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EP-4735504-A1 - POLYMERIZABLE COMPOSITION OF CYCLIC OLEFINIC MONOMERS AND ASSOCIATED RING-OPENING METATHESIS POLYMERIZATION PROCESS

EP4735504A1EP 4735504 A1EP4735504 A1EP 4735504A1EP-4735504-A1

Abstract

There is provided a polymerizable composition comprising: • monomers, said monomers comprising cyclic olefinic monomers having a ring strain of greater than 85 kJ/mol, preferably greater than 100 kJ/mol; • one or more 18-electron Schrock alkylidene adducts chosen from complexes of 14-electron Schrock alkylidene compounds and bidentate ligands, and • less than 10 wt.% of an inert solvent, based on the weight of the polymerizable composition, preferably less than 5 wt.%. Also provided is a ring-opening metathesis polymerization process and a polymerized article obtainable by said process.

Inventors

  • Drozdzak-Matusiak, Renata Anna
  • Daemen, Alexander Pieter Maria
  • NISHIOKA, NAOKI
  • GULYÁS, Henrik
  • TSCHAN, Mathieu, Jean-Luc, Joseph

Assignees

  • Telene SAS
  • Rimtec Corporation

Dates

Publication Date
20260506
Application Date
20240627

Claims (15)

  1. 1. Polymerizable composition comprising: • monomers, said monomers comprising cyclic olefinic monomers having a ring strain of greater than 85 kJ/mol, preferably greater than 100 kJ/mol; • one or more 18-electron Schrock alkylidene adducts chosen from complexes of 14-electron Schrock alkylidene compounds with bidentate ligands according to formula (I): wherein R a , R b , R c , R d , R e , R f , R g and R h are independently selected from the group consisting of H, halogen, nitro, cyano, trifluoromethyl, C1-C12- alkoxycarbonyl, Ci-Ci2-alkyl, 5- to 18-membered aryl, Ci-Ci2-alkyloxy and di- (Ci-C4-alkyl)amino, or residues R d and R e are connected to one another while forming a 6-membered ring wherein R d and R e together form a group C(R‘)=C(R j ) wherein R 1 and R 1 are independently selected from the group consisting of H, halogen, nitro, cyano, trifluoromethyl, Ci-Ci2-alkoxycarbonyl, Ci-Ci2-alkyl, 5- to 18-membered aryl, Ci-Ci2-alkyloxy and di-(Ci-C4- alkyl) amino, wherein the one or more 18-electron Schrock alkylidene adducts have a stability constant K greater than 250,000 L-mol' 1 at 25°C in deuterated benzene (CeDe) as determined in accordance with the protocol defined in the detailed description, preferably greater than 500,000 L-mol' 1 ; and less than 10 wt.% of an inert solvent, based on the weight of the polymerizable composition, preferably less than 5 wt%.
  2. 2. Polymerizable composition according to claim 1, wherein the one or more 18-electron Schrock alkylidene adducts are chosen from the group represented by formula (II): wherein: M is Mo or W, A is O or N-R 3 , R 1 and R 2 are independently selected from the group consisting of H, Ci-Ci2-alkyl and 5-to 18-membered aryl, which Ci-Ci2-alkyl and 5-to 18-membered aryl in turn may be substituted with one or more of Ci-Ci2-alkyl, 5- to 18-membered aryl, Ci- Ci2-alkyloxy, di- (Ci-C4-alkyl) amino, halogen, trifluoromethyl, cyano and nitro residues, with the proviso that only one of R 1 and R 2 can be hydrogen at the same time, R 3 is selected from the group consisting of Ci-Ci2-alkyl and 5- to 18-membered aryl, which in turn may be substituted with one or more of Ci-Ci2-alkyl, 5- to 18- membered aryl, Ci-Ci2-alkoxy, di-(Ci-C4-alkyl)amino, halogen, trifluoromethyl, cyano and nitro residues, X and Y are independently selected from the group consisting of halogen, methanesulfonyloxy, trifluoromethanesulfonyloxy, benzenesulfonyloxy, toluenesulfonyloxy, pyrrolyl, indolyl, pyrazolyl, Ci-Ci2-alkyloxy, 5- to 18- membered aryloxy, tri(Ci-Ci2-alkyl)silyloxy, tri(C6-Ci8-aryl)silyloxy, di(Ci-Ci2- alkyl)(C6-Ci8-aryl)silyloxy, (Ci-Ci2-alkyl)di(C6-Ci8-aryl)silyloxy and tri(Ci-Ci2- alkyloxy) silyloxy, which in turn may be substituted with one or more of Ci-Ci2-alkyl, 5-to 18-membered aryl, Ci-Ci2-alkyloxy, di-(Ci-C4-alkyl)amino, halogen, trifluoromethyl, cyano and nitro residues, or wherein groups X and Y together form the structure of formula (III-A), (III-B) or (III-C): (III-A) (III-B) (IH-C) wherein R A , R B , R c , R D , R E , R F , R G and R H are independently selected from the group consisting of H, halogen, nitro, cyano, trifluoromethyl, C1-C12- alkoxycarbonyl, Ci-Ci2-alkyl, 5- to 18-membered aryl, Ci-Ci2-alkyloxy and di-(Ci- C4-alkyl)amino.
  3. 3. Polymerizable composition according to claim 1 or 2, wherein the one or more 18- electron Schrock alkylidene adducts are chosen from formula (II- A) and (II-B): wherein M, A, X, Y, R 1 and R 2 are as defined in claim 2.
  4. 4. Polymerizable composition according to any one of claims 1 to 3, wherein the one or more 18-electron Schrock alkylidene adducts are chosen from formula (II-C) and formula (II-D): (II-D), wherein M is Mo or W, preferably Mo, and wherein iPr represents isopropyl.
  5. 5. Polymerizable composition according to any one of claims 1 to 4, wherein the cyclic olefinic monomers having a ring strain of greater than 85 kJ/mol are chosen from the group consisting of dicyclopentadiene (DCPD), norbomene or derivatives thereof, norbomadiene or derivatives thereof and combinations thereof.
  6. 6. Polymerizable composition according to any one of claims 1 to 5, further comprising cyclic olefinic monomers chosen from the group consisting of cyclopentene, 1,4- cyclohexadiene, cycloheptene, czs-cyclooctene, cis, cis- 1,5-cyclooctadiene, 1, 3,5,7- cyclooctatetraene, cyclododecene, trans, trans, cis- 1 ,5,9-cyclododecatriene, derivatives thereof and combinations thereof.
  7. 7. Polymerizable composition according to any one of claims 1 to 6, wherein the monomers constitute at least 20 wt.% of the weight of the polymerizable composition, preferably at least 50 wt.%, more preferably at least 90 wt.%.
  8. 8. Polymerizable composition according to any one of claims 1 to 7, wherein cyclic olefinic monomers constitute at least 80 mol% of the monomers, preferably at least 90 mol%.
  9. 9. Polymerizable composition according to any one of claims 1 to 8, wherein the monomers comprise dicyclopentadiene (DCPD), cz‘5,cz5-l,5-cyclooctadiene (COD) and optionally ethylidene norbornene (ENB) and/or tricyclopentadiene (TCPD).
  10. 10. Polymerizable composition according to any one of claims 1 to 9, wherein the molar ratio of the cyclic olefinic monomers to the one or more 18-electron Schrock alkylidene adducts is between 500 and 200000, preferably between 10000 and 150000, more preferably between 20000 and 80000.
  11. 11. Polymerizable composition according to any one of claims 1 to 10, wherein the polymerizable composition does not comprise MgCh, MgB . Mgh, MnCh, MnB . Mnh, FeCh, AlCh, CuCh, ZnCh, ZnB . Znh, Zn(triflate)2 and Zn(trifluoroacetate)2.
  12. 12. Ring-opening metathesis polymerization process comprising the steps of: (a) providing a polymerizable composition according to any one of claims 1 to 11; and (b) subjecting the polymerizable composition to ring-opening metathesis polymerization.
  13. 13. Ring-opening metathesis polymerization process according to claim 12, wherein no MgCh, MgBr 2 , Mgl 2 , MnCl 2 , MnBr 2 , Mnl 2 , FeCh, A1C1 3 , CuCl 2 , ZnCl 2 , ZnBr 2 , Znh, Zn(triflate)2 and Zn(trifluoroacetate)2 are added.
  14. 14. Ring-opening metathesis polymerization process according to claim 12 or 13, wherein step (a) comprises injecting the polymerizable composition into a mold, casting the polymerizable composition into a mold, and/or providing the polymerizable composition into a bath for wetting reinforcing fibers.
  15. 15. Polymerized article comprising between 5 and 100 ppm of the combined amounts of the metals Mo and W, based on the weight of the polymerized article, obtainable by the ring-opening metathesis polymerization process according to any one of claims 12 to 14.

Description

POLYMERIZABLE COMPOSITION OF CYCLIC OLEFINIC MONOMERS AND ASSOCIATED RING-OPENING METATHESIS POLYMERIZATION PROCESS FIELD OF THE INVENTION The present invention relates to a polymerizable composition comprising monomers, said monomers comprising cyclic olefinic monomers. The invention also relates to a ringopening metathesis polymerization (ROMP) process that makes use of the polymerizable composition. The invention finally concerns novel polymerized articles obtainable by the ROMP process. BACKGROUND OF THE INVENTION Preparation of polymers and copolymers by ring opening metathesis polymerization (ROMP) of cyclic olefinic monomers is well known in the art. A good example is the production of polydicyclopentadiene polymer (PDCPD) by using dicyclopentadiene monomers and a metathesis catalyst system. Examples of other monomers that may be used to copolymerize with DCPD include monocyclic olefins which contain 3 or more carbon atoms and one or more double bonds. Typical examples include cyclooctadiene (COD), tricyclopentadiene (TCPD) and ethylidene norbornene (ENB) monomers. ROMP of cyclic olefinic monomers may be catalysed by organometallic complexes having a transition metal atom as centre atom. Transition metals such as tantalum, molybdenum, tungsten, ruthenium, and osmium may be mentioned. Molybdenum (Mo) and tungsten (W) alkylidene complexes - referred to as Schrock catalysts - are among the most promising catalysts for olefin metathesis reactions, such as the group of Mo(VI) and W(VI) alkylidene complexes. Although such catalysts may be effective in catalysing ROMP of cyclic olefinic monomers, they are known in the art to frequently lack stability in air which makes them more difficult to handle and often restricts their usefulness, in particular in processes that cannot be carried out under inert circumstances. WO2012/116695A1, which is incorporated in the present application in its entirety, has proposed a solution to overcome the lack of air stability by complexing such catalysts with bidentate heterocycles such as 1,10-phenanthroline and 2,2’-bipryridine. In such process, 18-electron molybdenum or tungsten alkylidene complexes for instance are formed by a 14- electron molybdenum or tungsten alkylidene complex (herein referred to as a ‘parent complex’) and a 1,10-phenanthroline or a 2,2’ -bipyridine as a neutral bidentate ligand. Unfortunately, it turned out that such air stable catalysts were not active catalytically, and they had to be chemically activated by exposure to a Lewis acid such as MgCh, MgBr2, Mgl2, MnCl2, MnBr2, Mnl2, FeCh, A1C13, CuCl2, ZnCl2, ZnBr2, Znl2, Zn(triflate)2 or Zn(trifluoroacetate)2 for instance. Having to add such Lewis acid is cumbersome in many production processes, for instance because of producing undesirable by-products, and should preferably be avoided. WO2021/239891A1 discloses Schrock-alkylidene complexes comprising a phenanthrene ligand. The inventors of WO2021/239891A1 discovered that such Schrock-alkylidene complexes having a finite stability constant in the range of from 5 L-mol'1 to 250,000 L-moF 1 when measured at 25°C and when the complex is dissolved in a solvent, may be airstable and catalytically active in an olefinic metathesis reaction without the necessity of removing the bidentate ligand by means of a Lewis acid, and hence unnecessarily forming the corresponding by-products. Such complexes appear to be autoactivating when dissolved. However, it appears difficult to control ROMP kinetics with these catalysts, in particular for polymerizing compositions that at least comprise cyclic olefinic monomers having a ring strain of greater than 85 kJ/mol. Therefore, it is an object of the present invention to provide a polymerizable composition of monomers, said monomers comprising cyclic olefinic monomers having high ring strain, which allows simplified handling in processing without a chemical activation and without the risk of a premature and uncontrollable ROMP reaction. Other objects of the present invention provide a safe moulding operation, and a practical manufacturing method that can be scaled up easily. A further object provides a ring-opening metathesis polymerization (ROMP) process that makes use of the polymerizable composition, as well as novel polymerized articles obtainable using the invented ROMP process. SUMMARY OF THE INVENTION This and other objects are achieved by a polymerizable composition in accordance with claim 1. The polymerizable composition comprises: • monomers, said monomers comprising cyclic olefinic monomers having a ring strain of greater than 85 kJ/mol, preferably greater than 100 kJ/mol; • one or more 18-electron Schrock alkylidene adducts chosen from complexes of 14- electron Schrock alkylidene compounds and bidentate ligands according to formula (I): wherein Ra, Rb, Rc, Rd, Re, Rf, Rg and Rh are independently selected from the group consisting of H, halogen, nitro, cyano, trifluoromethyl, Ci-Ci2-alkoxycarbonyl, Ci- Ci