind energy, automotive and transport solutions, as well as advanced building constructions. We look forward to a continued good cooperation with Diab,” says Anders Spetz, CEO at Nexam Chemical.

Of great importance is the following detail: Nexam is able to deliver already during Q4.

Another milestone that not yet has solidified financial impact is the following announcement:

11/15/2017

Nexam Chemical has received a first order from one of the leaders within high performance PET-foam. The order value amounts to approximately SEK 400 thousand and will be delivered during the fourth quarter.

Nexam Chemical develops and manufacture property enhancing additives under the brand NEXAMITE®. NEXAMITE® is delivered in a pre-blended mix, a so-called masterbatch. Through masterbatch NEXAMITE® can be added to customers’ existing production equipment, which simplifies the production process and ensures a high and stable product quality. This is the third leading company within PET-foam manufacturing that Nexam Chemical deliver masterbatch to.

“It is very pleasing to see that our determined work now start to become fruitful. The customer has tested our products for some time and we have now been trusted in delivering the first volume going directly into their production of high performance PET-foam. We look forward to further deepen our cooperation for increased volumes in the future,” says Anders Spetz, CEO at Nexam Chemical.

Additional CESI blog posts are available here [Source link]. Personally, CESI is most interested in the PE pipe business segment reviewed here [Source link]

CESI has also refreshed his memory by re-reading all previous interim reports. A collection of information defined as interesting is attached below:

Slide2Slide3Slide4Slide5

And worth highlighting is also the namned partner in the recent successful MATPAX project:

11/14/2017

MATPAX, a two year Eurostars/Vinnova funded collaboration project between Nexam Chemical and two European project partners, has been completed according to plan. The aim was to develop new polyamide resins and a new manufacturing process with the goal to address light weight applications within, for example the electronic and automotive industry. Based on the positive results so far, the partners have agreed to further develop the technology.

The main focus of the project was to develop a system solution comprising a tailored resin, with embedded reactive functionality (cross-linkers), and a production process to manufacture crosslinked parts from this resin. The test results displayed significantly enhanced mechanical properties. These results create opportunities for new applications where, for instance product performance could be retained in parts made with less material than existing products – enabling weight reduction.

“The MATPAX-project was successful and the participants are optimistic about this technology. We are developing a new solution with an interesting future and we have gained a lot new knowledge about plastics materials development”, says Dane Momcilovic, CTO.

For more information about the project visit www.vinnova.se (only in Swedish). Nexam Chemical has received half of the project cost as contribution from Vinnova. Total contribution received during the project amounts to approximately SEK 2.4 million.

Partner info:

http://www.emsgrivory.com/en/about-ems-grivory/about-ems-grivory/ems-grivory-at-a-glance/

EMS Grivory product overview:

http://www.emsgrivory.com/en/products-markets/products/product-overview/

Best regards, CESI

The author, Cutting Edge Science Invest, is a Nexam Chemical share holder. Cutting Edge Science Invest can not guarantee, or take into  accountability, the content of truth and accuracy of the information in this article/post.Thus, Cutting Edge Science Invest requires that a possible reader gather complimentary information if any type of investment in the company described above is considered. Cutting Edge Science Invest provides personally biased information and at best also “general information and opinions”. The article/post does not contain professional investment advice. 

One of Polyone´s business verticals is “Specialty Engineered Materials”.

Below is a quote from the company´s  homepage (source link)

“A leading provider of specialty polymer formulations, services and solutions for designers, assemblers and processors of thermoplastic materials across a wide variety of markets and end-use applications. Our product portfolio, which we believe to be one of the most diverse in our industry, includes specialty formulated, high-performance polymer materials that are manufactured using thermoplastic resins and elastomers, which are then combined with advanced polymer additives, reinforcement, filler, colorant and /or biomaterial technologies.”

With +7000 associates, the company´s distribution comprehends “more than 3,500 grades of engineering and commodity grade resins, including PolyOne-produced solutions, PolyOne Distribution principally serves the North American and Asian markets. Products are sold to more than 6,000 custom injection molders and extruders who, in turn, convert them into plastic parts that are sold to end-users in a wide range of industries. Representing over 25 major suppliers, PolyOne Distribution offers a broad product portfolio, just-in-time delivery from multiple stocking locations and local technical support. Recent expansion in Central America and Asia has bolstered PolyOne distribution’s ability to serve the specialized needs of customers globally.

In the following work resulting in a patent application which subsequently was published in July 28 2016, Nexam Chemical was stated as the commercial source in “TABLE-US-00002” (see source link below).  

Source link

Application Number: 15024833 Application Date: 24.09.2014
Publication Number: 20160215095 Publication Date: 28.07.2016

Patent application title (US20160215095):

PREPARATION OF IMIDE OLIGOMERS VIA CONCURRENT REACTIVE EXTRUSION

Patent application abstract:

“Reactive extrusion can be used in a continuous, solvent-less preparation of imide oligomers involving two competing reactions among three ingredients, the first reaction between a dianhydride and a diamine and the second reaction between an endcap and the same diamine. The imide oligomer can form a composite via conventional production methods or via formation of a film from imide oligomer re-melted in an extruder before being impregnated into tape or fabric.”

https://patentscope.wipo.int/search/en/detail.jsf?docId=US175460705&recNum=10&maxRec=79&office=&prevFilter=&sortOption=Pub+Date+Desc&queryString=ALL%3A%28Nexam%29&tab=PCTDescription

More interestingly, Polyone seems to be a perfect customer. Why? Well, let´s look at the product portfolio. A bullish CESI believes it might be reasonable that Polyone is “generally interested” to boost internal technology and properties of products where possible.

 

CESI speculative conclusion: Potentially, Polyone might be one of the “later generation” customers. Time will tell.

Best regards, C.E.S.I.

The author, Cutting Edge Science Invest, is a positively biased Nexam Chemical share holder. Cutting Edge Science Invest can not guarantee, or take into accountability, the content of truth and accuracy of the information in this article/post.Thus, Cutting Edge Science Invest requires that a possible reader gather complimentary information if any type of investment in the company described above is considered. Cutting Edge Science Invest provides personally biased information and at best also “general information and opinions”. The article/post does not contain professional investment advice. 

Findings like these makes CESI believe that the positive statements from the CEO Anders Spetz is based on fundamental progress and near future acceleration of turnaround and subsequent revenue. The Q2 report burnrate of approximately 5 MSEK (of total cash ~138 M SEK) was positively explained with “cost associated with stockpiling”.

WO 2017098179 A1
Publication date: June 15, 2017
Reactive compositions made from semi-crystalline amino polyamide prepolymer and unsaturated extender for thermoplastic composite materials

Source link : https://www.google.com/patents/WO2017098179A1?cl=en

Composite materials and, more particularly, composite materials comprising a polymeric matrix impregnated reinforcing fibers are increasingly used in many technical fields, especially in aeronautical applications, aerospace, wind, automobile , rail, marine. These applications mainly require composites with high mechanical performance, especially at high operating temperatures and with structural lightweight parts by weight relative to the metal and recyclable equivalent parts.

“To improve the impregnation of reinforcing fibers in the case of a thermoplastic composite material, reactive compositions precursors of the composite material based on a reactive prepolymer and a coreactive chain extender them have been proposed.
Preparation of polyamide polymer by chain extension with an extender a2)
Of the oligomer 1 above dried and ground is mixed in the solid state with 4- anhydride (methyl ethynyl) phthalic (APME, Mn = 186.2 g / mol) sold under the name ® A32 Nexamite by the company Nexam Chemical anhydride or trimellitic phenyl ethynyl (PETA, Mn = 276.3 g / mol) sold under the name Nexamite A56 ® by the company Nexam Chemical at different molar ratios a2) / NH2. The amounts are calculated so that the mixing weight is equal to 12 g.”

About Arkema:

+19000 employees and total sales roughly in the range of € 7 billion (!)

https://www.arkema.com/en/arkema-group/organization/
https://www.arkema.com/en/investor-relations/financials/key-figures/

 

Best regards, C.E.S.I.

The author, Cutting Edge Science Invest, is a positively biased Nexam Chemical share holder. Cutting Edge Science Invest can not guarantee, or take into accountability, the content of truth and accuracy of the information in this article/post.Thus, Cutting Edge Science Invest requires that a possible reader gather complimentary information if any type of investment in the company described above is considered. Cutting Edge Science Invest provides personally biased information and at best also “general information and opinions”. The article/post does not contain professional investment advice. 

This might be one of the most exiting CESI finding published. Why? In December 17, 2014, the market expectations and the Nexam share price instantly plunged after the first key sentence of this specific Nexam press release:

“Nexam Chemical and BASF have jointly decided not to extend the exclusivity agreement regarding polyamide 66 compounds containing Nexam Chemical´s crosslinker, which was signed between the parties in February 2014, and which ends during the second quarter of 2015. The reason for this decision is that Nexam would like to include polyamide 66 in the projects it has with other partners in the polyamide area.

The collaboration will however continue between the parties and test material based on BASF’s polyamide 66 and Nexam Chemical’s additives will be tested in components by e.g. the automotive industry during spring 2015.

For more information, please contact:
Lennart Holm, Chairman of the Board: +46 (0)706 30 8562″

Despite additional information regarding continued activities, the market obviously concluded that minimal true value remained in the Nexam-BASF collaboration and since the market has not found incentives to update this opinion. Updates indicating continued activities have been absent both from external news agents, inofficial content from independent forums as well as from Nexam and BASF.

In the light of this introduction, the new BASF patent publication (described below) resulted in an increased CESI pulse and a few questions after yet another thorough scan of the December 17, 2014 press release:

“The reason for this decision is that Nexam would like to include polyamide 66 in the projects it has with other partners in the polyamide area. [..] The collaboration will however continue between the parties and test material based on BASF’s polyamide 66 and Nexam Chemical’s additives will be tested in components by e.g. the automotive industry during spring 2015.”

To the best of CESI´s knowledge, no specific information is available for outsiders regarding status in Nexam projects with other partners. However, attached below is a very recent indication that BASF is progressing well within polyamide 6 and 66 and – most importantly for the Nexam share holder – BASF is adding specific Nexam cross-linkers…

Pub. No.: WO/2015/140016 International Application No.: PCT/EP2015/055018

Original Source Link (click here)

Title: CROSS-LINKED POLYAMIDES

Publication Date: 24.09.2015 

International Filing Date: 11.03.2015 (3 months after termination of the exclusivity agreement!)

In this patent, BASF claims a thermoplastic molding material containing a polyamide + glass fibers + Nexam cross-linkers + miscellaneous additives and/or fillers. To CESI´s excitement, the Nexam cross-linkers has a central role in this patent and in addition BASF states that these cross-linkers are available from Nexam (!)

CESI Diclaimer: The patent quotes attached below was subject to automated translation by the web browser and this resulted in a few grammatical errors below. To conserve the true message and accuracy, CESI decided not to edit these grammatical errors.

“It has now been found that the profile of properties of glass fiber reinforced PA can be significantly improved by the addition, inter alia ethynylmodifizierten Phthalsäureanhydri-to or imides. The additives are this compounded at very low temperatures in the polyamide, which the amino end groups of the polymer “endcap-pen”, a cross-linking but not / or will take place in the melt in just such a small scale, so that the polymer can still be processed. The triple bonds of the additives are then thermally activated in a further step, for example by introducing high shear forces during injection molding or by annealing below the melting point of the polymer. The thus obtained crosslinked polyamides have an improved property profile. in- cluding a lower water absorption, higher heat resistance and improved creep. is also reduced by the lower water absorption of the deterioration of the mechanical properties in the conditioned state.”

[…]

“Process for the preparation of the unsaturated compounds C) are known from the EP-A 2 444 387, WO 2010/36175, WO 2010/36170 and WO 2012/52550. Such compounds are available as Nexamite ® from Nexam Chem., SE commercially.”

Very particular preference is given in the novel thermoplastic molding compositions of polyamides, which are selected from the group consisting of Polyhexamethylenadipin acid amide (nylon 66, polyamide 66), a mixture of polyamides with a polyamide 66 component of at least 80 wt .-% or a copolyamide whose blocks at least 80 wt .-% of adipic acid and hexamethylenediamine are derivable, polycaprolactam (nylon-6, nylon 6), or mixtures thereof.”

Component C1 equals NEXAMITE®A32 (Nexam Chem.) (4- (Methylethynyl) Phthalic Anhydride (CAS: 1240685-26-0)

Component C2 equals NEXAMITE®A33 (Nexam Chem.) (Hexamethylene-1, 6-di- (4-methylethynyl) phthalimide)

The mechanical properties were determined in dry and conditioned state.

[…]

Component H) thermoplastic molding compositions of the invention may comprise the usual processing aids, such as stabilizers, antioxidants, heat stabilizers and UV stabilizers, lubricants and release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, and so forth.

Examples of antioxidants and heat stabilizers are hindered Phos-phite and amines (eg TAD), hydroquinones, aromatic secondary amines, such as diphenylamines, various substituted representatives of these groups and mixtures thereof, in concentrations up to 1 wt .-%, based on the weight of called thermoplastic molding compositions.

UV stabilizers, which are generally present in amounts up to 2 wt .-%, based on the molding composition, are various substituted resorcinols, salicylates, Benzotriazo-le and benzophenones.

Inorganic pigments, such as titanium dioxide, ultramarine blue, iron oxide and carbon black, and organic pigments such as phthalocyanines, quinacridones, perylenes, and dyes such as anthraquinones, are added as colorants.

Flame retardants phosphorus, P- and N-containing compounds may be mentioned.

As nucleating agent sodium phenyl, alumina, silica, and preferably talc may be used.

The thermoplastic molding compositions according to the invention can be prepared according to known Ver-go, by mixing the starting components in conventional mixing apparatus, such as screw extruders, Brabender mixers or Banbury mixers, and then extruding them. After extrusion, the extrudate can be cooled and comminuted. It can also be individual components are premixed and then the remaining starting materials and / or likewise mixed. The mixing temperatures are generally from 230 to 320 ° C.

The molding compositions and moldings of the invention are distinguished by a good heat resistance, chemical resistance, low water absorption, better mechanical properties in the conditioned state, scratch resistance, dimensional stability and creep.

[…]

“The molding compositions are suitable for the production of moldings of any type, especially in the automotive sector.

Some examples are mentioned: cylinder head covers, motorcycle covers, intake manifolds on, intercooler end caps, connectors, gears, impellers, cooling water tanks.

In the E / E department can with improved-flow polyamides are plugs, plug components, plug connectors, membrane switches, PCB assemblies, microelectronic components, coils, I / O connectors, connectors for printed circuit boards (PCB), connector for flexible circuit boards (FPC) connectors for flexible integrated circuits (FFC), high-speed connectors, terminal blocks, connector, Connectors, wiring harness components, cable mounts, cable mount components, three-dimensional molded interconnect devices, electrical connectors, mechatronic components.

In the car-interior is a use for dashboards, steering column switches, seat components, headrests, center consoles, gearbox components, and door modules, and possible automobile exterior door handles, exterior mirror components, windshield wiper components, windshield wiper protective housings, grille, roof rails, sunroof frames, engine covers, cylinder head covers, intake manifolds (in particular intake manifold), windshield wipers, and exterior bodywork parts.

For the kitchen and household sector, the use of improved-flow polyamides for the production of components for kitchen equipment, eg fryers, smoothing irons, buttons, and applications in the garden and leisure sector, for example components for irrigation systems or even-tengeräte and door handles is possible.”

These stated BASF applications also aligns well with the application stated in the original Nexam Chemical press release (Nexam Chemical source link):

“Nexam signs co-operation agreement with BASF

2011-11-23

Nexam Chemical and BASF have signed an exclusive co-operation agreement regarding development and commercialization of crosslinked PA 66 (nylon 66).

The goal is to develop a PA 66, containing Nexam’s crosslinkers, which can be processed as usual to then be crosslinked using heat activation, and that the crosslinked material gets properties that are substantially better than current PA 66 based materials.

Initial application segments consist, among other things, of the automotive, electrical and electronics industry.

For more information, please contact:

Lennart Holm, Chairman of the Board: +46 (0)706 30 8562
Per Palmqvist Morin, CEO, +46 (0)706 55 55 82″

BASF patent WO/2015/140016 Summary (CESI)

  • Roughly 10 % less water content using a formulation containing Nexam cross-linker(s).
  • Roughly 20 % stiffer material (a +20 % E module number is stated). Slightly different results at different temperature. Higher stiffness at all temperatures was obtained using a formulation containing Nexam cross-linker(s).
  • Roughly 15 % better heat resistance using a formulation containing Nexam cross-linker(s)
  • Higher tensile strength (+10 %)
  • DRAMATICALLY higher gel content (BASF states higher is better): 400% after injection in the comparison between formulation 1V and formulation 2. Formulation 2 contains NEXAMITE®A32 and NEXAMITE®A33. The gel content after heating at 220 ° C is roughly 50% for formulation 2 compared to < 5% for formulation 1V.

Conclusion (CESI)

CESI does not interpret this patent as a BASF strategy to actively delay or block Nexam cross-linkers from the market. Why? All stated result data is superior to “Nexam free polyamide”. BASF should have strong incentives to capitalize on this formulation / innovation. In fact, the claimed applications are aligned well with the previous statements (Nexam:The collaboration will however continue between the parties and test material based on BASF’s polyamide 66 and Nexam Chemical’s additives will be tested in components by e.g. the automotive industry during spring 2015″). Presumably, the patent filing date (Mars 11, 2015) might indicate that these tests were successful and that the collaboration is in fact still an active collaboration. In addition, BASF clearly states that the cross-linkers are Nexam derivatives AND also states that they are commercially available from Nexam. Therefore, CESI does not believe that BASF plans to produce these cross-linkers in-house. 

So what did happen back in December 2014?

Due to the complexity of the formulations stated in this patent (i. d. the large number of “ingredients”), CESI is relatively convinced that the earlier BASF exclusivity agreement was in fact terminated by Nexam (as officially and originally stated) primarily due to delays in the formulation work performed at BASF. Logically, BASF had no ambitions to buy large volumes of cross-linkers without a confirmed successful formulation. Speculatively (with this patent as the guide), it seems like BASF did not solve prior formulation issues until in the beginning of 2015. Therefore, CESI also believes that only the exclusivity agreement was terminated (not the collaboration). Furthermore, Nexam´s input in terms of “hands on late stage formulation optimization” has likely been limited since (compared to 2014 when CESI got the impression that Nexam and BASF worked next to each other on a daily basis). In conclusion, this has potentially freed up resources and therefore Nexam logically and easily could take the strategic and intelligent decision to (temporarily?) exclude nylons as a focus area. Another key game stopper for top prioritization of polyamides could be “unknown time to market” for cross-linked BASF Nylons (containing Nexam cross-linkers). CESI believes that a similar strategy will be applied for other current polyamide collaboration partners with a small twist :This time, Nexam aims to charge for consulting. Finally, CESI speculatively predicts a future BASF market launch containing Nexam cross-linkers and that Nexam ultimately will capitalize on future BASF polyamides (nylons) after all. CESI embraces this potential BASF counter-strike within yet another gigantic polymer market segment. 

Note: Slightly more reading in SwedishClick here if of interest (a Dec, 2014 email from L. Holm to Six News, source: Aktiespararna):

Best regards, C.E.S.I.

The author, Cutting Edge Science Invest, is a Nexam Chemical share holder. Cutting Edge Science Invest can not guarantee, or take into accountability, the content of truth and accuracy of the information in this article/post.Thus, Cutting Edge Science Invest requires that a possible reader gather complimentary information if any type of investment in the company described above is considered. Cutting Edge Science Invest provides personally biased information and at best also “general information and opinions”. The article/post does not contain professional investment advice. 

Nexam Chemical Holding AB develops, manufactures and markets crosslinking chemicals for the polymer industry. The company is listed on NASDAQ OMX First North (ISIN SE0005101003, ticker symbol: NEXAM). 

CESI: A very interesting quote from the brand new Nexam patent application background section:

“PEPA, PETA and MEPA, the triple bonds will eventually react and cross-link to provide a cross-linked polymeric material, whereby improving the heat and chemical resistance, as well as the mechanical strength of the material. Using PEPA will require a heating to at least 350°C to cure the PETI (cf. US 5,567,800) and even somewhat higher, i.e. 380 to 420°C, to cure PEPA end-capped polyimides (cf. US 5,493,002).

However, for some applications such a high curing temperature profile may be considered a problem. For instance, the properties (such as the coefficient of thermal expansion) of flexible polyimide films, having a melting temperature below 350°C, may be improved via cross-linking. However, the high temperature (above 350 °C) needed to initiate cross-linking will make the processing impossible. Further, also for economic reasons the possibility to lower the curing temperature and/or increase the curing rate may be advantageous. Often such polymers are still to be processed above 300°C. PEPA may accordingly not always be replaced with an alternative cross-linker, e.g. MEPA, in applications requiring a lower curing temperature or a higher curing rate. Further, PEPA has the advantage of withstanding processing temperatures up to and even above 300°C without curing being initiated.

A process for modifying the curing temperature profile of PEPA-based system would thus be highly interesting, as it would allow for processing of “inert” acetylenical polymers, which subsequently may be activated and cured at temperatures tolerated by the molecular backbone.

As already described also acetylenical cross-linkers for thermoplastic polymers are available in the art. Thermoplastic polymers are processed in a wide temperature span above their softening point (Tg or melting point), but below their degradation temperature. It is often desired to affect the thermal curing behavior within this window to mirror/suit the process or parts manufacture. Especially, semi-aromatic polyamides end-capped by PEPA, as well as PA46 and PA66 end-capped by PEPA, represent types of acetylenical polymers, which would benefit from an altered thermal curing behavior.”

 

CESI: A very interesting quote from the brand new Nexam patent application Embodiments section:

“Upon continuously increasing the temperature of a composition comprising an acetylenical cross-linker, such as a polyimide end-capped with PEP A, the carbon-carbon triple bonds in the system will eventually start to react with each other. The cross-linking is believed to include a sequence of exothermic reaction steps, including chain-extension, probably due to ethynyl-to-ethynyl reactions, of the material and subsequent cross-linking, probably due to pericyclic reactions, e.g. Diels- Alder reactions and ene -reactions. Typically, the curing temperature profile may be studied by differential scanning calorimetry (DSC), as well as melt rheology measurements. DSC will provide information regarding the temperature required to initiate curing, while melt rheology will provide insight into the curing onset as well as into the degree of chain-extension and cross-linking, as such reactions will increase the viscosity of the material.

The melt viscosity of a polymer affects its processablity. A too high melt viscosity will make it difficult to process the composition, as the shear forces to generate sufficient flow will be extremely high. Thus, polymers are often processed at temperatures well above their softening point (glass transition temperature – Tg – or melting point – Tm). An increased processing temperature results in lowered viscosity, which may facilitate processing. However, the degradation temperature for the polymer of concern sets an upper limit for the processing temperature. Thus, polymers are processed at temperatures in between the softening point and the degradation temperature.

In processing and curing of compositions comprising an acetylenical cross-linker, not only the temperature required for initiating curing, but also the curing rate is of interest. Provided that the curing rate not is too high, some curing may be tolerated already during processing without rendering further processing, such as extrusion and injection molding, impossible.

As can be seen in FIG. 1, a peak corresponding to exothermic heat flow, i.e. curing, is seen upon continuously increasing the temperature of an oligomer end-capped with an acetylenical cross-linker. The exact shape of the peak, e.g. the temperature at which cross-linking is initiated and completed, as well as the temperature curing maximum, will depend on the temperature ramping profile applied. While the temperature at which cross-linking is initiated in principle is constant, the shape of the exotermic peak will, at least partly, be affected, by the temperature ramping profile applied.

The curing temperature profile of different acetylenical cross-linkers is different. In general, the chemical groups next to the carbon-carbon triple bond will through electronic and steric effects determine the curing temperature profile.

Furthermore, the mobility of the system of which the acetylenical cross-linkers is part, will affect the curing temperature profile, but to less extent. As can be seen from FIG. 2 the curing temperature profile of low molecular weight PEPA end-capped phenylene diamine, a model system for studying curing of PEPA, is similar to the one of oligoimide end-capped with PEPA (cf. FIG 1).

The present inventors have surprisingly found that combination of PEPA on one hand and MEPA on the other provides systems having another thermal curing behavior than the two individual cross-linkers if cured separately (cf. FIG 3). While the onset temperature for the curing is approximately the same, DSC-scans indicate that the curing mechanism is another. Especially, the curing of PEPA is completed at significantly lower temperatures and the curing of MEPA, from one perspective, seems to require higher temperatures to complete. The relative molar amount of the two cross-linkers will affect the thermal curing behavior.

Further, as can be seen from FIG 4b exchanging the cross-linker on the polymer does not affect the ultimate melt viscosity. However, the onset of the viscosity increase is shifted and the time required to attain the ultimate viscosity is prolonged. The somewhat higher initial viscosity for the PA-MEPA compared to the PA-PEP A indicates that some curing of MEPA has taken place already during compounding of PA-MEPA. FIG 4c shows that it is not as effective in this case to exchange the cross-linker of the oligomer/molecule as it retards the reaction too much for the specific example. The high initial viscosity for the PA-MEPA//HD-MEPA compound indicates that curing of MEPA has taken place already during compounding of the system.

As can be seen from Fig. 5, it was possible to affect the curing rate also in an acetylenical, semi-aromatic polyamide, i.e. PEPA end-capped PPA. Replacing HD-PEPA with HD-MEPA increased the curing rate (measured as pressure build up) of PPA-PEPA. Replacing also the end-capper, i.e. PEPA, with MEPA resulted in vary rapid build up of pressure, indicating that curing of PPA-MEPA//HD-MEPA at 340°C is rapid process.

Thus, it has been revealed that combined use of two distinct acetylenical cross-linkers, having different thermal curing behavior, provides a way of altering, and in some applications even tuning, the thermal curing behavior for a given polymer.

Accordingly, such combinations may be used to provide system with cross-linkers having thermal curing behavior adapted to suit that processing temperature and degradation temperature of concern.”

The full patent Source link is attached here

 

Best regards, CESI

The author, Cutting Edge Science Invest, is a Nexam Chemical share holder. Cutting Edge Science Invest can not guarantee, or take into accountability, the content of truth and accuracy of the information in this article/post. Thus, Cutting Edge Science Invest requires that a possible reader gather complimentary information if any type of investment in the company described above is considered. Cutting Edge Science Invest provides personally biased information and at best also “general information and opinions”. The article/post does not contain professional investment advice. 

This Nexam article primarily aims to highlight the improvement of material properties gained by applying Nexam cross-linking technology:

“Nexam develops crosslinkers that fit optimally into different kinds of polymers including polyimides, nylon, polyethylene, polypropylene, polycarbonates and PEEK. The technology, which is based on previous developments carried out by NASA, has now been further developed and new patents have been applied for. The new crosslinkers result in improved processing properties such as controlled melt behaviour and they can be tailored to work with almost any polymer.

NEXAM PLASTICS, STRONGER AT ELEVATED TEMPERATURE, EVEN WHEN DILUTED WITH FILLER

“Formerly, fillers were used predominantly to cheapen end products, in which case they are called extenders. Among the 21 most important fillers, calcium carbonate (CaCO3) holds the largest market volume and is mainly used in the plastics sector.[2] While the plastic industry mostly consumes ground calcium carbonate the paper industry primarily uses precipitated calcium carbonate that is derived from natural minerals.” Source link, Wikipedia

Effect of temperature and filler. A few CESI conclusions:

Nexam demonstrates an example that a plastic´s tensile strenght is lowered ( – 33 %, at 210 °C ) when dilued with 60 % (mass weight) of calcium carbonate (CaCO3). However, for the same plastic crosslinked with 2.5 % of Nexam cross-linker, the plastic´s original tensile strength is retained even if “diluted” with ~60 % (mass weight) of CaCO3 (!)

Furthermore, in the same example at 210 °C, the cross-linked plastic (containing 2.5 % of Nexam cross-linker) is stronger compared to the original plastic (not containing Nexam cross linker), even if diluted with 10 % CaCO3 (+>40 MPa tensile strenght versus +>30 MPa tensile strenght in the highlighted example).

Source link (t =19:20, in Swedish): ref: https://redeye.solidtango.com/video/nexam-smabolagsdagen-2015

NEXAM CROSS LINKED PE PIPES vs PE100 PIPES

– IMPRESSIVE SLOW CRACK GROWTH DATA

PE100 is an ISO designation for a grade of pressure rated PE material. The designation means simply that the material is polyethylene, PE, and that the material qualifies for a 10 MPa (100 bar, 1450 psi) MRS rating at 20°C Source link, wlplastics.com 

For PE pressure piping materials, slow crack growth (SCG), is the long term failure mode. SCG is not brittleness. Stress such as internal pressure causes cracks to develop and grow through the pipe wall from stress concentrations Source link, wlplastics.com 

Japan Polychem Corporation (wholly owned by Mitsubishi Chemical Corporation) claims that:

“Polyethylene, especially PE100 Resin has been steadily increasing its use in pressure pipes for water and gas based on its superior property balance. Of all the properties required for PE100, when we consider the defects on the pipe surface and the stress concentrations on the fitting of complicated shape, the most important for the lifetime of pipe should be the resistance to Slow Crack Growth (SCG). Recent requirements for cost reduction by no-dig or no-sand installation have been enhancing the need for the improvement of SCG resistance”

And:

“Polyethylene(PE) has already established its position as a major material for many pipe applications,
such as gas and water distributions (pressure pipes), sewerage, drainage and conduit, based on it’s
excellent characteristics such as light weight/ flexibility for easy handling and chemical stability for
corrosion resistance. The strength of PE pipe line system to the earthquake according to its ability to
follow the ground movement and excellent fusion-welding strength is now well acknowledged. In
Japan, there have been several strong earthquakes with the magnitude of more than 6 such as the
Great Hanshin-Awaji earthquake (Magnitude 7.3, 1995) and the Niigata-ken Chuetsu earthquake
(Magnitude of 6.8, 2004). Although there were a lot of damages observed to iron, steel and PVC
pipes in those earthquakes, there was no report of the damage to the PE gas and water pipe line
system. Therefore, the usage of PE pipes to the lifelines like water and gas is increasing year after
year also in Japan.”

PE for pipes, especially PE100 resin, has been steadily increasing its use all over the world and is
expected to grow further. Together with the spreading of PE100 resin, the requirements for cost
competitive installation methods like no-dig or no-sand methods are also increasing. In these
installation methods, however, we can not avoid the surface defect by scratching and the
concentrated local stress by stone or something like that in the backfill material. These defect and
stress concentration can give the pipe more stress than anticipated and may cause the failure of the
pipe, if the material’s resistance to stress crack or slow crack growth (SCG) is not strong enough.”

Source link: http://www.pochem.co.jp/jpe/reference/pdf/20061113-1.pdf

In the most recent Nexam presentation, the CEO Anders Spetz presented that SCG for PE100 pipes containing Nexamite equals a 307 % improvement compared to PE100 pipes containing no Nexam cross linker (reference). 

Source link (t =19:40, in Swedish): ref: https://redeye.solidtango.com/video/nexam-smabolagsdagen-2015

NEXAM vs PE100 PIPES

– IMPRESSIVE HYDROSTATIC LEAK TEST DATA

Hydrostatic testing is universally known and accepted as the primary means of demonstrating the fitness for service of a pressurized component (Source link, Plastic Pipe Institute)

  • An indoor video example of a hydrotest

https://www.youtube.com/watch?v=dG-FQvjn9C0

  • An outdoor video example of a hydrotest

https://www.youtube.com/watch?v=dG-FQvjn9C0

Hydrostatic leak tests typically use cooler liquids so the liquid filled test section will tend to equalize to a lower temperature near test liquid temperature. Source link, Plastic pipe 

In the most recent Nexam presentation, the CEO Anders Spetz also presented results from a hydrotest. PE100 pipes containing Nexamite equals a 320 % improvement compared to PE100 pipes containing no Nexam cross linker (reference).

Sourcelink, Nexam at småbolagsdagen 2015 (In Swedish, t = 19:40)

PE pipe status note, Nexam 2014 Annual report: Other promising partnerships Other promising partnerships include PE applications (polyethylene), in which full-scale testing will be conducted by pipe manufacturers during the first six months of 2015. The aim is to develop a manufacturing process using crosslinkers from Nexam Chemical that results in plastic pipes with greater stability. This would enable the manufacture of pipes in larger diameters, while maintaining production speed

NEXAM POLYIMIDES

Du Pont:

“There is a need for a new method for making polyimide nanowebs with suitable mechanical properties from high concentration solutions; polyimide nanowebs comprising nanofibers of a cross-linked polyimide; separator comprising polyimide nanowebs; and multilayer articles and electrochemical cells comprising separator.”

In  this patent, Du Pont demonstrates that mechanical and electrical properties were improved using the Nexam products EPA (ethynyl phthalic anhydride) and PEPA (4-phenylethynylphthalic anhydride)! Additionally, Du Pont specifically states that PETA was obtained from Nexam (WO 2013/181333 A1; E. I. DU PONT)

Addition Curable Polyimides – Summary from the Nexam – Evonik Webinar

Processability

•Increased coating build and / or line speed
•Removal of solvents
•Controlled thermal activation

Properties

•Retention of properties at high temperatures
•Solvent resistance
•Low void content

Source link: Nexam Evonik Webinar.

IMPORTANT NOTE : Webinar available only until September 24, 2015 (!)

A new Nexam resin: NEXIMID® MHT-R in short Source link

Nexam Chemical introduces a new ”easy to process” resin that is primarily intended for use within the aerospace industry. Other areas, such as machine, general industry and transport sectors will also benefit from this high property material. The new resin, NEXIMID® MHT-R, is intended for small to medium sized production volumes of high-temperature composites by Resin Transfer Moulding (RTM). Temperature properties such as Tg is superior to most other materials and polyimides on the market.

  • Binders for fixation of fibre preforms:
    Reactive binders for fixation of a fiber pre-form are available. The binders are NEXIMID® A57 and A58.  A57 is a mono functional binder that reacts with the resin and A58 is a bi functional binder. Each binder melts at a specific temperature and upon cooling glues the pre-form together. During processing the binders react with the resin upon curing. The reaction is an addition reaction and no volatiles are formed during the process.

NEXAM POLYAMIDES

From Nexam patent US8492507 B2 Source link 

“Polyamides are recognised as exhibiting good abrasion resistance, low friction coefficient, good resistance to heat and good impact resistance. Polyamides are in dry conditions good electrical insulators. Polyamides are typically hygroscopic and absorb water. This absorption will change some properties, such as insulation, tensile strength and stiffness. The impact resistance is increased by a higher content of water.

There are, despite the fact that polyamides have excellent physical and chemical properties and for a long time have been widely used for resins, films, fibres, moulded articles and so on, demands for improved and/or modified properties, such as increased operational temperatures and retained properties during and after exposure to for instance harsh temperature, atmosphere, mechanical and radiation conditions.

It has now quite unexpectedly been found that an acetylenic polyamide can be obtained by incorporation of one or more carbon-carbon triple bonds into a polyamide, for instance as endcapping group(s), as pendant group(s) along the molecular backbone and/or as group being part of the molecular backbone. The acetylenic polyamide of the present invention meets said demands for improved and/or modified properties exhibiting an excellent combination of toughness, resistance and thermooxidative stability” […]

The purpose of the present invention is to modify the mechanical properties of polyamides and compositions comprising polyamides. Among these modifications of properties can be mentioned: higher softening temperature, higher E-modulus and improved ability to counteract creep strain.

Note: E-modulus = Elastic modulus =  A number that measures an object or substance’s resistance to being deformed elastically (i.e., non-permanently) Source Link, Wikipedia

RECYCLED PET – POTENTIAL NEXAM CHEMICAL IMPACT IN SECOND GENERATION PROCESSED RECYCLED PET:

PET bottles exposed to UV light negatively impact next generation bottles – Plastic Engineering

http://www.plasticsengineering.org/News/article.aspx?ItemNumber=22506

Described above is a “storage issue” of PET bottles produced from recycle material. In fact, Nexam might potentially already have principal solutions at hand to this issue, both in respect to chain extenders (= PBO = “repair agents”), UV protection during second generation production of recycled PET (see bold font below) and the original and new Nexam cross linking approaches (see bold font below). One example:

  • Nexam patent US20140018460 – COMPOSITIONS FOR IMPROVING POLYESTERSPublication Date:16.01.2014

SUMMARY

“Accordingly, the present invention preferably seeks to mitigate, alleviate, eliminate or circumvent one or more of the above-identified deficiencies in the art and disadvantages singly or in any combination and solves at least the above mentioned problems by providing a method for altering the melt characteristics, such as the melt strength, of a polyester.” […]

“According to an embodiment, also blowing agent, such as carbon dioxide, nitrogen, alcohols, ketons, methyl formate, hydrofluorocarbon a hydrocarbon, e.g. n-hexane, iso- or n-pentane, cyclopentane and n-heptane, or a gas mixture thereof, an expanding agent, a foaming agent, nucleating agent, such as talc, kaolin, silica gel, and TiO2, a flame retardant, such as a halogenated, charforming (like phosphorus-containing) or water-releasing compound, a plasticizer, a lubricant, such as an ester of a fatty acid, an impact modifier, insulation modifier, a pigment, a filler, an antioxidant, a UV-stabilizer and/or a color improver is melt mixed with the polyester” […]

“The cross-linker and chain extender comprising at least two groups being able to react with a carboxy group and a phenolic hydroxyl group will act as chain extender, e.g. by connecting terminal carboxy groups of two separate polyester molecules, as well as cross-linker, e.g. by connecting non-terminal pending carboxy groups of two separate polyester molecules. The molar ratio of polyester and tetracarboxylic dianhydride, will affect the number of non-terminal pending carboxy groups being present and hence also the degree of cross-linking. Further, the cross-linker and chain extender will act as water/acid scavenger, as any water in the material will result in hydrolyzed polyester generating an acid and an alcohol, these acids can be tide back to the polymers by the cross-linker and chain extender if such is present in the material.”

In fact, the above described cross linking approach is not based on the earlier reviewed and described 2+2+2 cyclotrimerization (the Berthelot reaction). This polyester cross linking approach is based on another type of chemical reaction. If time allows, CESI will describe this specific reaction in a more pedagogic approach that hopefully also can be understood by a non chemist.

Furthermore, the Armacell patent EP 2 163 577 A1 is refered:

“As taught by EP 2 163 577 A1, it is known within the art that a combination of PMDA (pyromellitic anhydride), PBO (1,3-phenylene-bis-oxazoline), and a sterically hindered phenol, i.e. a compound comprising a 4-hydroxy-3,5-di-tert-butyl-phenyl moiety, may be used to improve the properties of PET. The sterically hindered phenols are stated to be believed to act as hydrogen donor, wherein radical scavenger neutralizes the alcoxy or peroxy radicals generated by hydrolytic or thermal degradation, and does thus terminate the chain propagation of degradation processes. It also stated that, by adding sterically hindered phenols, the effectiveness of functional anhydride groups remain, therefore, intact for further upgrading reactions.”

“The present inventors have unexpectedly found that the addition of poly functional compounds comprising at least two non-sterically hindered phenolic hydroxyl groups rather than sterically hindered phenols, as taught be EP 2 163 577A1, improves the PET further. Further, the present inventors have also found that the non-sterically hindered phenolic hydroxyl groups may be replaced or complemented with carboxy groups.”

CESI Conclusions: A or B or C 

  • A: Nexam and Armacell is working closely togheter (= very positive)
  • B: Nexam is fully or partly taking the role as a sheer (successful) innovator in Armacell´s- and other competitor´s core PET research areas thereby securing IP and potential near future business value also within this segment (= positive)
  • C: Nexam aims to independently and additionally capitalize on the invention in PET areas not covered by the current PET foam exclusivity agreement (= positive, exlusivity agreement source link)

Is Armacell planning to purchase PBO (on scale) from Nexam? Was this a key driver for the recent Nexam PBO commercialization? Time will tell.

Best regards, C.E.S.I.

The author, Cutting Edge Science Invest, is a Nexam Chemical share holder. Cutting Edge Science Invest can not guarantee, or take into  accountability, the content of truth and accuracy of the information in this article/post.Thus, Cutting Edge Science Invest requires that a possible reader gather complimentary information if any type of investment in the company described above is considered.

Cutting Edge Science Invest provides personally biased information and at best also “general information and opinions”.

The article/post does not contain professional investment advice. 

CESI is proud to present the following observation: Nexam has delivered two (speciality) compounds to Victrex (4-fluorophenylethynylbenzophenone (4-FPEB) and 3-fluorophenylethynylbenzophenone (3-FPEB) and Victrex has subsequently filed a patent application WO 2015087059 A1 (published June 18, 2015). Due to additional information presented below in this blog post, CESI believes Victrex end cappers might indicate substantial (near) future business. Why? In this blog post the author aims to answer this question.

VICTREX – The World Leader in High Performance Aromatic Polyketone Solutions (PAEK) Victrex source link 

“For more than three decades, Victrex has collaborated with customers to help turn their toughest challenges into tangible benefits. As a product leadership company, our proactive approach in monitoring the trends of the industries we serve and engaging in open dialogue with industry leaders enables us to deliver what is required to maximise performance today and tomorrow.

Victrex is largely integrated into its key raw material supplies, alongside complementary supply from non-Victrex sources. This is a unique position as a PAEK manufacturer and allows us to ensure security of supply for our customers, as well as consistent and technically advantageous products, meaning high-quality products that will be delivered on time and in-full. 

A company with cutting-edge polymeric solutions, streamlined production facilities, application development expertise and unmatched technical support – that’s a future performance partner.”

What is PAEK (and PEEK)?  Source link (wikipedia)

“Polyaryletherketones (PAEK) has a continuous operating temperature of 250 °C (482 °F) and under short-term loads can function up to 350 °C (662 °F). When burned it has the least toxic and corrosive fumes. It also has a low heat output when burned, so it qualifies for use in interior aviation applications. It also has good overall chemical resistance.  

Plastics that fall within this family include:[3]

  • PEK
  • PEEK
  • PEKK
  • PEEKK
  • PEKEKK (polyetherketoneetherketoneketone)”           

WO2015087059 – POLYMERIC MATERIALS. VICTREX MANUFACTURING LIMITED

Publication Date: 18.06.2015 International Filing Date: 08.12.2014

“Polyaryletherketones (PAEKs) are produced which are end-capped with a phenylethynyl- containing moiety. The end-capped material, having a relatively low molecular weight, may be subjected to a thermal cycle to produce a higher molecular weight material having excellent mechanical properties, a relatively high level of crystallinity and acceptable Tm and Tg […]

The following materials are referred to hereinafter:

4-fluorophenylethynylbenzophenone (4-FPEB) – obtained from Nexam Chemicals […]

3-fluorophenylethynylbenzophenone (3-FPEB) – obtained from Nexam Chemicals

[…] Source link: http://google.com/patents/WO2015087059A1?cl=en&hl=sv

“Mechanical properties of moulded samples were assessed and compared to commercially available PEEK 90, PEEK 150 and PEEK 450 materials. Results are provided in Table 6.

[…] Source link: http://google.com/patents/WO2015087059A1?cl=en&hl=sv

Table 6 It will be appreciated from Table 6, that moulding the example 9 polymer having the same starting RV as PEEK 90, yields a polymer with properties more like PEEK 150. Similarly, Example 1 1 , having the same starting RV as PEEK 150, has properties after moulding which are more like PEEK 450.

Advantageously, it is found that the shear heating and injection moulding process promotes the majority of the curing of the polymers and thus an increase in RV and improved properties. A post-cure step (e.g. heating at 400°C for 2 hours) is not found to lead to a significant further increase in fracture toughness over “as moulded” samples.

Alternative phenylethynyl compounds which may be used as described above for 4- FPEB include the following:”

CESI decided to graphically visualize the content of the patent… 

Nexam slide 1 PAEK fixed

CLICK PICTURE TO ENLARGE CESI SCHEME 1!

Nexam slide 2 PAEK fixed fixed

CLICK PICTURE TO ENLARGE CESI SCHEME 2!

Now, why is CESI thrilled to stumble across a new patent from Victrex containing Nexam endcappers? Well, the timing seems appropriate…

“Thornton Cleveleys (UK) – Victrex has successfully commissioned the first production stream of its £90 million third Polyaryletherketone (PAEK) manufacturing plant as it focuses on offering even greater security of supply to customers, as well as delivering complete solutions. The capacity increase is also a further foundation to progress Victrex’s pipeline of future opportunities, including seven mega programmes, which will help grow the company over the coming years.” Source link, Victrex.com

“The new PAEK plant serves as the backbone to develop core growth and future opportunities. With long term megatrends being supportive across Victrex’s markets of automotive, aerospace, energy, electronics and medical, the company has focused its pipeline on a smaller number of larger opportunities. These include for example aerospace brackets, applications for mobile devices, orthopaedic knees and oil & gas pipes through its partnership with Magma. Victrex recently identified the overall market potential for the high-performing thermoplastic PAEK as being over 80,000 tonnes.” Source link, Victrex.com

Additionally, on page 5 in the Nexam interim report Q2 2014 we find a full one-pager covering PAEK (PolyArylEtherKetone) and related Nexam Chemical projects. Nexam stated:  “Victrex is now synonymous with PEEK material around the world and accounts for around 80 percent of the total market for PAEK plastics”

Even more interestingly, Nexam has in fact rigorously protected PAEK in respect to intellectual property (IP)!

“Nexam Chemical’s products to PAEK plastics Since it was started in 2009, the Company has collaborated with the majority of the PAEK plastic producers on the market. This has resulted in a PAEK plastic patent and several products. A couple of the products developed can be used to improve the process properties of PAEK plastics, which enables more complicated components to be manufactured. The plastic becomes less viscous during forming and the improved properties are recreated in the final phase of the process. In the continuing service life of the component, Nexam Chemical’s products give the material self-reinforcing properties. Another of Nexam Chemical’s development projects also makes it possible to improve properties by adding our crosslinker as an additive to the finished PAEK plastic. The improvement is strong enough to allow the plastic to successfully compete with polyimide plastics, which are more expensive and cost more to manufacture. This creates opportunities for increased sales growth of PAEK plastics, mainly for new applications, but also enables Nexam Chemical to provide users of PAEK plastics with additives for manufacturing special solutions. In this way, Nexam Chemical gets access to an expanded potential market in addition to the companies that produce PAEK plastics. Nexam Chemical products for the PAEK market are marketed under the NEXAMITE name.”

Now, the Nexam share holder has learned not to trust all single statements from the former CEO Per Morin. Therefore, CESI decided to personally control the quality of the Nexam patents (CESI has ~15 years of industrial organic synthesis experience , patent searches included). The CESI patent search resulted in two relevant hits:

Already after a quick glance, CESI is satisfied. In the first section of the patents, the relevant core (compound) structures are claimed and the relevant schemes are attached. Furthermore, the linker subunit and “all” free positions of the phenyls/aryls are claimed. An impressing array of R groups are specified. To the authors delight, applications are also depicted. These statements may be difficult to digest for a non chemist. A simplified conclusion is that “most relevant structural variations that one can imagine of the molecules also are claimed”. In total the patent(s) contain roughly 150 specific claims within this specific PEEK/PAEK IP space. CESI decided to quote a few  (claims 19-23):

“[0019] It has now unexpectedly been found that cross-linkable aromatic polyetherketones may be obtained by incorporation of acetylenic residues comprising carbon-carbon triple bonds, for instance as endcapping residue(s) [CESI: the Victrex application…], as pendant residue(s) along the molecular backbone and/or as residue(s), wherein the carbon-carbon triple bond(s) is part of the polymer chain, in aromatic polyetherketones.

[0020] The carbon-carbon triple bond allows for cross-linking, such as acetylenic cross-linking, of the cross-linkable aromatic polyetherketone, as alternative and/or additional cross-linking mechanism, thus implying that improved and/or changed properties, such as changed E-module value, changed impact strength and improved resistance towards thermo-oxidative, thermal, oxidative and/or mechanical degradation may be achieved. Also the Tg may be affected by such cross-linking.

[0021] The acetylenic residues were found to be compatible with normal thermoplastic processing methods. Thus, cross-linkable aromatic polyetherketones may be processed using normal thermoplastic processing methods, before cross-linking is initiated. Further, a by-product free (contamination free) material may be obtained. In addition, the Tg (glass transition temperature) may be increased to such a level that the cross-linked polymer may be used in high temperature applications without traditional thermoplastic drawbacks jeopardizing the application performance. Furthermore, the cross-linking enhances the already good wear resistance of PAEK. Thus, for cross-linkable aromatic polyetherketone may be used in primary structures in aerospace applications were extraordinary level of thermal resistance is required.

[0022] Further, cross-linked aromatic polyetherketone may replace polyimides in high temperature applications, such as in airplanes, aerospace and other structural applications were good temperature and creep properties are required.

[0023] Also, metal-replacement in applications where light weight and big volume production are required would become possible. Applications where wear and low friction is necessary would be another target where polyimides may be replaced, especially if it comes to applications that are subjected to low cost high volume requirement because exchange will be done periodically. Applications with demands on being exposed to a high heat in a humid environment and where low creep is a demand would be typically applications for this cross-linked PAEK material, especially if there is a demand on high volume production availability for the material used in order to minimize tolerance deviations high production costs.”

Conclusion: CESI is thrilled and currently experiencing Déjà vu. Why? Below is a quote from my first ever Nexam post:

“C.E.S.I. can not understand that a high quality process company with a vibrant creative environment should, per default, fail to copy the Nexam cross-linkers with roughly the same production cost (or even at lower production). Therefore, securing the intellectual Property (IP) must at all times be on top of Nexam´s highest priority agenda. From the massive IP press release news flow from Nexam, C.E.S.I. concludes that the Nexam CEO and the Nexam board has understood this key issue. Thus, C.E.S.I. is thrilled of excitement. Now, it seems that analysts and the market “demand” a big order from a key industry process company. Today, C.E.S.I. does not share the analyst’s and the market´s demand. C.E.S.I. would like to see even a few more “new patent press releases” prior to the announcement of the first big order. However, the recent small order announcement is a key milestone (see below). This order is a another “proof of concept” i. e. it is a solid proof that the nexam technology is not solely of academic interest… C.E.S.I. predicts that Nexam will be a key player in the next industry revolution (New superior bulk- and advanced materials).”

Source link: https://cuttingedgescienceinvest.com/2014/09/28/nexam-chemical-nexam-genius-applications-of-the-148-year-old-berthelot-reaction/

In CESI´s opinion, the Nexam case has never been stronger.

Today, CESI stumbled across a very amusing and hopefully ironic comment by alias Nexbim on the Swedish stock market forum Placera. The comment is attached below (slightly edited and translated by CESI):

“It´s sad that the pipes are hollow. If pipes would be solid, think about the amount of plastics they would contain”

This quote triggered a google image search using the following phrase “polyethylene pipe IRPC”. But first, two notes of clarification:

  • HDPE is the abbreviation for high density polyethylene and known for its large strength-to-density ratio
  • IRPC has passed the development phase for PE pipes in the IRPC-Nexam collaboration (more info below)

The primary aim of the links attached below is to graphically highlight potential volumes associated with large PE pipes…

  • IRPC sends first shipment of Marine Pipe Grade for CP project

http://www.irpc.co.th/en/news_detail.php?txtNo=TWpRNQ==&page=15

  • Borouge and IRPC are members of the PE100+ association. Note: The new Nexam CMO Lars Öhrn recently held a position as market application manager at Borouge.

http://www.pe100plus.com/PE-Pipes/pe100/pe100/r1017.html

  • In the Q1 2015 IRPC analyst meeting presentation, PE pipes are highlighted as a 2014 milestone.

See page 24 here:

http://irpc.listedcompany.com/misc/PRESN/20150518-irpc-am-1q2015.pdf

Why is this interesting? “Nexam Chemical entered into a cooperation agreement with its polyethylene partner IRPC over the summer for development and commercialization of modified polyolefins. IRPC has informed us that they now have passed the development phase, with respect to a polyethylene quality for pipes, and will begin testing the quality for approval together with their end client in the autumn/winter. This will be an interesting and potentially large application area for our company” (Source: Nexam Chemical 2014 Q3 interim report page 4)

  • Maybe most interestingly, from a “polyethylene wikipedia” search, this image was the result:

https://en.wikipedia.org/wiki/File:Hdpe_pipe_installation.jpg

Conclusion: Dear Nexbim, I totally agree. It is sad that pipes are hollow 🙂

Best regards, CESI

The author, Cutting Edge Science Invest, is a Nexam Chemical share holder. Cutting Edge Science Invest can not guarantee, or take into  accountability, the content of truth and accuracy of the information in this article/post.Thus, Cutting Edge Science Invest requires that a possible reader gather complimentary information if any type of investment in the company described above is considered. Cutting Edge Science Invest provides personally biased information and at best also “general information and opinions”. The article/post does not contain professional investment advice. 

Nexam and the Nexam technology / future expected impact has previously been highlighted here:

https://cuttingedgescienceinvest.com/2014/09/28/nexam-chemical-nexam-genius-applications-of-the-148-year-old-berthelot-reaction/

https://cuttingedgescienceinvest.com/2015/03/28/nexam-full-scale-tests-in-a-double-digit-growth-industry-the-global-plastic-pipes-market/


Logically, within the cutting edge polymer cross linking research area, confidentiality and confidentiality agreements lowers the accuracy of outsider speculation. Furthermore, it is difficult to decipher the relationships between the major key market leaders.  Very recently, one or several Placera bloggers (Placera = A Swedish stock market forum) suggested that a near future joint Evonik-Nexam webinar together with joint sales of a specific molecule (PBO), could be potential clues to an ongoing Nexam-Evonik collaboration

PBO= 1,3-Phenylene-Bis-Oxazoline  (Nexam PBO link and Evonik PBO link).

Let´s check the Evonik patent landscape:

Evonik US 20140163165 A1 (published June 12, 2014)

Low molecular weight products and use thereof as reversible or permanent low-temperature crosslinking agent in diels-alder reactions

The invention relates to low molecular mass products and to their preparation and use as reversible or permanent crosslinkers in polymers or polymer networks where the linking or crosslinking of the resultant polymers is brought about via Diels-Alder reactions.

CESI: The Diels Alder reaction is related to the original Nexam cyclotrimerization reaction. Both reactions produce 6 membered rings after heat activation. The Nexam cyclotrimerization produces a substituted benzene ring and the Evonik 4+2 cycloaddition produces a cyclohexene ring. If fully unsaturated rings are desired using Diels Alder methodology (= non reversible cross linking = substituted phenyl derivatives = the Nexam cyclotrimerization target product), the Diels Alder approach is potentially less straight forward and necessitates a post elimination of substituents or (normally) a subsequent oxidation:

Benzene DA

The graphic example above is attached solely to explain how a phenyl derivative can be synthesized via a Diels Alder synthetic sequence. This example is not related to any announced Evonik activities.

However, CESI´s initial conclusion is that Evonik primarily is focusing on reversible low temperature applications using an alternative strategy and primarily within the following areas (as highlighted in the patents final sections):“Adhesive, moulding compounds, inks, sealants, coating materials, composite materials, or use in the production of mouldings for example via rapid prototyping methods. One example of application in the rapid prototyping sector for the crosslinking and uncrosslinking materials described here is to be found in the sector of FDM (Fused Deposition Modelling) or in 3D printing by inkjet methods using low-viscosity melts.”

Reversibility is stated as a strength by Evonik. CESI believes that reversibility equals a limitation of scope. In other words: The Evonik concept might be limited to low temperature special applications. However, the Evonik marketing strategy seems excellent and the market potential for the actual special applications should also be large…

Evonik wants to facilitate bulk production of composites

  • New technology is designed to significantly reduce manufacturing costs for composites
  • Hybrid polymer systems form the technology base and are scheduled to be launched on the market in late 2018
  • In the composites business, Evonik aims for medium-term sales in the lower triple-digit million € range

With a chemical trick, Evonik Industries combines the best from two worlds—the characteristics of two types of plastic which were said to be incompatible until now. In doing so, the specialty chemicals company wants to provide an answer for one of the central questions of the composites industry: How can we succeed in producing composites more efficiently? Composites are made of extremely strong fibers embedded in a polymer (plastic). The polymer primarily determines the composite processing. Hybrid polymer systems are the heart of Evonik’s innovation—they combine good processability of thermoplastic polymers and good mechanical properties of thermosetting plastics.

Composites are already in great demand in many different application fields: In lightweight design in the automotive and aviation industry, for example, they reduce the fuel consumption. According to experts, every 100 kilogram of weight saved in a car saves around 0.3 to 0.5 liters of fuel per 100 kilometers. In wind turbines, composites guarantee enormous stability and make bigger and thus more efficient energy plants possible.

But, the production of composites is still complex and costly. Since late 2014, Evonik demonstrates in pilot plants at its Marl site that the material concept of hybrid polymer systems can save time and costs in manufacturing composites. First potential customers have already received samples for testing. First hybrid polymer systems are expected to be ready for the market in 2018.

“Our technology will help to significantly reduce manufacturing costs for composites,” says Chief Innovation Officer Ulrich Küsthardt with conviction, adding that “We want to contribute to leading the way to bulk production of composites.” Evonik that already offers numerous innovative products for composites wants to continue strengthening its position in this growth market.

The company is aiming for sales in the lower triple-digit million € range in the composites market in the medium term. For the market of carbon fiber-reinforced plastics alone, CCeV, a network of companies and research institutes in the fiber composites field, is expecting stabile annual growth of an average of 9 percent by 2020.

Composites are a key technology for lightweight design because of their ability to combine very good mechanical properties and low weight. Their processing properties are mainly determined by the polymer. Thermosetting plastics have very good mechanical properties but do require longer processing times compared to thermoplastic materials. But then again, thermoplastic polymers are easy to process, quick to reshape and to recycle, however, they rarely demonstrate the excellent mechanical properties of thermosetting plastics.

There is a reason for the very different properties: polymer chains in thermosetting plastics are crosslinked whereas in thermoplastics they are not. Switching between crosslink and no link is usually not possible because a chemical crosslinking process is irreversible.

Special Diels-Alder reaction as chemical switch

However, this is exactly what Evonik achieved in cooperation with the Karlsruhe Institute of Technology in producing hybrid polymer systems. They are able to crosslink without using catalysts in a completely reversible process. Heating causes de-crosslinking and allows the system to be reshaped. During the cooling phase, the crosslink is created again and its shape becomes stabile.

A special Diels-Alder reaction causes this phenomenon where the crosslink is almost chemically switched on and off. Material properties are maintained even with repeated heating and cooling.

“We’re cooperating closely with suppliers of semifinished products, plant producers, and processing companies of fiber-reinforced plastics to develop appropriate processing chains for our hybrid polymers,” explains Sandra Reemers, head of Evonik’s Composites Project House. “We aim at offering system solutions that enable an efficient production process for semifinished products as well as final parts.”

The Composites Project House founded in April 2013 develops new materials, processes, and system solutions for composite materials. Project houses are a part of Evonik’s strategic innovation unit Creavis. In the project houses, the company pools expertise from various operative units, bringing in additional external experts. Together, they research topics that expand the existing product and technology portfolio and advance these projects to application stage.

Company information

Evonik, the creative industrial group from Germany, is one of the world leaders
in specialty chemicals. Profitable growth and a sustained increase in the value of the company form the heart of Evonik’s corporate strategy. Its activities focus on the key megatrends health, nutrition, resource efficiency and globalization. Evonik benefits specifically from its innovative prowess and integrated technology platforms.

Evonik is active in over 100 countries around the world. In fiscal 2014 more than 33,000 employees generated sales of around €12.9 billion and an operating profit (adjusted EBITDA) of about €1.9 billion.

Now, let´s highlight an Evonik patent:

Low molecular weight products and use thereof as reversible or permanent low-temperature crosslinking agent in diels-alder reactions  US 20140163165 A1 (Source link: http://www.google.com/patents/US20140163165:)

The invention relates to low molecular mass products and to their preparation and use as reversible or permanent crosslinkers in polymers or polymer networks where the linking or crosslinking of the resultant polymers is brought about via Diels-Alder reactions.

Methods for the reversible crosslinking of polymers are of great interest for a broad field of applications. In adhesive applications, for example, diverse possibilities for the automotive industry or the semiconductor industry have been described. In the context of the construction of machines, precision mechanical devices, or in the building industry as well, however, such adhesives are of interest.

Besides adhesive applications, reversibly crosslinkable polymers may also be of interest in sealants, coating materials such as varnishes or paints, or in the production of mouldings for example via rapid prototyping methods.

The best-known crosslinker molecules for Diels-Alder crosslinking reactions are the bismaleimide units (COMPIMIDE® from Evonik AG) that have already been available commercially for a considerable time.

For a number of years, primarily within academia, methods for constructing block copolymers have been researched under the generic heading of “click chemistry”. In this chemistry, two different homopolymers with linkable end groups are combined with one another and are joined to one another by means, for example, of a Diels-Alder reaction, Diels-Alder-analogous reaction or another cycloaddition. The objective of this reaction is to construct thermally stable, linear and possibly high molecular mass polymer chains. Inglis et al. (Macromolecules 2010, 43, pp. 33-36), for example, describe, for this purpose, polymers with cyclopentadienyl end groups which are obtainable from polymers prepared by means of ATRP. These cyclopentadiene groups are able to react very rapidly in hetero-Diels-Alder reactions with polymers which carry electron-deficient dithioesters as end groups (Inglis et al. Angew. Chem. Int. Ed. 2009, 48, pp. 2411-2414).

The use of monofunctional RAFT polymers for linking with monofunctional polymers which a dihydrothiopyran group by way of a hetero-Diels-Alder reaction is found in Sinnwell et al. (Chem. Comm. 2008, 2052-2054). This method can be used to realise AB diblock copolymers.

Rapid variants of this hetero-Diels-Alder linkage for the synthesis of AB block copolymers with a dithioester group which is present after a RAFT polymerization, and with a dienyl end group, are described in Inglis et al. (Angew. Chem. Int. Ed. 2009, 48, pp. 2411-14) and in Inglis et al. (Macromol. Rapd Commun. 2009, 30, pp. 1792-98). The analogous preparation of multiarm star polymers is found in Sinnwell et al. (J. Pol. Sci.: Part A: Pol. Chem. 2009, 47, pp. 2207-13).

U.S. Pat. No. 6,933,361 describes a system for producing transparent mouldings that are easy to repair. The system consists of two polyfunctional monomers which polymerize by a Diels-Alder reaction to form a highly dense network. One functionality in this system is a maleimide, and the other functionality is a furan. The thermal switching of a highly dense network of this kind is used for its repair. Crosslinking takes place at temperatures above 100° C. The partial reverse reaction at even higher temperatures.

In Syrett et al. (Polym. Chem. 2010, DOI: 10.1039/b9py00316a), star polymers are described for use as flow improvers in oils. These polymers have self-healing properties that can be controlled by means of a reversible Diels-Alder reaction. For that purpose, monofunctional polymethacrylate arms are combined with polymethacrylates which in the middle of the chain, as a fragment of the initiator employed, possess a group which can be used in a reversible Diels-Alder reaction.

Patent application DE102010001987.9 discloses crosslinkable systems which feature a thermoreversible crosslinking mechanism based on a Diels-Alder or hetero-Diels-Alder reaction. DE102010001992.5 discloses analogous systems which have a controllable viscosity by means of the same thermoreversible mechanism.

U.S. Pat. No. 4,513,125 A discloses a composition for special cathodic electrodeposition coatings, where a polydiene-functionalized epoxy-amine reacts with a polydienophile-functionalized polyisocyanate oligomer at elevated temperatures. The polydienophile-functionalized polyisocyanate oligomers have a functionality of at least 3. Cited specifically are furfuryl alcohol and/or furfurylamine, 2-hydroxymethyl-1,3-butadienes, 2-aminomethyl-1,3-butadiene or mixtures thereof. Sorbic alcohol derivatives, however, are not cited.

Object

“It was an object of the present invention to find low molecular mass crosslinker molecules, easy to synthesize and with diverse possible uses, for Diels-Alder reactions at preferably low temperatures, and with the possibility of a retro-Diels-Alder reaction for reversible crosslinkings, these molecules additionally being particularly ecological.”

[…]

“Surprisingly it has been found that the compounds according to the invention can be crosslinked with dienophiles even at room temperature or at only slightly elevated temperatures and that the crosslinking can be made at least 50% reversible at a higher temperature.

It has been found that these systems crosslink very rapidly even at room temperature, optionally with addition of a crosslinking catalyst. It has also been found that these networks can be returned to a thermoplastic state again, simply and almost completely, even at very low temperatures of, for example, somewhat above 80° C. It has additionally been found, very surprisingly, that subsequently a further crosslinking can take place, without further addition of crosslinker and/or catalyst, by means, for example, of pure cooling. A particular effect, furthermore, is that these cycles of crosslinking and conversion back into a thermoplastic can be carried out at least three times, preferably at least five times, without any substantial loss in properties of the network.”

To the best of the authors knowledge, there are no available information describing a hands on collaboration between Nexam and Evonik (within PBO, cyclotrimerizations or Diels Alder reactions). Therefore, CESI disqualifies this hypothesis until such information is formally released. Thus, to the best of the author´s knowledge and on the molecular level, Evonik pursues an alternative concept and should – until the opposite is announced – be classified as a potential future Nexam competitor primarily within low temperature segments. CESI is fully convinced that the Nexam future is very bright. Reversibility is stated as a strength by Evonik. CESI believes that reversibility equals a limitation of scope. In other words and again: The Evonik concept should be limited to low temperature special applications. Regardless, the total market is gigantic and will allow a number of key market players. Furthermore, CESI believes the near future joint webinar will be beneficial for both Nexam and Evonik. However, the Nexam Evonik collaboration is, as expected, a soft collaboration.

Any marketing Synergy effect? CESI: Yes, most likely.

The last weekend Nexam – Evonik webinar is attached here: http://www.globalspec.com/events/eventdetails?eventid=685&evtsrc=EvonikShare)

At t= 36:45. Moderator:

“We have quite a number of questions so far. I´ll start with Jeff Dimmit:

How are Nexam and Evonik working togheter in this area?”

“We realized in the recent past that our dianhydride products and Nexam cross linkers would be often used in the same or similar applications and by similar customers and it just made sense to give us better coverage in the market place if we could work togheter as a team sharing market information and better service to the market with both of our products”

– Jeff Dimmitt, Vice President of Technology and Business Development Evonik Jayhawk Fine


EDIT September 7 2015 🙂

Press release: Evonik Jayhawk and Nexam Chemical form Joint Marketing Program with focus on Polyimide Solutions.

2015-09-07

Evonik Jayhawk Fine Chemicals Corporation and Nexam Chemical AB have begun a joint-marketing program, whereby Evonik’s JAYHAWK dianhydrides and Nexam Chemical’s NEXIMID® cross-linkers will be offered in a coordinated effort to the growing polyimide market sector.

Evonik and Nexam Chemical will collaborate on modifying and improving polyimide processing, while offering physical and mechanical property enhancements. Customers will benefit from consultation in product selection, pairing and optimal dosing to achieve desired properties of their polyimide coatings, films, fibers, foams and resins.

Said Dr. Jeff Dimmit, VP Technology for Evonik Jayhawk, “Our first collaboration was the “Empowering Polyimides” webinar, narrated by Dr. Carlos Solano, Product Manager for Nexam Chemical. The participation and lively Q&A period frankly overwhelmed us. This positive proof that the industry is thirsty for knowledge on how to use our products together has led us to move into a market collaboration.”

Best regards, CESI

The author, Cutting Edge Science Invest, is a Nexam Chemical share holder. Cutting Edge Science Invest can not guarantee, or take into accountability, the content of truth and accuracy of the information in this article/post. Thus, Cutting Edge Science Invest requires that a possible reader gather complimentary information if any type of investment in the company described above is considered. Cutting Edge Science Invest provides personally biased information and at best also “general information and opinions”. The article/post does not contain professional investment advice.