Posts Tagged ‘cross-linking’

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.

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.