JPH01304113A - Polymer molded item, preparation thereof and combination of reactive solutions - Google Patents
Polymer molded item, preparation thereof and combination of reactive solutionsInfo
- Publication number
- JPH01304113A JPH01304113A JP13449288A JP13449288A JPH01304113A JP H01304113 A JPH01304113 A JP H01304113A JP 13449288 A JP13449288 A JP 13449288A JP 13449288 A JP13449288 A JP 13449288A JP H01304113 A JPH01304113 A JP H01304113A
- Authority
- JP
- Japan
- Prior art keywords
- metathesis
- weight
- polymer
- mol
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title description 5
- 239000000178 monomer Substances 0.000 claims abstract description 49
- 238000005649 metathesis reaction Methods 0.000 claims abstract description 33
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005977 Ethylene Substances 0.000 claims abstract description 18
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000000465 moulding Methods 0.000 claims abstract description 13
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 9
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 claims abstract description 7
- 125000005250 alkyl acrylate group Chemical group 0.000 claims abstract description 7
- 230000003213 activating effect Effects 0.000 claims abstract description 4
- 239000002685 polymerization catalyst Substances 0.000 claims description 15
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 36
- 238000006116 polymerization reaction Methods 0.000 description 34
- 238000000034 method Methods 0.000 description 19
- 229920001577 copolymer Polymers 0.000 description 16
- 239000000203 mixture Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- -1 cyclic olefins Chemical class 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 230000000977 initiatory effect Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 229920006037 cross link polymer Polymers 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- 150000003658 tungsten compounds Chemical class 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 4
- 229920001038 ethylene copolymer Polymers 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000002879 Lewis base Substances 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 150000007527 lewis bases Chemical class 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 238000010107 reaction injection moulding Methods 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 2
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- QMXMUMFLBFAAGK-UHFFFAOYSA-N 2,3-dibromobicyclo[2.2.1]hept-5-ene Chemical compound C1C2C(Br)C(Br)C1C=C2 QMXMUMFLBFAAGK-UHFFFAOYSA-N 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- CTYWXRDQWMRIIM-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)prop-2-enoic acid Chemical compound CC(C)(C)C1=CC(C=CC(O)=O)=CC(C(C)(C)C)=C1O CTYWXRDQWMRIIM-UHFFFAOYSA-N 0.000 description 1
- PKLSXHWGONEQNK-UHFFFAOYSA-N 4-(5-bicyclo[2.2.1]hept-2-enyl)pyridine Chemical compound C1=CC2CC1CC2C1=CC=NC=C1 PKLSXHWGONEQNK-UHFFFAOYSA-N 0.000 description 1
- MNMOMAVDNURDKD-UHFFFAOYSA-N 5-(2,4-dibromophenyl)bicyclo[2.2.1]hept-2-ene Chemical compound BrC1=CC(Br)=CC=C1C1C(C=C2)CC2C1 MNMOMAVDNURDKD-UHFFFAOYSA-N 0.000 description 1
- IILGONGLRASCAC-UHFFFAOYSA-N 5-(2-methylphenoxy)bicyclo[2.2.1]hept-2-ene Chemical compound C1(=C(C=CC=C1)OC1C2C=CC(C1)C2)C IILGONGLRASCAC-UHFFFAOYSA-N 0.000 description 1
- JGLIHSMBVDZMSA-UHFFFAOYSA-N 5-(cyclohexen-1-yl)bicyclo[2.2.1]hept-2-ene Chemical compound C1=CC2CC1CC2C1=CCCCC1 JGLIHSMBVDZMSA-UHFFFAOYSA-N 0.000 description 1
- PSCJIEZOAFAQRM-UHFFFAOYSA-N 5-chlorobicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(Cl)CC1C=C2 PSCJIEZOAFAQRM-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- PGNNHYNYFLXKDZ-UHFFFAOYSA-N 5-phenylbicyclo[2.2.1]hept-2-ene Chemical compound C1=CC2CC1CC2C1=CC=CC=C1 PGNNHYNYFLXKDZ-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- KNOVZEUMNAFMCY-UHFFFAOYSA-N C12CCC(C=C1)C2.C21CCC(C=C2)C1.C=C Chemical compound C12CCC(C=C1)C2.C21CCC(C=C2)C1.C=C KNOVZEUMNAFMCY-UHFFFAOYSA-N 0.000 description 1
- FSJIGHAYBSSMFD-UHFFFAOYSA-N C1C(C(C2)C(O)=O)C=CC12CCC1(C=C2)CC(C(=O)O)C2C1 Chemical compound C1C(C(C2)C(O)=O)C=CC12CCC1(C=C2)CC(C(=O)O)C2C1 FSJIGHAYBSSMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 description 1
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 1
- BMAXQTDMWYDIJX-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carbonitrile Chemical compound C1C2C(C#N)CC1C=C2 BMAXQTDMWYDIJX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- BWKCCRPHMILRGD-UHFFFAOYSA-N chloro hypochlorite;tungsten Chemical compound [W].ClOCl BWKCCRPHMILRGD-UHFFFAOYSA-N 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000001925 cycloalkenes Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- GNPSMYTXIPVJDU-UHFFFAOYSA-N dioctylalumane Chemical compound C(CCCCCCC)[AlH]CCCCCCCC GNPSMYTXIPVJDU-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002316 fumigant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 125000005462 imide group Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- AGQPHHBPENBBIO-UHFFFAOYSA-M iodo(dioctyl)alumane Chemical compound [I-].CCCCCCCC[Al+]CCCCCCCC AGQPHHBPENBBIO-UHFFFAOYSA-M 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- AEBDJCUTXUYLDC-UHFFFAOYSA-N methyl 5-methylbicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OC)(C)CC1C=C2 AEBDJCUTXUYLDC-UHFFFAOYSA-N 0.000 description 1
- RMAZRAQKPTXZNL-UHFFFAOYSA-N methyl bicyclo[2.2.1]hept-2-ene-5-carboxylate Chemical compound C1C2C(C(=O)OC)CC1C=C2 RMAZRAQKPTXZNL-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- XFCTVRBFLKBUFQ-UHFFFAOYSA-N trideca-2,8-diene Chemical compound CCCCC=CCCCCC=CC XFCTVRBFLKBUFQ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Landscapes
- Injection Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
Description
【発明の詳細な説明】
ａ、産業上の利用分野
本発明は、メタセシス重合性モノマーをメタセシス重合
触媒系の共存下成型鋳型内に流し込み、該型内でバルク
重合と同時に成型を行う方法、それによって得られた重
合体成型物およびそのための反応性Ｆｇ液の組合せに関
するものである。DETAILED DESCRIPTION OF THE INVENTION a. Industrial Application Field The present invention relates to a method of pouring a metathesis-polymerizable monomer into a mold in the coexistence of a metathesis-polymerization catalyst system, and performing molding simultaneously with bulk polymerization in the mold; This invention relates to a combination of a polymer molded product obtained by the method and a reactive Fg liquid therefor.
更に詳しくは上記の技術において特定のポリマーを共存
させることによって架橋重合体成型物の耐ｗＩ撃性、耐
熱性を顕著に改良せしめるとともに、上記バルク重合反
応を有利に調節する方法に関するものである。More specifically, the present invention relates to a method of significantly improving the wI impact resistance and heat resistance of a crosslinked polymer molded product by coexisting a specific polymer in the above technique, and advantageously controlling the bulk polymerization reaction.
ｂ、従来技術
環状オレフィンかメタセシス重合触媒系によって開環し
架橋重合体を与えることは公知である。b. Prior Art It is known that cyclic olefins can be ring-opened by metathesis polymerization catalyst systems to give crosslinked polymers.
そこでジシクロペンタジェンのように安価に得られかつ
メタセシス重合性の基を２個有するモノマーを液状の状
態で鋳型に流し込み、その型内でバルク重合せしめ、重
合と同時に成型を一段で行う方法が提案された（例えば
特開昭５８−１２９０１３号公報参照）。Therefore, there is a method in which a monomer such as dicyclopentadiene, which can be obtained at low cost and has two metathesis-polymerizable groups, is poured into a mold in a liquid state, bulk polymerized in the mold, and molded simultaneously with polymerization in one step. proposed (for example, see Japanese Patent Laid-Open No. 129013/1983).
かかる方法によれば、安価な鋳型を用いて、大型の成型
物が得られるため広範な用途に使用出来る可能性を有す
る。According to this method, a large-sized molded product can be obtained using an inexpensive mold, so it has the possibility of being used in a wide range of applications.
しかしながら、重合体成型物を特に大型の成型物に実用
化するにあたっては、いくつかの改良が必要なことが判
ってきた。その内で大なるものは耐衝撃性、耐熱性１重
合反応速度の調節をあげることが出来る。However, it has been found that some improvements are necessary in putting polymer moldings into practical use, especially in large-sized moldings. Among these, the major ones are impact resistance, heat resistance, and adjustment of polymerization reaction rate.
即ち、大型の成型物は、その剛性を保持しつつ、耐衝撃
性の良好なものが必要である。ジシクロペンタジェン単
独の重合体成型物の場合、常温でのノツチ付アイゾツト
衝撃強度は一般に１０ｋＩｒｃｚ／（２）以下であり、
かかる成型品の場合少なくとも、２０ｋｇ（２）／（２
）以上か好ましくは、４０ ｋｔ■／（２）以上が望ま
れる。また耐熱性においてら、ジシクロペンタジェン単
独の重合体成型物の場合、軟化点が９０”Ｃ前後である
が、１００℃以上であることが望まれる。That is, large-sized molded products need to have good impact resistance while maintaining their rigidity. In the case of a polymer molded product containing dicyclopentadiene alone, the notched Izot impact strength at room temperature is generally 10 kIrcz/(2) or less,
In the case of such molded products, at least 20 kg(2)/(2
) or more, preferably 40 kt/(2) or more. In addition, in terms of heat resistance, in the case of a polymer molded product containing only dicyclopentadiene, the softening point is around 90''C, but it is desirable that it be 100''C or higher.
一方、大型成型品をつくる場合、液状のモノマーが型内
に充填されるまでの間に固化してしまうと不部会であり
、充填期間に対応する誘導期間を有するようになってい
ることが好ましい。On the other hand, when making large molded products, it would be a waste if the liquid monomer solidified before being filled into the mold, so it is preferable to have an induction period corresponding to the filling period. .
ところで剛性を保持しながらの耐ｍ撃性の改良には、モ
ノマーに可溶性のエラスｌ〜メリックなポリマーを添加
することが効果があることが判っている。ところが、か
かるポリマーについてはその種類によって、得られる成
型物の耐熱性が大きく影響されることか判ってきた。By the way, it has been found that adding a soluble elastomeric polymer to the monomer is effective in improving impact resistance while maintaining rigidity. However, it has been found that the heat resistance of the resulting molded product is greatly affected by the type of such polymer.
一方、上記の重合開始時間の調節には、エステルやエー
テル等のルイスペースである極性化合物の添加が効果が
あることが判っている。ところがかかる極性化合物は、
重合体成型物中にそのまま残留することになるなめ、得
られた重合体の耐熱性を損う等の問題を惹起することが
判ってきた。On the other hand, it has been found that addition of a polar compound such as ester or ether, which is a Lewis space, is effective in controlling the above-mentioned polymerization initiation time. However, such polar compounds
It has been found that since it remains as it is in the polymer molding, it causes problems such as impairing the heat resistance of the obtained polymer.
そこで本発明者は、耐衝撃性を改良するためのエラスト
マーとして、耐衝撃性ばかりでなく、耐熱性をも改良し
えて、かつ極性基を有することにより、重合開始調節作
用をも、加え得るものが見出し得ないかと考え、鋭意検
討の結果、本発明に到達したものである。Therefore, the present inventors have developed an elastomer for improving impact resistance, which can improve not only impact resistance but also heat resistance, and can also add a polymerization initiation regulating effect by having a polar group. As a result of intensive research, we have arrived at the present invention.
Ｃ９発明の構成
本発明者は、エチレン−酢酸ビニル共重合体及びエチレ
ン−アクリル酸エステル共重合体に着目したものである
。かかるポリマーは、ゴムや熱可塑性エラストマー或は
、柔軟な熱可塑性プラスチックス用として、広範な共重
合範囲、重合度のものが工業的に生産され入手の容易な
ポリマーといえる。C9 Structure of the Invention The present inventor has focused on ethylene-vinyl acetate copolymers and ethylene-acrylic acid ester copolymers. Such polymers can be industrially produced in a wide range of copolymerization ranges and degrees of polymerization for use in rubber, thermoplastic elastomers, or flexible thermoplastic plastics, and can be said to be readily available polymers.
かかるポリマーは主鎖が化学的に安定な飽和炭化水素鎖
よりなり、かつ側鎖に弱いルイスペースであるエステル
基を含有しており、従って、上記の如き改良に使用出来
る可能性に着目したがさらに詳細な検討の結果、特定の
エチレン含有範［ｍのものがその目的を達しうろことを
見出し得たものである。The main chain of such polymers is composed of chemically stable saturated hydrocarbon chains, and the side chains contain ester groups, which are weak Lewis spaces. Therefore, we focused on the possibility that they could be used for the above-mentioned improvements. As a result of more detailed study, it was discovered that a specific ethylene content range [m] would most likely achieve the purpose.
即ち、本発明は下記の発明を包古する。That is, the present invention encompasses the following inventions.
（１）メタセシス重合性モノマーを、メタセシス重合触
媒系の共存下に重合と成型とを同時におこなって得られ
る重合体成型物において、エチレン７０〜９５モル％、
酢酸ビニル又は低級アルキルアクリレート３０〜５モル
％より実質的になるポリマーであって、かつジシクロペ
ンタジェン９０重量％、エチリデンノルボルネン１０重
量％よりなる混合溶媒に対し、３０℃において少なくと
も５重量％は実質的に溶解するものを少なくとも一種該
メタセシス重合性モノマーに添加して得られた重合体成
型物。(1) In a polymer molded product obtained by simultaneously polymerizing and molding a metathesis polymerizable monomer in the coexistence of a metathesis polymerization catalyst system, 70 to 95 mol% of ethylene,
A polymer consisting essentially of 30 to 5 mol% of vinyl acetate or lower alkyl acrylate, and at least 5% by weight at 30°C in a mixed solvent consisting of 90% by weight of dicyclopentadiene and 10% by weight of ethylidene norbornene. A polymer molded product obtained by adding at least one substance that is substantially soluble to the metathesis polymerizable monomer.
（２） メタセシス重合性モノマーをメタセシス重合
触媒系の共存下に重合と成型を同時におこなう重合体成
型物の製造方法において、エチレン７０〜９５モル％、
酢酸ビニル又は低級アルキルアクリレート３０〜５モル
％より実質的になるポリマーであって、かつジシクロペ
ンタジェン９０重量％、エチリデンノルボルネン１０重
量％よりなる混合溶媒に対し、３０℃において少なくと
も５重量％は、実質的に溶解するものを少なくとも一種
該メタセシス重合性モノマーに添加しておこなうことを
特徴とする重合体成型物の製造方法。(2) In a method for producing a polymer molded product in which polymerization and molding of a metathesis polymerizable monomer are simultaneously performed in the coexistence of a metathesis polymerization catalyst system, 70 to 95 mol% of ethylene;
A polymer consisting essentially of 30 to 5 mol% of vinyl acetate or lower alkyl acrylate, and at least 5% by weight at 30°C in a mixed solvent consisting of 90% by weight of dicyclopentadiene and 10% by weight of ethylidene norbornene. A method for producing a polymer molded article, characterized in that at least one substance that is substantially soluble is added to the metathesis-polymerizable monomer.
（３１ａ）メタセシス重合触媒系の触媒成分を含むメタ
セシス重合性モノマーめ反応性溶液（溶液Ａ）および
ｂ）メタセシス重合触媒系の活性化成分を含むメタセシ
ス重合性モノマーの反応性溶液（溶液Ｂ）
より少なくともなる反応性溶液の組合せにおいて、これ
らの溶液Ａ及び溶液Ｂの少なくとも一方に、エチレン７
０〜９５モル％、酢酸ビニル又は低級アルキルアクリレ
ート３０〜５モル％より実質的になるポリマーであって
、かつジシクロペンタジェン９０重量％、エチリデンノ
ルボルネン１０重量％よりなる混合溶媒に対し、３０℃
において少なくとも５重量％は、実質的に溶解するもの
を少なくとも一種含有せしめてなる反応性溶液の組合せ
。(31a) A reactive solution of metathesis polymerizable monomers containing a catalyst component of a metathesis polymerization catalyst system (solution A) and b) A reactive solution of metathesis polymerizable monomers containing an activating component of a metathesis polymerization catalyst system (solution B) In the combination of at least one reactive solution, at least one of these solutions A and B contains ethylene 7
0 to 95 mol%, vinyl acetate or lower alkyl acrylate 30 to 5 mol%, and a mixed solvent consisting of 90% by weight of dicyclopentadiene and 10% by weight of ethylidene norbornene at 30°C.
A combination of reactive solutions containing at least 5% by weight of at least one substance that is substantially soluble in the combination.
エチレンが７０モル％未満、酢酸ビニル３０モル％以上
の共重合体は、溶解性は良好であるが、重合の遅延効果
が大きくなり過ぎることを得られた重合体の耐熱性改良
の効果が充分でない。A copolymer containing less than 70 mol% of ethylene and 30 mol% or more of vinyl acetate has good solubility, but the polymerization retardation effect becomes too large and the effect of improving the heat resistance of the obtained polymer is insufficient. Not.
またエチレンが７０モル％未満、アクリル酸エステル３
０モル％以上のものについてもモノマーに対して溶解性
が悪くなる傾向がありかつ重合遅延効果等で同じ傾向が
みちれ好ましくない。Also, ethylene content is less than 70 mol%, acrylic acid ester 3
If the amount is 0 mol % or more, the solubility in the monomer tends to deteriorate, and the same tendency occurs due to polymerization retardation effects, etc., which is not preferable.
一方、両方の共重合モノマーに対して、エチレンが９５
モル％を超すと結晶性が大きくなりすぎ、溶解性が不充
分となり＃＃衝撃性の改良も充分でなくなる。On the other hand, for both copolymerized monomers, ethylene is 95
If it exceeds mol%, the crystallinity becomes too large, the solubility becomes insufficient, and the improvement in impact resistance becomes insufficient.
従って、上記したエチレンの含有範囲のものが、効果が
大きいことが判ったものである。特に、エチレン７５〜
９５モル％の範囲のものが好ましい、アクリル酸エステ
ルとしては、炭素数３以下の低級アルキルエステルのう
ちで、特にエチルエステルが好ましい。Therefore, it has been found that those containing ethylene in the above-mentioned range are highly effective. In particular, ethylene 75~
Among the lower alkyl esters having 3 or less carbon atoms, ethyl ester is particularly preferred as the acrylic ester, which is preferably in the range of 95 mol%.
上述した如き組成のエチレン共重合体はプラスチックと
して押し出し、射出成型用、熱可塑性エラストマー、ゴ
ム用、ホットメルト接着剤用、感圧粘着剤ブレンド用等
、広範な用途に用いられており、その用途に応じてエチ
レンの組成ばかりでなく、重合度についても、広範なも
のが工業的に利用可能である。Ethylene copolymers having the above-mentioned composition are extruded as plastics and used in a wide range of applications, including injection molding, thermoplastic elastomers, rubber, hot melt adhesives, and pressure-sensitive adhesive blends. A wide range of ethylene compositions and degrees of polymerization can be used industrially depending on the requirements.
かかる本発明に用いる共重合体の重合度と添加量につい
ては上述した３点の改良のどれに特に主眼をおいて改良
するかによって好適な範囲を選ぶことが出来る。Regarding the degree of polymerization and the amount added of the copolymer used in the present invention, a suitable range can be selected depending on which of the above-mentioned three points of improvement is particularly focused on.
即ち、耐衝撃性の改良に主眼をおく場合は、エチレン含
量低目でかつ高重合度のもの用いるのが好ましく、逆に
耐熱性に重点をおく場合にはエチレン含量の高目のもの
が好ましい、また重合度と添加量は反応性溶液の粘度に
影響するがかかる粘度は成型プロセスとの相関によって
好適な範囲がきまっているという相関関係にある０例え
ば、かかる反応性溶液を反応射出成型型に用いる場合に
は、注入温度において２００〜１０００ｃｐｓ特に３０
０〜５００Ｃ１］Ｓぐらいの粘度が好ましく、従って、
好適な組成と重合度が決まると、添加量は好適な粘度を
与える量が用いられるのが一般である。That is, when the main focus is on improving impact resistance, it is preferable to use a material with a low ethylene content and a high degree of polymerization; conversely, when the focus is on heat resistance, a material with a high ethylene content is preferable. In addition, the degree of polymerization and the amount added affect the viscosity of the reactive solution, but the viscosity is correlated with a suitable range depending on the relationship with the molding process.For example, when such a reactive solution is put into a reaction injection molding mold, When used, 200 to 1000 cps at the injection temperature, especially 30
A viscosity of about 0 to 500C1]S is preferred, and therefore,
Once a suitable composition and degree of polymerization are determined, the amount to be added is generally determined to provide a suitable viscosity.
さらに、重合度の低いものを用いたため、性能改良上の
必要量を添加しても、粘度が不足する場合には、後述す
る如き他のエラストマー等の可溶性ポリマーを添加する
ことも出来る。Furthermore, since a material with a low degree of polymerization was used, if the viscosity is insufficient even after adding the required amount for performance improvement, soluble polymers such as other elastomers as described below may be added.
一般に、添加量は、２〜３０ｗｔ％の範囲が用いられ、
特に３〜２０ｗｔ％の範囲が好適に用いられる。Generally, the amount added is in the range of 2 to 30 wt%,
In particular, a range of 3 to 20 wt% is preferably used.
なお、かかる共重合体は実質的にエチレン及び酢酸ビニ
ル或はアクリル酸エステルよりなるが、それ以外の共重
合モノマーをかかる共重合体の特徴を損わない範囲で、
含有しているものも、本発明において用いることが出来
る。The copolymer essentially consists of ethylene and vinyl acetate or acrylic acid ester, but other copolymer monomers may be added to the extent that the characteristics of the copolymer are not impaired.
Those containing the same can also be used in the present invention.
また、かかる可溶性共重合体とともに重合体成型物を形
成するために用いられるメタセシス重合性モノマーとし
ては、メタセシス重合によってバルク重合して成型物を
与え得るものであれば、いかなるものでも差支えないが
一般にメタセシス重合性シクロアルケン基を１〜４個含
有゛するものが用いられる。特にノルボルネン型の結合
を有するものが好ましい、特に炭化水素系のものが好ま
しく、具体例としては、ジシクロペンタジェン、ジヒド
ロジシクロペンタジェン、シクロペンタジェン−メチル
シクロペンタジェン共二量体、５−エチリデンノルボル
ネン、５−ビニルノルボルネン。Furthermore, the metathesis-polymerizable monomer used to form a polymer molded product together with such a soluble copolymer may be any monomer as long as it can be bulk-polymerized by metathesis polymerization to give a molded product. Those containing 1 to 4 metathesis-polymerizable cycloalkene groups are used. Particularly preferred are those having a norbornene type bond, and particularly preferred are those having a hydrocarbon type bond. -ethylidenenorbornene, 5-vinylnorbornene.
ノルボルネン、５−シクロへキセニルノルボルネン、１
．４−メタノ−１，４，４ａ、５，６，７，８．８ａ−
オクタヒドロナフタレン、 １，４，５．８−ジメタノ
−１，４，４ａ。Norbornene, 5-cyclohexenylnorbornene, 1
．． 4-methano-1,4,4a,5,6,7,8.8a-
Octahydronaphthalene, 1,4,5.8-dimethano-1,4,4a.
５、６．７．８．８ａ−オクタヒドロナフタレン、６−
エチリデン−１，４，５，８−ジメタノ−１，４，４ａ
、 ５．７．８．８ａ−ヘプタヒドロナフタレン、 １
，４，５．８−ジメタノ−１，４，４ａ、５，８，８ａ
−へキサヒドロナフタレン、トリシクロ［８，２，１，
０］ トリデカ−５，１１−ジエン、ノルボルナジェン
、５−フェニルノルボルネン、エチレンビス（５−ノル
ボルネン）などをあげることができる、就中特にジシク
ロペンタジェン或いはそれを５０％以上より好ましくは
７０％以上含有するモノマー混合物が好ましい。5, 6.7.8.8a-octahydronaphthalene, 6-
Ethylidene-1,4,5,8-dimethano-1,4,4a
, 5.7.8.8a-heptahydronaphthalene, 1
,4,5.8-dimethano-1,4,4a,5,8,8a
-hexahydronaphthalene, tricyclo[8,2,1,
0] Trideca-5,11-diene, norbornadiene, 5-phenylnorbornene, ethylene bis(5-norbornene), etc., among others, dicyclopentadiene or 50% or more, preferably 70% or more of dicyclopentadiene. Monomer mixtures containing are preferred.
また必要に応じて酸素、窒素などの異種元素を有する極
性基を含むメタセシス重合性モノマーも用いることがで
きる。かようなメタセシス重き性モノマーもノルボルネ
ン補遺単位を有するものが好ましくかつ極性基としては
、エステル基、エーテル基、シアノ基或いはＮ−置換イ
ミド基などが好ましい。Further, if necessary, a metathesis polymerizable monomer containing a polar group having a different element such as oxygen or nitrogen can also be used. Such a metathesis-heavy monomer preferably has a norbornene supplementary unit, and the polar group is preferably an ester group, an ether group, a cyano group, or an N-substituted imide group.
かかる極性基はルイスペースとして、本発明における共
重合体側鎖のエステル基とともに、メタセシス重合反応
の開始を調節する作用を有しており、また生成した重合
体成型物中に極性基を導入しうる効果もあり、さらにノ
ルボルネン化重合体（ワ）の種類によってはその溶解性
を増す効果らありうるので、それらの作用の必要性に応
じて好適に用いられる。Such a polar group, as Lewis space, has the function of regulating the initiation of the metathesis polymerization reaction together with the ester group of the side chain of the copolymer in the present invention, and can also introduce a polar group into the formed polymer product. Depending on the type of norbornened polymer (wa), it may even have the effect of increasing its solubility, so it is suitably used depending on the necessity of the action.
かかる極性モノマーとしては、（５−ノルボルネニル）
メチル−フェニルエーテル、ビス［（５−ノルノルネニ
ル）メチル］エーテル、５−メトキシカルボニルノルボ
ルネン、５−メトキシカルボニル−５−メチル−ノルボ
ルネン、５［（２−エチルへキシロキシ）カルボニル］
ノルボルネン、エチレン−ビス（５−ノルボルネンカル
ボキシレート）、５−シアノノルボルネン、６−ジアツ
ー１゜４．５．８−ジメタノ−１，４，４ａ、５，６，
７，８．８ａ−オクタヒドロナフタレン、Ｎ−プチルナ
ディク酸イミド。Such polar monomers include (5-norbornenyl)
Methyl-phenyl ether, bis[(5-nornornenyl)methyl]ether, 5-methoxycarbonylnorbornene, 5-methoxycarbonyl-5-methyl-norbornene, 5[(2-ethylhexyloxy)carbonyl]
Norbornene, ethylene-bis(5-norbornenecarboxylate), 5-cyanonorbornene, 6-diatwo 1゜4.5.8-dimethano-1,4,4a, 5,6,
7,8.8a-Octahydronaphthalene, N-butylnadic imide.
５−（４−ピリジル）−ノルボルネンなどを挙げること
が出来る。Examples include 5-(4-pyridyl)-norbornene.
また、難燃性や軟化温度の向上のために含ハロゲン・メ
タセシス重合性モノマーも用いることが出来る。かかる
モノマーの具体例としては、５−クロロノルボルネン、
５−ブロモノルボルネン。Furthermore, halogen-containing metathesis polymerizable monomers can also be used to improve flame retardancy and softening temperature. Specific examples of such monomers include 5-chloronorbornene,
5-bromonolbornene.
５．５．６−ドリクロロノルボルネン、 ５，５，６．
６−チトラクロルノルボルネン、５．６−ジブロモノル
ボルネン、５−（２，４−ジブロモフェニル）ノルボル
ネンなどを挙げることが出来る。5.5.6-drichloronorbornene, 5,5,6.
Examples include 6-titrachlornorbornene, 5,6-dibromonorbornene, and 5-(2,4-dibromophenyl)norbornene.
上述した如きメタセシス重合性モノマーはすべてメタセ
シス重合触媒を阻害する不純物の含有量は極力小さいも
のが好ましい。All of the metathesis-polymerizable monomers mentioned above preferably have as low a content of impurities that inhibit the metathesis-polymerization catalyst as possible.
本発明で重合体成型物を得るのに用いられるメタセシス
重合触媒系は、知られているように一般に触媒成分と活
性化剤成分の二成分からなる。As is known, the metathesis polymerization catalyst system used to obtain the polymer molded product in the present invention generally consists of two components: a catalyst component and an activator component.
しかしながら、メタセシス重合反応は、一般に発熱反応
であり、−旦重合が開始されると、系がさらに加熱され
反応が加速されることになる。However, the metathesis polymerization reaction is generally an exothermic reaction, and once the polymerization starts, the system is further heated and the reaction is accelerated.
そこで前述の如く、モノマーと触媒成分より主としてな
る溶液（溶液Ａ）と、モノマーと活性他剤成分より主と
してなる溶液（溶液Ｂ）との二つの溶液を予め調製して
おき、衝突混合（ＲＩＭ方式）やスタティックミキサー
などの手段によって急速混合し直ちに鋳型に注入し、賦
形した後、型内で硬化させる方法が好適に使用出来る。Therefore, as mentioned above, two solutions were prepared in advance: a solution consisting mainly of monomers and catalyst components (solution A), and a solution consisting mainly of monomers and other active agent components (solution B), and collisional mixing (RIM method) was carried out. ) or a static mixer, the mixture is immediately poured into a mold, shaped, and then hardened within the mold.
その場合、モノマーの組成は、両液で同じであることは
必要でなく、モノマーの機能によって任意に変更するこ
とが出来る。また前記共重合体の添加量を両液によって
変えることもできるが、一般に反応射出成型法において
は、両液の粘度が等しい方がミキシングが効果的に行わ
れるのでその方がより好ましい。In that case, the composition of the monomers does not need to be the same in both liquids, and can be arbitrarily changed depending on the function of the monomers. Although the amount of the copolymer added can be varied depending on the two solutions, it is generally preferable in the reaction injection molding method that the two solutions have the same viscosity, since mixing can be performed more effectively.
もう一つの重合体成型物を得る方法として、前述の如く
メタセシス重合の開始を遅延する調節剤として働くルイ
スペース、或いはかかるルイスペースを有するメタセシ
ス重合性モノマーを加えて、重合開始を遅延し、予め生
成したプレミックスを型内に流入する方法、即ち、レジ
ン・インジェクションの方式もとることが出来る０本発
明の共重合体のエステル＠鎖はかかる遅延効果をも発揮
しうろことは前述のとおりである。この場合は型内にガ
ラス繊維マットなどを予め付置しておくことにより、繊
維強化成型物を得るのに有利である。Another method for obtaining a polymer molded product is to delay the initiation of polymerization by adding Lewis space, which acts as a regulator to delay the initiation of metathesis polymerization, or a metathesis-polymerizable monomer containing such Lewis space, as described above. A method of flowing the generated premix into a mold, that is, a resin injection method can also be used.As mentioned above, the ester chain of the copolymer of the present invention can also exhibit such a retarding effect. be. In this case, it is advantageous to place a glass fiber mat or the like in the mold in advance to obtain a fiber-reinforced molded product.
ＲＩＭ方式においても、かかるガラス繊維マットを型内
において用いることも出来る。In the RIM method, such a glass fiber mat can also be used in the mold.
メタセシス重合触媒系における触媒成分としてはタング
ステン、レニウム、タンタル、モリブデンなどのハライ
ドなどの塩類が用いられるが、特にタングステン化合物
が好ましい、かかるタングステン化合物としては、タン
グステンハライド。Salts such as halides such as tungsten, rhenium, tantalum, and molybdenum are used as catalyst components in the metathesis polymerization catalyst system, and tungsten compounds are particularly preferred.Tungsten halides are particularly preferred as such tungsten compounds.
タングステンオキシハライドなどが好ましくより具体的
には、タングステンへキサクロライド、タングステンオ
キシクロライドなどが好ましい、また、有機アンモニウ
ムタングステン酸塩またはモリブデン酸塩なども用いる
ことが出来る。かがるタングステンハライド系化合物は
、直接モノマーに添加すると、直ちにカチオン重合を開
始することが判っており好ましくない、従ってかかるタ
ングステンハライド系化合物は不活性溶媒例えばベンゼ
ン、トルエン、クロロベンゼン等に予め懸濁し、少量の
アルコール系化合物またはフェノール系化合物を添加す
ることによって可溶化させて使用するのが好ましい。Tungsten oxyhalide is preferable, and more specifically, tungsten hexachloride, tungsten oxychloride, etc. are preferable, and organic ammonium tungstates, molybdates, etc. can also be used. It is known that when a tungsten halide compound is added directly to a monomer, it immediately starts cationic polymerization, which is undesirable. It is preferable to use it by solubilizing it by adding a small amount of an alcoholic compound or a phenolic compound.
さらに、上述した如き、好ましくない重合を予防するな
めにタングステン化合物１モルに対し、約１〜５モルの
ルイス塩基またはキレート化剤を添加することが好まし
い、かかる添加剤としてはアセチルアセトン、アセト酢
酸アルキルエステル類、テトラヒドロフラン、ベンゾニ
トリルなどを挙げることができる４本発明で用いられる
共重合用極性モノマーは、前述の如く、そのものがルイ
ス塩基である場合があり、上記の如き化合物を特に加え
なくてもその作用を有している場合もある。Furthermore, in order to prevent undesirable polymerization as mentioned above, it is preferable to add about 1 to 5 mol of a Lewis base or a chelating agent to 1 mol of the tungsten compound. Examples of such additives include acetylacetone, alkyl acetoacetate, etc. As mentioned above, the polar monomer for copolymerization used in the present invention may include esters, tetrahydrofuran, benzonitrile, etc., and may itself be a Lewis base. In some cases, it has that effect.
かくして、触媒成分を含むモノマー溶液（溶液Ａ）は、
実用上充分な安定性を有することになる。Thus, the monomer solution containing the catalyst component (solution A) is
It has sufficient stability for practical use.
一方メタセシス重合触媒系における活性他剤成分は、周
期律表第１〜第■族の金属のアルキル化物を中心とする
有機金属化合物、特にテトラアルキルスズ、トリアルキ
ル水素錫、トリアリール水素錫、アルキルアルミニウム
化合物、アルキルアルミニウムハライド化合物が好まし
く、具体的には、塩化ジエチルアルミニウム、ジ塩化エ
チルアルミニウム、トリオクチルアルミニウム、ジオク
チルアルミニウムアイオダイド、テトラブチル鍋などを
挙げることができる。これら活性他剤成分としての有機
金属化合物を、原料単量体に溶解することにより、もう
一方の溶液（溶液Ｂに相当する）が形成される。On the other hand, the active component in the metathesis polymerization catalyst system is an organometallic compound mainly containing alkylated products of metals of Groups 1 to 2 of the Periodic Table, especially tetraalkyltin, trialkylhydrogentin, triarylhydrogentin, and alkyltin. Aluminum compounds and alkyl aluminum halide compounds are preferred, and specific examples include diethyl aluminum chloride, ethyl aluminum dichloride, trioctyl aluminum, dioctyl aluminum iodide, and tetrabutyl pot. The other solution (corresponding to solution B) is formed by dissolving the organometallic compound as the active ingredient in the raw material monomer.
本発明においては、基本的に前記溶液Ａおよび溶液Ｂを
混合することによって、重合体成型物を得ることができ
るが、上記組成のままでは、重合反応が非常に速く開始
されるので、成形用鋳型に充分流れ込まない間に硬化が
起ることがあり、度々問題となる場合が多く、その防止
のために本発明の共重合体に含有されるエステル基が効
果を有しているが、場合によって、それでも不充分な場
合には、前述の如く、活性調節剤を用いるのが好ましい
。In the present invention, a polymer molded product can basically be obtained by mixing the solutions A and B, but if the above composition is used as it is, the polymerization reaction will start very quickly. Curing may occur while the copolymer of the present invention does not flow sufficiently into the mold, which is often a problem, and the ester groups contained in the copolymer of the present invention are effective in preventing this. However, if this is still insufficient, it is preferable to use an activity modifier as described above.
かかる調節剤としては、ルイス塩基類が一般に用いられ
、就中エーテル類、エステル頚、ニトリル類などが用い
られる。具体例としては安息香酸エチル、ブチルエーテ
ル、ジグライムなどをあげることが出来る。前述と同様
にルイスペース基を有する共重合モノマーを使用する場
合には、それが調節剤としての効果を発揮する場合があ
る。As such regulators, Lewis bases are generally used, among which ethers, esters, nitriles, etc. are used. Specific examples include ethyl benzoate, butyl ether, and diglyme. As mentioned above, when a copolymerizable monomer having a Lewis space group is used, it may exhibit an effect as a regulator.
メタセシス重合触媒系の使用量は例えば触媒成分として
タングステン化合物を用いる場合は、上記原料単量体に
対するタングステン化合物の比率は、モル基準で、約１
０００対１〜１５０００対１、好ましくは２０００対１
の付近でありまた、活性止剤成分はアルキルアルミニウ
ム類を用いる場合には１．Ｅ記原料単量体に対するアル
ミニウム化合物の比率は、モル基準で約１００対１〜約
２０００対〜１、好ましくは約２００対１〜約５００対
１の付近が用いられる。更に上述した如き、マスク剤や
調節剤については、実験によって上記触媒系の使用量に
応じて、適宜、調節して用いることが出来る。The amount of the metathesis polymerization catalyst system used is, for example, when a tungsten compound is used as a catalyst component, the ratio of the tungsten compound to the raw material monomer is about 1 on a molar basis.
000:1 to 15000:1, preferably 2000:1
In addition, when an alkyl aluminum is used as the active inhibitor component, the value is close to 1. The ratio of the aluminum compound to the raw material monomers in E is about 100:1 to about 2000:1, preferably about 200:1 to about 500:1 on a molar basis. Further, as described above, the masking agent and the regulating agent can be appropriately adjusted and used depending on the amount of the catalyst system to be used through experiments.
本発明により架橋重合体成型物には、実用に当って、そ
の特性を改良または維持するために、さらに各種添加剤
を配合することができる。かかる添加剤としては、充填
材、含量、酸化防止剤、光安定剤、Ｂ燻化剤、高分子改
良剤、ＴＡ留モノマー減少剤などがある。このような添
加剤は、本発明の重合体が形成されて後は添加すること
が不可能であるから、添加する場合には予め前記しな原
料溶液に添加しておく必要がある。In practical use, various additives can be added to the crosslinked polymer molded product of the present invention in order to improve or maintain its properties. Such additives include fillers, fillers, antioxidants, light stabilizers, B fumigants, polymer modifiers, TA residue monomer reducers, and the like. Since such additives cannot be added after the polymer of the present invention is formed, it is necessary to add them to the above-mentioned raw material solution in advance.
その最も容易な方法としては、前記溶ＭＡおよび溶液Ｂ
のいずれか又は両方に前もって添加しておく方法をあげ
ることが出来るが、その場合、その液中の反応性の強い
触媒成分や、活性止剤成分と実用上さしつかえある程度
には反応せず、かつ重合を阻害しないものでなくてはな
らない、どうしても、その反応がさけえないが共存して
も、重合は実質的に阻害しないものの場合は、単量体と
混合して、第三液を調整し、重合直前に、混合使用する
ことも出来る。また、固体の充填剤の場合であって、両
成分が混合されて、重合反応を開始する直前あるいは重
合をしながら、その空隙を充分にうずめ得る形状のもの
については、成形用モールド中に、充填しておくことも
可能である。The easiest method is to use the solution MA and solution B.
One method is to add it in advance to either or both of the above, but in that case, it does not react with the highly reactive catalyst component or deactivator component in the liquid to a practical extent, and It must be something that does not inhibit polymerization. If the reaction cannot be avoided, but it does not substantially inhibit polymerization even if it coexists, mix it with the monomer and prepare the third liquid. They can also be mixed and used immediately before polymerization. In the case of a solid filler, in the case of a filler in a shape that can sufficiently fill the voids immediately before starting the polymerization reaction or during polymerization when both components are mixed, in the mold for forming the filler, It is also possible to fill it.
添加剤としての補強材又は充填剤は、曲げモジュラスを
向上するのに効果がある。かかるものとしてはガラス繊
維、雲母、カーボンブラック、ウオラストナイトなどを
あげることが出来る。これらを、いわゆるシランガプラ
ーなどによって表面処理したものも好適に使用できる。Reinforcements or fillers as additives are effective in improving the flexural modulus. Examples of such materials include glass fiber, mica, carbon black, and wollastonite. Those surface-treated with a so-called silanga puller can also be suitably used.
また、本発明の架橋重合体成型物は、酸化防止剤を添加
しておくことが好ましく、そのためフェノール系又はア
ミン系の酸化防止剤を予め溶液中に加えておくことが望
ましい、これら酸化防止剤の具体例としては、２．６−
ｔ−ブチル−ｐ−クレゾール、Ｎ、Ｎ’−ジフェニル−
ｐ−フェニレンジアミン、テトラキス［メチレン（３，
５−ジ−ｔ−ブチル−４−ヒドロキシシンナメート）］
メタンなどがあげられる。Further, it is preferable to add an antioxidant to the crosslinked polymer molded product of the present invention, and therefore it is desirable to add a phenol-based or amine-based antioxidant to the solution in advance. As a specific example, 2.6-
t-Butyl-p-cresol, N,N'-diphenyl-
p-phenylenediamine, tetrakis[methylene (3,
5-di-t-butyl-4-hydroxycinnamate)]
Examples include methane.
本発明においては、前述の如き、エチレン共重合体の添
加によって耐衝撃性、耐熱性の改良と重合開始時間調節
を達成しようとするものであるが、前述の如く、粘度の
調節やその他を目的として、一般の可溶性エラストマー
類をら、併用として用いることも出来る。In the present invention, as mentioned above, the purpose is to improve impact resistance and heat resistance and to adjust the polymerization initiation time by adding the ethylene copolymer. As such, general soluble elastomers can also be used in combination.
かかる目的に用いられるエラスト°７−としては、スチ
レン−ブタジェン−スチレントリブロックゴム、スチレ
ン−イソプレン−スチレントリブロックゴム、ポリブタ
ジェン、ポリイソプレン、ブチルゴム、エチレンプロピ
レンゴム、エチレンプロピレン−ジェンターポリマーな
どをあげることが出来る。Examples of elastomers used for this purpose include styrene-butadiene-styrene triblock rubber, styrene-isoprene-styrene triblock rubber, polybutadiene, polyisoprene, butyl rubber, ethylene-propylene rubber, ethylene-propylene-genterpolymer, and the like. I can do it.
また、本発明においては残留モノマーが成型物中に、多
くなると軟化点が下がるばかりでなく、特有の臭いを発
する場合があり、出来るだけ残留モノマーが少ないこと
が好ましい。かがる残留モノマーを減少せしめるため添
加剤として、α、α。Furthermore, in the present invention, if the amount of residual monomer in the molded product increases, it not only lowers the softening point but also may emit a characteristic odor, so it is preferable to have as little residual monomer as possible. α, α as additives to reduce residual monomers.
α−トリクロルトルエン、ＬＷ−ジクロルジフェニルメ
タン、フタル酸クロライド、安息香酸無水物、ベンゼン
スルホン酸クロライド、オキシ塩化リン等のハライド類
や酸無水物類を極く、少量添加することが出来る。Very small amounts of halides and acid anhydrides such as α-trichlorotoluene, LW-dichlorodiphenylmethane, phthalic chloride, benzoic anhydride, benzenesulfonic acid chloride, and phosphorus oxychloride can be added.
本発明の架橋重合体成型物は、前記した如く、重合成型
とを同時に行うことによって製造される。The crosslinked polymer molded product of the present invention is produced by simultaneously carrying out the polymerization process as described above.
かかる成型法としては前述の如く、触媒系とモノマー混
合物を前もって、混合したプレミックスを型の中に流入
せしめるレジンインジェクション方式、触媒系を２つに
分けた溶液Ａと溶液Ｂをヘッド部で衝突混合せしめてそ
のまま型に流し込むＲＩＭ方式をとることが出来る。い
ずれの場合も鋳型（モールド）への注入圧力は比較的低
圧であることができ、従って安価な鋳型を使用すること
が可能である。As mentioned above, such molding methods include the resin injection method in which a premix of the catalyst system and monomer mixture is flowed into the mold, and the resin injection method in which the catalyst system is divided into two parts, solution A and solution B, collided at the head part. It is possible to use the RIM method in which the mixture is mixed and poured directly into a mold. In either case, the injection pressure into the mold can be relatively low, making it possible to use inexpensive molds.
また、型内の重合反応が開始されると反応熱によって型
内の温度は急速に上昇し、短時間に重合反応が終了する
。ポリウレタン−ＲＩＭの場合と異なり、モールドから
離脱は容易であり、特別の離型剤を必要としない場合が
多い。Further, when the polymerization reaction inside the mold starts, the temperature inside the mold rapidly rises due to the reaction heat, and the polymerization reaction ends in a short time. Unlike polyurethane-RIMs, they are easy to release from the mold and often do not require special mold release agents.
成型物は、表面に酸化層が出来ることによってエポキシ
やポリウレタン等の一般に使用される塗料への付着性は
良好である。The molded product has good adhesion to commonly used paints such as epoxy and polyurethane due to the formation of an oxidized layer on the surface.
かくして得られた成型物は、従来のものに比して、前述
の如く、耐衝撃性、耐熱性が改良されておりかつ重合開
始時間の調節が可能となり、自動車等を含めた各種運ａ
ｍ器の部材、電気、電子機器のハウジングなど、特に大
型の成型物に好適に使用出来る。The molded product thus obtained has improved impact resistance and heat resistance compared to conventional products, and the polymerization start time can be adjusted, making it suitable for use in various vehicles including automobiles.
It can be particularly suitably used for large-sized molded products, such as parts for electronic equipment and housings for electrical and electronic devices.
以下に実施例を掲げて本発明を詳述する。なお実施例は
説明のためであってそれに限定するものではない。The present invention will be described in detail with reference to Examples below. Note that the examples are for illustrative purposes only and are not intended to be limiting.
実施例１〜５．比較例１〜２
［主触媒源ａ液の調製〕
高純度六塩化タングステン１９．８０ ｋＫ（０，０５
モル）を乾燥トルエン９０ｍ１に窒素気流下で添加し、
ｔ−ブタノール０．９２５ ｇを５ ｍｌのトルエンに
溶解したものを加え１時間撹拌し、次いでノニルフェノ
ール１１．０５ ｋｇ （０，０５モル）及びトルエン
５１Ｉ１１よりなる溶液を添加し１時間窒素パージ下に
撹拌する。１０ｇのアセチルアセトンを混合物に加え、
副生ずる塩化水素ガスを追い出しながら窒素パージ下に
一晩撹拌を継続し、その後、一部留出したトルエンを補
い０．５Ｍタングステン含有触媒濃縮液を調製しな。Examples 1-5. Comparative Examples 1 to 2 [Preparation of main catalyst source liquid a] High purity tungsten hexachloride 19.80 kK (0.05
mol) was added to 90 ml of dry toluene under a nitrogen stream,
A solution of 0.925 g of t-butanol dissolved in 5 ml of toluene was added and stirred for 1 hour. Then, a solution consisting of 11.05 kg (0.05 mol) of nonylphenol and 51I11 of toluene was added and the mixture was kept under nitrogen purge for 1 hour. Stir. Add 10g of acetylacetone to the mixture;
Stirring was continued overnight under a nitrogen purge while purging by-produced hydrogen chloride gas, and then some of the toluene distilled off was supplemented to prepare a 0.5M tungsten-containing catalyst concentrate.
［活性止剤濃縮液の調製］
ジーｎ−オクチルアルミナムアイダイド５．７０ｇ、ト
リーｎ−オクチルアルミニウム３１．１７ ｆ 。[Preparation of activated inhibitor concentrate] 5.70 g of di-n-octylaluminum idide, 31.17 f of tri-n-octylaluminium.
ジグライム１３．４２ ｇを窒素気流下で混合し、次い
でジシクロペンタジェン（ＤＣＰ）を添加し全体で１０
０ｍ１になるように希釈し１．０Ｍアルミニウム含含有
活性化製濃縮液得た。13.42 g of diglyme was mixed under nitrogen flow, then dicyclopentadiene (DCP) was added to make a total of 10 g.
The solution was diluted to 0ml to obtain an activated concentrate containing 1.0M aluminum.
［反応性溶液の調製］
市販のＤＣＰを蒸留精製した精製ＤＣＰと表１にしめず
如きエチレン共重合体を表２にしめず如き組成の反応性
溶液Ａ、Ｂを調製した。[Preparation of Reactive Solutions] Reactive solutions A and B having the compositions shown in Table 2 were prepared by using purified DCP obtained by distilling and purifying commercially available DCP and ethylene copolymers shown in Table 1.
［重合体成型物の調製とその性質測定］かかる上記の触
媒成分溶液（溶液Ａ ） １０ｍ１ 。[Preparation of polymer molded product and measurement of its properties] 10 ml of the above catalyst component solution (solution A).
活性止剤成分溶液（溶液Ｂ ） １０１１１１を所定の
温度としな後充分窒素でおきかえたシリンジ内に各々取
り出した。かかる二つのシリンジから液を一定速度で両
方を同時に撹拌機つきガラスフラスコ内に急速撹拌下に
押し出し、急速混合した後撹拌機をあげ熱電対を押入し
、液のシリンジからの注入が終わった時点から１００℃
に到達した時間を測定した。After the activator component solution (solution B) 101111 was brought to a predetermined temperature, it was taken out into a syringe which had been sufficiently replaced with nitrogen. The liquid from these two syringes is extruded simultaneously at a constant speed into a glass flask equipped with a stirrer under rapid stirring, and after rapid mixing, the stirrer is raised and a thermocouple is pushed in. When the injection of liquid from the syringe is finished, to 100℃
The time it took to reach was measured.
さらに、固化した架橋樹脂を取り出し切片を切り出し窒
素気流中、ＴＭＡ法−針侵入モードで軟化点を測定した
。その結果を同様に表２に併記した。Furthermore, the solidified crosslinked resin was taken out, cut into sections, and the softening point was measured using the TMA method in the needle penetration mode in a nitrogen stream. The results are also listed in Table 2.
表１
表２
活性化剤の使用割合は、使用エチレン共重合体によって
１００°Ｃまでの到達時間が最短になる濃度を選んだも
のであるが共重合体のエステル含量の多くなるに従って
到達時間がながくなっており、本発明の共重合体の使用
による重合開始時間を調節する機能を有することが判る
。ただ、ニスナル含量が本発明の範囲外となる共重合体
Ｅの場合（比較例２）は、かなりアルミ濃度を増やして
も重合を開始しにくいことが判る。軟化温度は、かかる
共重合体を用いない場合に比して大巾に向上している、
即ち耐熱性が向上していることが判る。Table 1 Table 2 The ratio of the activator used was selected to be the concentration that would minimize the time required to reach 100°C depending on the ethylene copolymer used, but as the ester content of the copolymer increased, the time required to reach 100°C decreased. It can be seen that the copolymer of the present invention has a function of adjusting the polymerization initiation time. However, in the case of copolymer E (Comparative Example 2) in which the Nisnal content is outside the range of the present invention, it is found that it is difficult to initiate polymerization even if the aluminum concentration is increased considerably. The softening temperature is greatly improved compared to when such a copolymer is not used.
That is, it can be seen that the heat resistance is improved.
特にエチレン含量が８５モル％以上の場合にそれが顕著
であることが判る。It can be seen that this is particularly noticeable when the ethylene content is 85 mol% or more.
なお得られた重合体成型物を薄片にカットし、ｉｌ衝撃
性の程度を定性的に判断したが、比較例１で得られた重
合体成型物に比して、乳白色を呈しており、耐衝撃性が
向上していることが判った。The obtained polymer molding was cut into thin pieces and the degree of IL impact resistance was qualitatively judged. Compared to the polymer molding obtained in Comparative Example 1, it had a milky white color and had poor resistance. It was found that the impact resistance was improved.
Claims (3)
媒系の共存下に重合と成型とを同時におこなって得られ
る重合体成型物において、エチレン７０〜９５モル％、
酢酸ビニル又は低級アルキルアクリレート３０〜５モル
％より実質的になるポリマーであって、かつジシクロペ
ンタジエン９０重量％、エチリデンノルボルネン１０重
量％よりなる混合溶媒に対し、３０℃において少なくと
も５重量％は実質的に溶解するものを少なくとも一種該
メタセシス重合性モノマーに添加して得られた重合体成
型物。(1) In a polymer molded product obtained by simultaneously polymerizing and molding a metathesis polymerizable monomer in the coexistence of a metathesis polymerization catalyst system, 70 to 95 mol% of ethylene,
A polymer consisting essentially of 30 to 5 mol% of vinyl acetate or lower alkyl acrylate, and at least 5% by weight at 30°C in a mixed solvent consisting of 90% by weight of dicyclopentadiene and 10% by weight of ethylidene norbornene. A polymer molded product obtained by adding at least one substance that is soluble in the metathesis polymerizable monomer to the metathesis polymerizable monomer.
系の共存下に重合と成型を同時におこなう重合体成型物
の製造方法において、エチレン７０〜９５モル％、酢酸
ビニル又は低級アルキルアクリレート３０〜５モル％よ
り実質的になるポリマーであって、かつジシクロペンタ
ジエン９０重量％、エチリデンノルボルネン１０重量％
よりなる混合溶媒に対し、３０℃において少なくとも５
重量％は、実質的に溶解するものを少なくとも一種該メ
タセシス重合性モノマーに添加しておこなうことを特徴
とする重合体成型物の製造方法。(2) In a method for producing a polymer molded product in which a metathesis polymerizable monomer is simultaneously polymerized and molded in the presence of a metathesis polymerization catalyst system, from 70 to 95 mol% of ethylene and 30 to 5 mol% of vinyl acetate or lower alkyl acrylate. A polymer consisting essentially of dicyclopentadiene 90% by weight and ethylidene norbornene 10% by weight
at 30°C for a mixed solvent consisting of at least 5
The method for producing a polymer molded article is characterized in that at least one substance that is substantially soluble in weight percent is added to the metathesis polymerizable monomer.
セシス重合性モノマーの反応性溶液（溶液Ａ）および ｂ）メタセシス重合触媒系の活性化成分を含むメタセシ
ス重合性モノマーの反応性溶液（溶液Ｂ） より少なくともなる反応性溶液の組合せにおいて、これ
らの溶液Ａ及び溶液Ｂの少なくとも一方に、エチレン７
０〜９５モル％、酢酸ビニル又は低級アルキルアクリレ
ート３０〜５モル％より実質的になるポリマーであって
、かつジシクロペンタジエン９０重量％、エチリデンノ
ルボルネン１０重量％よりなる混合溶媒に対し、３０℃
において少なくとも５重量％は、実質的に溶解するもの
を少なくとも一種含有せしめてなる反応性溶液の組合せ
。(3) a) a reactive solution of metathesis polymerizable monomers containing the catalyst component of the metathesis polymerization catalyst system (solution A); and b) a reactive solution of metathesis polymerizable monomers containing the activating component of the metathesis polymerization catalyst system (solution B). ), in which at least one of these solutions A and B contains ethylene 7
0 to 95 mol%, 30 to 5 mol% of vinyl acetate or lower alkyl acrylate, and a mixed solvent of 90% by weight of dicyclopentadiene and 10% by weight of ethylidene norbornene at 30°C.
A combination of reactive solutions containing at least 5% by weight of at least one substance that is substantially soluble in the combination.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13449288A JPH01304113A (en) | 1988-06-02 | 1988-06-02 | Polymer molded item, preparation thereof and combination of reactive solutions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13449288A JPH01304113A (en) | 1988-06-02 | 1988-06-02 | Polymer molded item, preparation thereof and combination of reactive solutions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01304113A true JPH01304113A (en) | 1989-12-07 |
Family
ID=15129588
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13449288A Pending JPH01304113A (en) | 1988-06-02 | 1988-06-02 | Polymer molded item, preparation thereof and combination of reactive solutions |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01304113A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005012427A1 (en) * | 2003-08-04 | 2005-02-10 | Zeon Corporation | Polymerizable composition and formed article using the same |
-
1988
- 1988-06-02 JP JP13449288A patent/JPH01304113A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005012427A1 (en) * | 2003-08-04 | 2005-02-10 | Zeon Corporation | Polymerizable composition and formed article using the same |
| US7465773B2 (en) | 2003-08-04 | 2008-12-16 | Zeon Corporation | Polymerizable composition and formed article using the same |
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