US4176220A
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Catalyst composition for ring-opening polymerization of norbornene derivatives and process for polymerizing same
Assignee: JSR Corp
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Filing: 1977-09-27
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Granted: 1979-11-27
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Expires: 1997-09-27
Abstract
Abstract A catalyst composition consisting essentially of a reaction mixture of (A) at least one member selected from the group consisting of compounds of W, Mo, Re and Ta, (B) at least one member selected from the group consisting of organometallic compounds of elements of Groups IA, IIA, IIB and IIIA of the Deming Periodic Table, and (C) at least one member selected from the group consisting of compounds of V, Cr, Mn, and elements of Groups IVB and VIII of the Deming Periodic Table, has a very high activity in the ring-opening polymerization of norbornene derivatives having at least one polar substituent selected from the group consisting of ester groups, nitrile groups, amide groups, imide groups, carboxylic acid anhydride groups and halogens. The metal atom ratio of (C)/(A) is usually 0.001-50, and the molar ratio of (B)/(A) is usually 1-10. At least one said norbornene derivative and at least one cycloolefin other than cyclohexene can also successfully be subjected to ring-opening copolymerization with said catalyst.
Inventors
- 👤 Hiroharu Ikeda
- 👤 Shuichi Matsumoto
- 👤 Kenya Makino
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-02 13:29
CPC Classifications
C; C08; C08G; C08G61/00; C08G61/02; C08G61/04; C08G61/06; C08G61/08; B; B01; B01J; B01J31/00; B01J31/02; B01J31/0201; B01J31/0211; B01J31/0212; B01J31/12; B01J31/14; B01J31/143; B01J31/16; B01J31/22; B01J31/2204; B01J31/2208; B01J31/2226; B01J31/223; B01J31/2234; B01J31/2282; B01J31/2295; B01J31/26; B01J31/34; B01J2531/00; B01J2531/40; B01J2531/46; B01J2531/48; B01J2531/50; B01J2531/56; B01J2531/60; B01J2531/62; B01J2531/70; B01J2531/72; B01J2531/80; B01J2531/84; B01J2531/842
Claims Analysis
Total Claims: 34
Claim 1
Independent Claim
171 words
A process for producing a polymer or copolymer of a norbornene derivative, which comprises contacting at least one norbornene derivative having at least one ester group, or a monomer mixture of at least one of said norbornene derivatives and at least one cycloolefin other than cyclohexene, with a catalyst composition consisting essentially of a reaction mixture of (A) at least one member selected from the group consisting of compounds of W, Mo, Re and Ta, (B) at least one member selected from the group consisting of organometallic compounds of elements of Groups IA, IIA, IIB and IIIA of the Deming Periodic Table, and (C) at least one member selected from the group consisting of oxides, hydroxides, nitrates, sulfates, phosphates, acetylacetone complexes, and ammine complexes of V, Cr and Mn; oxides, sulfates, phosphates, acetylacetone complexes, cyclopentadienyl complexes, hydride complexes and silicides of elements of Group IVB of the Deming Periodic Table; and oxides, peroxides, hydroxides, sulfates, phosphates, acetylacetone complexes, and ammine complexes of elements of Group VIII of the Deming Periodic Table.
Claim 2
Dependent Claim
171 words
A process for producing a polymer or copolymer of a norbornene derivative, which comprises contacting at least one norbornene derivative having at least one ester group, or a monomer mixture of at least one of said norbornene derivatives and at least one cycloolefin other than cyclohexene, with a catalyst composition consisting essentially of a reaction mixture of (A) at least one member selected from the group consisting of compounds of W, Mo, Re and Ta, (B) at least one member selected from the group consisting of organometallic compounds of elements of Groups IA, IIA, IIB and IIIA of the Deming Periodic Table, and (C) at least one member selected from the group consisting of oxides, hydroxides, nitrates, sulfates, phosphates, acetylacetone complexes, and ammine complexes of V, Cr and Mn; oxides, sulfates, phosphates, acetylacetone complexes, cyclopentadienyl complexes, hydride complexes and silicides of elements of Group IVB of the Deming Periodic Table; and oxides, peroxides, hydroxides, sulfates, phosphates, acetylacetone complexes, and ammine complexes of elements of Group VIII of the Deming Periodic Table.
Claim 3
Dependent Claim
205 words
A process according to claim 1, wherein the norbornene derivative is at least one compound selected from the group consisting of esters having the formulas, ##STR16## wherein R is a saturated or unsaturated hydrocarbon group having up to 20 carbon atoms; X is H, --(CH 2 ) m COOR 1 , --(CH 2 ) m OCOR 1 , a saturated or unsaturated hydrocarbon group having up to 10 carbon atoms, --(CH 2 ) m CN, --(CH 2 ) m CONR 2 R 3 , or a halogen, where R 1 is a saturated or unsaturated hydrocarbon group having up to 20 carbon atoms, R 2 and R 3 are independently H or a saturated or unsaturated hydrocarbon group having up to 10 carbon atoms, and m is an integer of 0 to 10; A and B are independently H or a saturated or unsaturated hydrocarbon group having up to 10 carbon atoms; and n is an integer of 0 to 10; tricyclic compounds having the formulas, ##STR17## wherein A and B are as defined above; and R 4 is an alkylene group having up to 10 carbon atoms, and tetracyclic compounds having the formula, ##STR18## wherein A, B, R, X and n as defined above.
Claim 4
Dependent Claim
57 words
A process according to claim 1, wherein the norbornene derivative is at least one ester selected from the group consisting of methyl 5-norbornene-2-carboxylate, ethyl 5-norbornene-2-carboxylate, butyl 5-norbornene-2-carboxylate, octyl 5-norbornene-2-carboxylate, lauryl 5-norbornene-2-carboxylate, oleyl 5-norbornene-2-carboxylate, phenyl 5-norbornene-2-carboxylate, ethyl 2-methyl-5-norbornene-2-carboxylate, ethyl 3-phenyl-5-norbornene-2-carboxylate, ethyl 3,3-dimethyl-5-norbornene-2-carboxylate, cyclohexyl 5-norbornene-2-carboxylate, allyl 5-norbornene-2-carboxylate, dimethyl 5-norbornene-2,3-dicarboxylate, allyl ethyl 5-norbornene-2,3-dicarboxylate, 5-norbornen-2-yl acetate, 2-methyl-5-norbornen-2-yl acetate and 5-norbornen-2-yl propionate.
Claim 5
Dependent Claim
27 words
A process according to claim 1, wherein the cycloolefin is selected from the group consisting of cyclobutene, cyclooctene, 1,5-cyclooctadiene, 1,5,9-cyclododecatriene, norbornene, 5-methylnorbornene, 5-phenylnorbornene, dicyclopentadiene, dihydrodicyclopentadiene and norbornadiene.
Claim 6
Dependent Claim
13 words
A process according to claim 1, wherein the norbornene derivative is methyl 5-norbornene-2-carboxylate.
Claim 7
Dependent Claim
44 words
A process according to claim 1, wherein the component (A) is selected from the group consisting of halides, oxyhalides, alkoxyhalides, alkenoxyhalides, phenoxyhalides, alkoxides, alkenoxides, phenoxides, carboxylates, acetylacetonates, oxyacetylacetonates, carbonyl complexes, acetonitrile complexes and hydride complexes of W, Mo, Re and Ta, and derivatives thereof.
Claim 8
Dependent Claim
151 words
A process according to claim 1, wherein the component (A) is selected from the group consisting of WCl 6 , WCl 5 , WCl 4 , WBr 6 , WF 6 , WI 6 , MoCl 5 , MoCl 4 , MoCl 3 , ReCl 5 , WOCl 4 , MoOCl 3 , ReOCl 3 , ReOBr 3 , W(OPh) 6 , WCl 2 (OPh) 4 , Mo(OC 2 H 5 ) 2 Cl 3 , Mo(OC 2 H 5 ) 5 , MoO 2 (acac) 2 , W(OCOR) 3 , W(CO) 6 , Mo(CO) 6 , Re 2 (CO) 10 , ReOBr 3 .PPh 3 , WCl 5 .PPh 3 , WCl 6 .C 5 H 5 N, W(CO) 5 .PPh 3 , W(CO) 3 (CH 3 CN) 3 , TaCl 5 and TaBr 5 , wherein Ph means phenyl, acac means acetylacetone residue, and R means a hydrocarbon group.
Claim 9
Dependent Claim
26 words
A process according to claim 1, wherein the component (A) is selected from the group consisting of halides, oxyhalides, alkoxyhalides and phenoxyhalides of W and Mo.
Claim 10
Dependent Claim
195 words
A process according to claim 1, wherein the component (B) is selected from the group consisting of n--C 4 H 9 Li, n--C 5 H 11 Na, C 5 H 5 Na, CH 3 MgI, C 2 H 5 MgBr, CH 3 MgBr, n--C 3 H 7 MgCl, t--C 4 H 9 MgCl, CH 2 ═CH--CH 2 MgCl, (C 2 H 5 ) 2 Zn, (C 2 H 5 ) 2 Cd, CaZn(C 2 H 5 ) 4 , (CH 3 ) 3 B, (C 2 H 5 ) 3 B, (n--C 4 H 9 ) 3 B, (CH 3 ) 3 Al, (C 2 H 5 ) 3 Al, (C 2 H 5 ) 3 Al.O(C 2 H 5 ) 2 , (C 2 H 5 ) 2 AlCl, C 2 H 5 AlCl 2 , (C 2 H 5 ) 2 AlH, (iso--C 4 H 9 ) 2 AlH, (C 2 H 5 ) 2 AlOC 2 H 5 , (iso--C 4 H 9 ) 3 Al, (C 2 H 5 ) 3 Al 2 Cl 3 , (n--C 6 H 13 ) 3 Al and (n--C 8 H 17 ) 3 Al.
Claim 11
Dependent Claim
24 words
A process according to claim 1, wherein the component (B) is selected from the group consisting of organometallic compounds of Al, Mg and Zn.
Claim 12
Dependent Claim
21 words
A process according to claim 1, wherein the component (B) is selected from the group consisting of organometallic compounds of Al.
Claim 13
Dependent Claim
32 words
A process according to claim 1, wherein the component (C) is selected from the group consisting of oxides, hydroxides, nitrates, sulfates, phosphates, acetylacetone complexes, and ammine complexes of V, Cr and Mn.
Claim 14
Dependent Claim
70 words
A process according to claim 12, wherein the component (C) is selected from the group consisting of V 2 O 5 , CrO 3 , MnO 2 , Cr(OH) 3 , Mn(OH) 2 , VSO 4 , Cr(NO) 3 ) 3 , Cr 2 (SO 4 ) 3 , MnSO 4 , V(acac) 2 , Cr(acac) 2 , VO(acac) 2 and Mn(acac) 3 , in which acac means acetylacetone residue.
Claim 15
Dependent Claim
38 words
A process according to claim 1 wherein the component (C) is selected from the group consisting of oxides, sulfates, phosphates, acetylacetone complexes, cyclopentadienyl complexes, hydride complexes and silicides of elements of Group IVB of the Deming Periodic Table.
Claim 16
Dependent Claim
57 words
A process according to claim 14, wherein the component (C) is selected from the group consisting of TiO 2 , ZrO 2 , HfO 2 , Ti(SO) 4 ) 2 , Ti(PO 4 ) 4 , Zr(PO 4 ) 4 , TiO(acac) 2 , Zr(acac) 4 , Hf(acac) 4 in which acac means acetylacetone residue, and TiSi.
Claim 17
Dependent Claim
37 words
A process according to claim 1, wherein the component (C) is selected from the group consisting of oxides, peroxides, hydroxides, sulfates, phosphates, acetylacetone complexes, and ammine complexes of elements of Group VIII of the Deming Periodic Table.
Claim 18
Dependent Claim
81 words
A process according to claim 16, wherein the component (C) is selected from the group consisting of Fe 2 O 3 , Ni 2 O 3 , Co 2 O 3 , RuO 2 , PtO 2 , OsO 4 , NiO 2 , NiO, Fe(OH) 3 , FeSO 4 , CoSO 4 .6H 2 O, NiSO 4 , nickel phosphate, Fe(acac) 3 , Fe(acac) 2 , Co(acac) 3 , Ni(acac) 2 and Pd(acac) 2 in which acac means acetylacetone residue.
Claim 19
Dependent Claim
41 words
A process according to claim 1, wherein the metal atom ratio of the component (C) to the component (A) is 0.001 to 50, and the proportion of the component (B) is 1 to 10 moles per mole of the component (A).
Claim 20
Dependent Claim
23 words
A process according to claim 18, wherein the metal atom ratio of the component (C) to the component (A) is 0.001 to 10.
Claim 21
Dependent Claim
24 words
A process according to claim 18, wherein the proportion of the component (B) is 1.5 to 5 moles per mole of the component (A).
Claim 22
Dependent Claim
19 words
A process according to claim 1, wherein the concentration of the norbornene derivative is at least 0.1% by weight.
Claim 23
Dependent Claim
31 words
A process according to claim 1, wherein the norbornene derivative or the monomer mixture is contacted with the catalyst at a temperature in the range from -30° C. to +200° C.
Claim 24
Dependent Claim
40 words
A process according to claim 1, wherein the norbornene derivative or the monomer mixture is contacted with the catalyst in an amount corresponding to 0.02 to 100 mmol. of the component (A) per mole of the monomer or monomer mixture.
Claim 25
Dependent Claim
25 words
A process according to claim 1, wherein the norbornene derivative or the monomer mixture is contacted with the catalyst in the presence of a solvent.
Claim 26
Dependent Claim
26 words
A process according to claim 24, wherein the solvent is at least one member selected from the group consisting of hydrocarbons, halogenated hydrocarbons, ethers and esters.
Claim 27
Dependent Claim
35 words
A process according to claim 24, wherein the solvent is selected from the group consisting of hexane, heptane, benzene, toluene, chloroform, 1,2-dichloroethane, chlorobenzene, diethyl ether, dibutyl ether, diphenyl ether, tetrahydrofuran, ethyl acetate and methyl propionate.
Claim 28
Dependent Claim
23 words
A process according to claim 1, wherein the norbornene derivative or the monomer mixture is contacted with the catalyst in an inert atmosphere.
Claim 29
Dependent Claim
15 words
A process according to claim 27, wherein the inert atmosphere is nitrogen, helium or argon.
Claim 30
Dependent Claim
27 words
A process according to claim 1, wherein the norbornene derivative or the monomer mixture is contacted with the catalyst in the presence of a molecular weight regulator.
Claim 31
Dependent Claim
26 words
A process according to claim 29, wherein the molecular weight regulator is a hydrocarbon having in the molecule at least one carbon-carbon double or triple bond.
Claim 32
Dependent Claim
128 words
A process according to claim 29, wherein the molecular weight regulator is a polar allyl compound represented by the formula, CH 2 ═CR I CR II R III X 4 or (CH 2 ═CR I CR II R III ) p Y 3 in which R I , R II and R III are independently hydrogen or a hydrocarbon having up to 10 carbon atoms, X 4 is a halogen atom or an --OR a , ##STR19## or --NR c R d group in which R a , R b , R c and R d are independently hydrogen or a saturated or unsaturated hydrocarbon group having up to 20 carbon atoms, Y 3 is a polybasic acid residue, and p is the basicity of the polybasic acid.
Claim 33
Dependent Claim
223 words
A process for producing a polymer or copolymer of a norbornene derivative, which comprises contacting at a temperature in the range of from -30° C. to +200° C. in an inert atmosphere at least one norbornene derivative having at least one ester group, or a monomer mixture of at least one of said norbornene derivative and at least one cycloolefin other than cyclohexene, with a catalyst composition consisting essentially of a reaction mixture of (A) at least one member selected from the group consisting of halides, oxyhalides, alkoxyhalides and phenoxyhalides of W and Mo, (B) at least one member selected from the group consisting or organometallic compounds of elements of Groups IA, IIA, IIB and IIIA of the Deming Periodic Table, and (C) at least one member selected from the group consisting of oxides, hydroxides, nitrates, sulfates, phosphates, acetylacetone complexes, and ammine complexes of V, Cr and Mn, oxides, sulfates, phosphates acetylacetone complexes, cyclopentadienyl complexes, hydride complexes and silicides of elements of Group IVB of the Deming Periodic Table and oxides, peroxides, hydroxides, sulfates, phosphates, acetylacetone complexes, and ammine complexes of elements of Group VIII of the Deming Periodic Table; the metal atom ratio of the component (C) to the component (A) being 0.001 to 50, and the proportion of the component (B) being 1 to 10 moles per mole of component (A).
Claim 34
Dependent Claim
223 words
A process for producing a polymer or copolymer of a norbornene derivative, which comprises contacting at a temperature in the range of from -30° C. to +200° C. in an inert atmosphere at least one norbornene derivative having at least one ester group, or a monomer mixture of at least one of said norbornene derivative and at least one cycloolefin other than cyclohexene, with a catalyst composition consisting essentially of a reaction mixture of (A) at least one member selected from the group consisting of halides, oxyhalides, alkoxyhalides and phenoxyhalides of W and Mo, (B) at least one member selected from the group consisting or organometallic compounds of elements of Groups IA, IIA, IIB and IIIA of the Deming Periodic Table, and (C) at least one member selected from the group consisting of oxides, hydroxides, nitrates, sulfates, phosphates, acetylacetone complexes, and ammine complexes of V, Cr and Mn, oxides, sulfates, phosphates acetylacetone complexes, cyclopentadienyl complexes, hydride complexes and silicides of elements of Group IVB of the Deming Periodic Table and oxides, peroxides, hydroxides, sulfates, phosphates, acetylacetone complexes, and ammine complexes of elements of Group VIII of the Deming Periodic Table; the metal atom ratio of the component (C) to the component (A) being 0.001 to 50, and the proportion of the component (B) being 1 to 10 moles per mole of component (A).
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