JPS63258920A - Molded products of plasticized polymer, its production and combination with reactive solution - Google Patents
Molded products of plasticized polymer, its production and combination with reactive solutionInfo
- Publication number
- JPS63258920A JPS63258920A JP9209987A JP9209987A JPS63258920A JP S63258920 A JPS63258920 A JP S63258920A JP 9209987 A JP9209987 A JP 9209987A JP 9209987 A JP9209987 A JP 9209987A JP S63258920 A JPS63258920 A JP S63258920A
- Authority
- JP
- Japan
- Prior art keywords
- metathesis
- monomer
- solution
- catalyst system
- polymerization catalyst
- 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.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- 239000000178 monomer Substances 0.000 claims abstract description 80
- 238000005649 metathesis reaction Methods 0.000 claims abstract description 44
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 16
- 125000000962 organic group Chemical group 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 31
- 239000002994 raw material Substances 0.000 claims description 11
- 239000012190 activator Substances 0.000 claims description 9
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 23
- 239000000203 mixture Substances 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 10
- 150000003658 tungsten compounds Chemical class 0.000 abstract description 8
- 238000007334 copolymerization reaction Methods 0.000 abstract description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 2
- 238000012662 bulk polymerization Methods 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 125000001931 aliphatic group Chemical group 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 239000000969 carrier Substances 0.000 abstract 1
- 230000035939 shock Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 47
- -1 cyclic olefins Chemical class 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229920001971 elastomer Polymers 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 239000011347 resin Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 10
- 239000005060 rubber Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 230000000977 initiatory effect Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 6
- 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 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229920006037 cross link polymer Polymers 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 150000003949 imides Chemical class 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- 239000002879 Lewis base Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000007527 lewis bases Chemical class 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 150000002902 organometallic compounds Chemical group 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000005462 imide group Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012985 polymerization agent Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ZRTXDTPRRCLUQW-UHFFFAOYSA-N 1-methyl-3-(3-methyl-2-nonylphenoxy)-2-nonylbenzene Chemical compound CCCCCCCCCC1=C(C)C=CC=C1OC1=CC=CC(C)=C1CCCCCCCCC ZRTXDTPRRCLUQW-UHFFFAOYSA-N 0.000 description 1
- IBTLFDCPAJLATQ-UHFFFAOYSA-N 1-prop-2-enoxybutane Chemical compound CCCCOCC=C IBTLFDCPAJLATQ-UHFFFAOYSA-N 0.000 description 1
- IOYHPUSEPWJJIJ-UHFFFAOYSA-N 2,3,3-trichlorobicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(Cl)C2(Cl)Cl IOYHPUSEPWJJIJ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-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
- SHUGUNYYEAYLKM-UHFFFAOYSA-N 3-(methoxymethyl)heptane Chemical compound CCCCC(CC)COC SHUGUNYYEAYLKM-UHFFFAOYSA-N 0.000 description 1
- KXYDGGNWZUHESZ-UHFFFAOYSA-N 4-(2,2,4-trimethyl-3h-chromen-4-yl)phenol Chemical compound C12=CC=CC=C2OC(C)(C)CC1(C)C1=CC=C(O)C=C1 KXYDGGNWZUHESZ-UHFFFAOYSA-N 0.000 description 1
- YKZUNWLMLRCVCW-UHFFFAOYSA-N 4-[2-(4-bicyclo[2.2.1]hept-2-enyl)ethyl]bicyclo[2.2.1]hept-2-ene Chemical compound C1CC(C2)C=CC21CCC1(C=C2)CC2CC1 YKZUNWLMLRCVCW-UHFFFAOYSA-N 0.000 description 1
- AWBJNWFQMKCPDV-UHFFFAOYSA-N 5-(2-bicyclo[2.2.1]hept-5-enyloxy)bicyclo[2.2.1]hept-2-ene Chemical compound C12C(CC(C=C1)C2)OC1C2C=CC(C1)C2 AWBJNWFQMKCPDV-UHFFFAOYSA-N 0.000 description 1
- MUIADVKDDBLDLO-UHFFFAOYSA-N 5-(5-bicyclo[2.2.1]hept-2-enylmethoxymethyl)bicyclo[2.2.1]hept-2-ene Chemical compound C1C(C=C2)CC2C1COCC1C(C=C2)CC2C1 MUIADVKDDBLDLO-UHFFFAOYSA-N 0.000 description 1
- NSWBXQFNYNTZMP-UHFFFAOYSA-N 5-(butoxymethyl)bicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(COCCCC)CC1C=C2 NSWBXQFNYNTZMP-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
- DWPPXNJBRSZQHD-UHFFFAOYSA-N 5-bromobicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(Br)CC1C=C2 DWPPXNJBRSZQHD-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
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 101100321817 Human parvovirus B19 (strain HV) 7.5K gene Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 101100208721 Mus musculus Usp5 gene Proteins 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
- ZGRBQKWGELDHSV-UHFFFAOYSA-N N.[W+4] Chemical compound N.[W+4] ZGRBQKWGELDHSV-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000014443 Pyrus communis Nutrition 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-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
- FYGUSUBEMUKACF-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carboxylic acid Chemical compound C1C2C(C(=O)O)CC1C=C2 FYGUSUBEMUKACF-UHFFFAOYSA-N 0.000 description 1
- ROPXFXOUUANXRR-YPKPFQOOSA-N bis(2-ethylhexyl) (z)-but-2-enedioate Chemical compound CCCCC(CC)COC(=O)\C=C/C(=O)OCC(CC)CCCC ROPXFXOUUANXRR-YPKPFQOOSA-N 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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- BWKCCRPHMILRGD-UHFFFAOYSA-N chloro hypochlorite;tungsten Chemical compound [W].ClOCl BWKCCRPHMILRGD-UHFFFAOYSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000001925 cycloalkenes Chemical group 0.000 description 1
- NOSWQDCFTDHNCM-UHFFFAOYSA-N cyclopenta-1,3-diene;1-methylcyclopenta-1,3-diene Chemical compound C1C=CC=C1.CC1=CC=CC1 NOSWQDCFTDHNCM-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- HANKSFAYJLDDKP-UHFFFAOYSA-N dihydrodicyclopentadiene Chemical compound C12CC=CC2C2CCC1C2 HANKSFAYJLDDKP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- RYFHUGPCQBOJBL-UHFFFAOYSA-N dioctylaluminum Chemical compound CCCCCCCC[Al]CCCCCCCC RYFHUGPCQBOJBL-UHFFFAOYSA-N 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 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
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- AGQPHHBPENBBIO-UHFFFAOYSA-M iodo(dioctyl)alumane Chemical compound [I-].CCCCCCCC[Al+]CCCCCCCC AGQPHHBPENBBIO-UHFFFAOYSA-M 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 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
- 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
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 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
- 230000007017 scission Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 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
- 238000012546 transfer Methods 0.000 description 1
- JFKBLKGQCUHUHJ-UHFFFAOYSA-N tricyclo[6.2.1.02,7]undec-9-ene Chemical compound C12CCCCC2C2CC1C=C2 JFKBLKGQCUHUHJ-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (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、メタごシス重
合触媒系の存在下で鋳型内に流し込んだ後バルク重合さ
せて、重合と同時に成型も行って得る重合体成型物の耐
衝撃性の改良に関するものである。更に詳しくは、上記
のメタセシス重合の際に、長鎖の側鎖を有するメタごシ
ス重合性モノマーを共重合せしめることにより、内部可
塑化して゛、生成する重合体成型物の耐衝撃性を改良す
ることに関するものである。Detailed Description of the Invention a. Industrial Field of Application The present invention involves bulk polymerizing a metathesis-polymerizable monomer after pouring it into a mold in the presence of a metathesis-polymerization catalyst system, and molding simultaneously with the polymerization. The present invention relates to improving the impact resistance of polymer molded products obtained by this method. More specifically, during the above metathesis polymerization, by copolymerizing a metathesis-polymerizable monomer having a long side chain, internal plasticization is achieved, thereby improving the impact resistance of the resulting polymer molded product. It's about things.
ｂ、従来技術
環状オレフィンが、メタセシス重合触媒系によって開裂
し小合体を与えることは公知である。そこで、ジシクロ
ペンタジェンの如く、安価に得られ、かつ、メタセシス
重合性の基を二つ有するモノマーを、液状の状態で鋳型
に流し込みその中でバルク重合を行い、重合と成型を一
段で得る方法が提案された（例えば、特開昭５８−１−
２９０１３号公報参照）。b. Prior Art It is known that cyclic olefins can be cleaved to give small polymers by metathesis polymerization catalyst systems. Therefore, 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 and bulk polymerization is performed therein, thereby achieving polymerization and molding in one step. methods have been proposed (for example, JP-A-58-1-
(See Publication No. 29013).
かかる方法は、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覆る。た
だ、かかる大型の成形品には、耐衝撃性が良好であるこ
とが要求される用途が多い。This method has the potential to be used in a wide range of applications because large molded products can be obtained using inexpensive molds. However, there are many applications in which such large molded products are required to have good impact resistance.
歯１１品方、一般に前記の如きメタセシス重合性モノマ
ー待に架橋性モノマー１を使用した場合、４ｇられる成
型物は耐衝撃性が不足していることが多い。Generally speaking, when a crosslinking monomer is used in addition to a metathesis-polymerizable monomer as described above, the molded product produced by 4 g often lacks impact resistance.
その改善法として、モノマー中に可溶性のゴムを共存さ
ｌ、重合体成型物を形成さぼる方法や、可塑剤を加える
方法が提案されている。可塑剤を加える方法は一般に加
えた可塑剤のブルーミングの問題などがあり、満足Ｊべ
ぎ方法とは古い難い。As methods for improving this, methods have been proposed that include coexisting soluble rubber in the monomer, omitting the formation of a polymer molded product, and adding a plasticizer. The method of adding a plasticizer generally has problems such as blooming of the added plasticizer, and the satisfactory method is outdated.
一方、ゴムを添加する方法は少量の添加でも、かなり大
きな効果が認められ有効な方法といえる。On the other hand, the method of adding rubber can be said to be an effective method as even a small amount of addition can produce a considerable effect.
しかしながら、かかるゴムの添加は、モノマーの反応性
溶液の粘度を人ｒｉＪにあげることになる。一方、モノ
マーの反応性溶液をｖｉ梨型中混合しながら効率にり流
し込むためには、低粘度である必要がある。かかる方法
において、最も粘度の高いモノマー液を扱える高圧衝突
混合を用いる反応射出成型法においてし、一般に数ポイ
ズの粘度のものを扱うに止まっており、ガラス繊維など
にモノマーのプレミックスを含浸固化させるレジン・１
〜ランスフアー・モールディングなどの方法ではより低
粘度のものが要求され、ゴム成分を溶解出来る間が、非
常に限られていることが判った。即ち、一般のゴムを添
加する方法では、モノマー液の粘度の関係から添加量が
制限され、より耐衝撃性の必要な用途に対して、充分対
処出来ないという問題があることが判った。However, the addition of such rubber will significantly increase the viscosity of the reactive solution of monomer. On the other hand, in order to efficiently pour the reactive solution of the monomer into the pear mold while mixing, it is necessary to have a low viscosity. In this method, the reaction injection molding method uses high-pressure impingement mixing that can handle monomer liquids with the highest viscosity, but generally only works with a viscosity of a few poise, and involves impregnating and solidifying monomer premixes into glass fibers etc. Resin 1
- It has been found that methods such as Lansforce molding require a lower viscosity, and the time in which the rubber component can be dissolved is extremely limited. That is, it has been found that the conventional method of adding rubber has a problem in that the amount added is limited due to the viscosity of the monomer liquid, and it cannot be used satisfactorily for applications requiring higher impact resistance.
そこで、本発明者は、より耐衝撃性の大きいエラスチッ
ク性の良好な、メタセシス重合による重合体成型物を得
る方法について鋭意研究の結果、本発明に到達したもの
である。Therefore, the present inventors have conducted intensive research on a method for obtaining a polymer molded product by metathesis polymerization that has higher impact resistance and good elasticity, and as a result, has arrived at the present invention.
Ｃ１発明の構成
即ち、本発明者は、可塑剤と同様に、ある程度以上の長
鎖の側鎖を有するメタセシス重合性モノマーを選択して
、共重合せしめることににり重合体を内部可塑化すれば
、ブルーミングなど通常の可塑剤を用いた場合の如き問
題のない重合体成型物が得られることを見出し得たもの
である。C1 Structure of the Invention That is, the present inventor selected a metathesis-polymerizable monomer having a certain long side chain or more, similar to a plasticizer, and copolymerized it to internally plasticize the polymer. For example, it has been found that a polymer molded product can be obtained without the problems caused by using a common plasticizer such as blooming.
本発明は、かかる知見に基いて到達されたものであって
下記発明を包含している。The present invention has been achieved based on this knowledge and includes the following inventions.
（１）分子中にメタセシス重合性基を少なくとも１個お
よび回転を阻害されない原子を５個以上有復る１価の鎖
状有Ｉａ基を少なくとも１個有りる単量体をメタセシス
用合性モノマー中の３〜５０モル％含有覆る’ＦＡ利単
量体をメタセシス重合触媒系の存在下バルク重合Ｕしめ
ることにＪこって得られた内部可塑化された重合体成型
物。(1) A monomer having at least one metathesis-polymerizable group and at least one monovalent chain Ia group having five or more atoms whose rotation is not inhibited in the molecule is used as a metathesis-polymerizable monomer. An internally plasticized polymer molded product obtained by bulk polymerizing a FA monomer containing 3 to 50 mole % in the presence of a metathesis polymerization catalyst system.
（２）メタセシス重合性モノマーをメタセシスｍ合触媒
系の存在下バルク重合せしめて重合体成型物を１ｑる方
法において、原料単量体として、分子中にメタセシス重
合性基を少なくとも１個および回転を阻害されない原子
を５個以上有Ｊる１価の鎖状有機基を少なくとも１個有
りる単量体をメタセシス蛋合性モノマー中の３〜５０モ
ル％含有する原料単量体を使用することを特徴とする内
部可塑化された重合体成型物の製造方法。(2) In a method of bulk polymerizing metathesis-polymerizable monomers in the presence of a metathesis-m polymerization catalyst system to produce 1q of polymer moldings, the raw material monomers include at least one metathesis-polymerizable group in the molecule and rotation. It is recommended to use a raw material monomer containing 3 to 50 mol% of a monomer having at least one monovalent chain organic group having 5 or more uninhibited atoms in the metathesis polymerizable monomer. A method for producing a characterized internally plasticized polymer molding.
（３）ａ）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−Ｅツマ−の反応性溶液（溶液Ａ）
ｂ）メタはシス重合触媒系の粘性止剤成分を倉むメタｅ
シス徂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、前記
溶液Ａおよび溶液Ｂのメタセシス重合性モノマーは、両
液を合せた組成が分子中にメタセシス手合性基を少なく
とも１個および回転を阻害されない原子を５個以上有す
る１価の鎖状有機基を少なくとも１個有する単量体をメ
タセシス重合性モノマー中の３〜５０モル％含有する原
料単量体であることを特徴とする反応性溶液の組合Ｖ。(3) a) Reactive solution (solution A) of metathesis polymerizable E-sumer containing the catalyst component of the metathesis polymerization catalyst system b) Meta is the metathesis polymerization agent containing the viscous stopper component of the cis polymerization catalyst system
Reactive solutions of cis-convergent monomers (solution B) In the combination of reactive solutions consisting of at least the following, the metathesis-polymerizable monomers of solution A and solution B have metathesis-polymerizable monomers in the molecule in which the composition of both solutions is combined. A raw material monomer containing 3 to 50 mol% of a monomer having at least one monovalent chain organic group having 5 or more atoms whose rotation is not inhibited in the metathesis polymerizable monomer. A combination V of reactive solutions characterized by:
本発明で用いられる側鎖含有メタセシス重合性モノマー
は、屈曲性を有する側鎖としては、環状構造や、ＳＰ２
結合等によって、鎖部分の屈曲性が阻害された部分を除
いて、回転を阻害されない原子を少なくとも５個それも
好ましくは連続で有するものであることが必要である。The side chain-containing metathesis polymerizable monomer used in the present invention has a cyclic structure, an SP2
It is necessary to have at least 5 atoms whose rotation is not inhibited, preferably consecutively, excluding the portions where the flexibility of the chain portion is inhibited by bonding or the like.
かかる側鎖は必ずしも炭化水素鎖のみからなる必要はな
く、酸素などを含んでいても差支えない。当然のことな
がら直鎖である必要はなく、適度に分岐を含んでいた方
が、にり効率的に可塑作用を発揮出来る場合が多い。し
かし、鎖長があまりに長くなると、蒸留などによるモノ
マー精製が困難になる場合かあり、一般には１６以下が
用いられる。Such side chains do not necessarily have to consist only of hydrocarbon chains, and may contain oxygen or the like. Naturally, it does not have to be a straight chain, but if it contains a suitable amount of branching, it can often exhibit its plasticizing action more efficiently. However, if the chain length is too long, it may become difficult to purify the monomer by distillation or the like, so a chain length of 16 or less is generally used.
また、メタセシス小合性基としては、一般にノルボルネ
ン）’Ｍ ｎを有りる基、特にノルボルネン基ぞのしの
が好適である。In addition, as the metathesis small merging group, a group having norbornene)'M n is suitable, in particular a norbornene group.
また、かかるメタセシス重合性モノマー【ユ、炭化水素
に限られる訳でなく、酸素、窒素、ハロゲン等の異種元
素を含んだものでも差支えない。Furthermore, such metathesis polymerizable monomers are not limited to hydrocarbons, and may also contain different elements such as oxygen, nitrogen, and halogen.
即ら、エステル、エーテル、Ｎ−置換イミドの如き非プ
ロトン性の極性基を含有していても差支えない。かかる
ルイスペースとしての作用を右する極性基はメタセシス
重合の開始をリタードＪる作用を右しているが、かかる
作用を積極的に利用して、前記の如きプレミックス状態
にしてから、型に移づレジントランスファ一方式に適用
するように出来る。かかる方式では、より低粘度の−Ｌ
ツマー液が必要であり、前）ホの如くゴムを添加するこ
とが非常に難しくなり、本発明の方法か好適に利用出来
ることになり、従ってかかる極性基含有モノマーは両方
の機能を利用出来ることになる。That is, it may contain an aprotic polar group such as ester, ether, or N-substituted imide. The polar group that acts as a Lewis space has the effect of retarding the initiation of metathesis polymerization, and this effect is actively utilized to form the premix state as described above and then form it into a mold. It can be applied to one type of resin transfer. In such a system, lower viscosity -L
Since Zimmer's solution is required, it becomes very difficult to add rubber as in the previous example (e), so the method of the present invention can be preferably used. Therefore, such a polar group-containing monomer can utilize both functions. become.
更に、本発明の側鎖含有上ツマ−の製造には、極性基を
有する中間体を利用することによって、工業的に−こり
容易に！Ａ清しやすい場合が多い。Furthermore, by using an intermediate having a polar group, the side chain-containing upper layer of the present invention can be easily produced industrially! A: It is often easy to clean.
かかる好適な極性基を有する側鎖含有モノマーとしては
以下の如き具体例をあげることが出来る。Specific examples of such suitable side chain-containing monomers having polar groups are as follows.
（２−エチルヘキシル）ノルボルネン−５−力ルポキシ
レー１〜
（２−エチルヘキシル）５−メチルノルボルネン−５−
カルボキシレート
ノブツク酸ジブヂルエステル
ブチルノルボルネン−５−カルボキシレー１〜これらナ
デック酸や５−ノルボルネンカルボン酸などの高級アル
キルエステルを好Ｊｊ Ｌ，い例としてあげることが出
来る。これらはその前駆体であるアクリル酸，メタクリ
ル酸，マレイン酸，フマル酸の高級アルキルニスデルが
、各種樹脂の内部可塑剤用として工業的に生産されてお
り、それが利用出来るため有利に製造出来る。(2-Ethylhexyl)norbornene-5-rupoxylate 1~ (2-ethylhexyl)5-methylnorbornene-5-
Preferred examples include carboxylates, dibutyl ester, butyl norbornene-5-carboxylate, and higher alkyl esters such as nadecic acid and 5-norbornenecarboxylic acid. These can be advantageously manufactured because their precursors, higher alkyl nisdels of acrylic acid, methacrylic acid, maleic acid, and fumaric acid, are produced industrially as internal plasticizers for various resins. .
また（５−ノルボルネニル）メヂルー（イソブチル）エ
ーテル
Ｃ（１３
ｌｂ
（ｂ−ノルボルネニル）メチル−（２−エチルヘキシル
）−エーテル
Ｃｌ−１２Ｃｌ−１３
＋ＯＪ−Ｃｌ−１２−０−ＣＨｚ ＣＩ−１−ＣＨｚ０
８２ Ｃｌ−１ｚ Ｃ＋−１３（５−ノルボルネニル）
メチル−ノニルフェニルエーテル
などのエーテル含有上ツマ−；ざらに
Ｎ−ノニルノブイックイミド
Ｃ
Ｎ−へキジルナディックイミド
などのＮ−置換イミド基含有モノマー；へどの極性基Ｓ
有−Ｅツマ−をあげることが出来る。Also, (5-norbornenyl) medyl-(isobutyl) ether C (13 lb (b-norbornenyl) methyl-(2-ethylhexyl)-ether Cl-12Cl-13 +OJ-Cl-12-0-CHz CI-1-CHz0
82 Cl-1z C+-13 (5-norbornenyl)
Ether-containing monomers such as methyl-nonylphenyl ether; monomers containing N-substituted imide groups such as N-nonylnobiic imide C;
I can give you an E-summer.
炭化水素系モノマーとしては ５−へブチルノルボルネン ＣＣＣ７ト１１５ ５−ドデシルベンビンノルボルネン などをあげることが出来る。As a hydrocarbon monomer 5-Hebutylnorbornene CCC7to115 5-Dodecylbenvinnorbornene etc. can be given.
一方、側鎖含有メタセシス単含性モノマーととしに用い
る他のメタごシス重合性−Ｅツマ−としては、モノマー
液としてメタセシス小合捌：媒系にＪ。On the other hand, other metathesis-polymerizable -E-summers used as side chain-containing metathesis single-containing monomers can be used as monomer liquids for metathesis synthesis and medium systems.
す、バルク手合して剛直な成型物を与えるものてあれぽ
いかなるものでも差支えないが、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。待に
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。Any material that can be bulk-combined to give a rigid molded product may be used, but those containing 1 to 4 metathesis-polymerizable cycloalkene groups are used. Particularly preferred are those having norbornene type bonds. Hydrocarbons are particularly preferred, and a specific example is dicyclopentadiene.
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−エヂリデンノ
ルボルネン、５−ビニルノルボルネン、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
、 ５． Ｇ、 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−へブタヒドロナフタレ
ン、 １，４，５．８−ジメタノ−１，４，４ａ、５，
８．８ａ−ヘキリーヒドロナフタレン、１〜リシクロ［
８，２，１，０１１−リゾカー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出来る。就
中、特にシクロペンタジェンか好ましい。Dihydrodicyclopentadiene, cyclopentadiene
Methylcyclopentadiene codimer, 5-edylidenenorbornene, 5-vinylnorbornene, norbornene,
5-cyclohexenylnorbornene, 1,4-methano-
1,4,4a,5,6,7,8,8a-octahydronaphthalene, 1,4,5.8-dimethano-1゜4,4a
, 5. G, 7.8.8a-octahydronaphthalene, 6-ethylidene-1,4,5,8-dimethano-1,
4,4a, 5.7.8.8a-hebutahydronaphthalene, 1,4,5.8-dimethano-1,4,4a,5,
8.8a-Hexylyhydronaphthalene, 1-licyclo[
Examples include 8,2,1,011-lysocar-5.11-diene, norbornadiene, 5-phenylnorbornene, and ethylenebis(5-norbornene). Among these, cyclopentadiene is particularly preferred.
また、必要に応じて酸素、窒素などの異種元素を右する
メタセシス手合性モノマーも用いることが出来る。かか
るメタセシス重合性〜Ｅツマ・−も、ノルボルネン４１
１１造単位を右するしのが好ましく、かつ、極性基とし
ては、エステル基、エーテルＢ（。Further, if necessary, a metathesis-prone monomer containing a different element such as oxygen or nitrogen can also be used. Such metathesis polymerizability ~ E-tsuma ~ also has norbornene 41
11 structural units are preferred, and the polar group is an ester group, ether B (.
シアノ基、Ｎ−置換イミド基などが好ましい。Preferred are a cyano group and an N-substituted imide group.
かかる極性基はルイスペースとして、メタセシス重合反
応の開始速度を調節覆る作用を有してｄ５す、また生成
した重合体成型物中に（※性基を導入しうる効果も併Ｖ
て有しており、それらの作用の必要な場合に好適に用い
られる。かかる極性上ツマ−としては、（５−ノルボル
ネニル〉メブルーフェニルエーテル、ビス［（５−ノル
ボルネニル）メチル］エーテル、５−メ（・キシカルボ
ニルノルボルネン、５−メｊ〜キシカルボニルー５−メ
ヂルーノルボルネン、エチレンビス（５−ノルボルネン
カル小キシレート）、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，／Ｉａ、５
、Ｇ、７，８，８ａ−Δクタヒドロプフタレン、Ｎ−ブ
ヂルノデイツク酸イミド、５−（−１−ピリジル）−ノ
ルボルネンなどをあげることが出来る。Such polar groups function as Lewis space and have the effect of regulating the initiation rate of the metathesis polymerization reaction, and also have the effect of introducing (※) groups into the formed polymer product.
It has the following properties and is suitably used when these effects are necessary. Such polar substances include (5-norbornenyl>mebruphenyl ether, bis[(5-norbornenyl)methyl]ether, 5-meth(·xycarbonylnorbornene), 5-methycarbonyl-5-medylnorbornene, , ethylene bis(5-norbornenecal small xylate), 5-cyanonorbornene, 6-dia2-1,4,5,8-dimethano-1,4,/Ia, 5
, G, 7,8,8a-Δtahydropphthalene, N-butylnoduccinimide, 5-(-1-pyridyl)-norbornene, and the like.
また、難燃性や軟化温度の向上に含ハロゲン・メタセシ
ス重合性モノマーも用いることが出来る。Further, halogen-containing metathesis polymerizable monomers can also be used to improve flame retardancy and softening temperature.
かかる−Ｅツマ−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、 ５，５．６−トリ
クロロノルボルネン、 ５，５，０．０−テトラクロル
ノルボルネン、５．６−ジプロモノルボルネン５−（２
，４−ジブロモフェニル）ノルボルネンなどをあげるこ
とが出来る。Specific examples of such -E-summers include 5-chloronorbornene, 5-bromonorbornene, 5,5,6-trichloronorbornene, 5,5,0.0-tetrachloronorbornene, 5,6-dipromonorbornene5. −(2
, 4-dibromophenyl)norbornene, etc.
上述した如きメタ上シス重合性モノマーは全てメタはシ
ス手合触媒を阻害する不純物の含有量は、極力少ないも
のが好ましい。All the meta-cis polymerizable monomers mentioned above preferably have as low a content of impurities that inhibit the meta-cis synthesis catalyst as possible.
本発明で用いられる側鎖含有メタ上シス重合性モノマー
は仝モノマー中一般に３〜５０モル％の範囲が用いられ
る。ざらに好適な範囲については、用いられる側鎖含有
メタ上シス重合性モノマーおよび主（１４′？ｆｉ用の
メタセシス小合性モノマーの種類、および成型物の性能
によって各々異なり、それに従って最適（史用割合を実
験によって定める必要がある。一般に１寺に好適な範囲
は５〜４０モル％の範囲でおる。。The side chain-containing meta-cis polymerizable monomer used in the present invention is generally used in an amount of 3 to 50 mol % in the monomer. Roughly preferred ranges vary depending on the side chain-containing meta-cis-polymerizable monomer and the main (14'?fi) metathesis small-polymerizable monomer used, as well as the performance of the molded product, and the optimum (historical) range is determined accordingly. It is necessary to determine the proportion to be used by experiment.In general, the suitable range for one temple is 5 to 40 mol%.
本発明で、重合体成型物を（ｑるのに用いられるメタセ
シスΦ合触媒系は、一般に触媒成分と活性化成分の２成
分から形成される。In the present invention, the metathesis Φ synthesis catalyst system used to prepare the polymer molded product is generally formed from two components: a catalyst component and an activation component.
かかるメタセシス重合反応は、発熱反応であり一旦重合
が開始されると系がざらに加熱され反応が加速されるこ
とになる。Such a metathesis polymerization reaction is an exothermic reaction, and once the polymerization starts, the system is heated roughly and the reaction is accelerated.
そこで前）小の如く、モノマーと触媒成分により主とし
てなる溶液（溶液Ａ）と、モノマーと活性化剤成分より
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）化合ヤスタティックミキリーなどによ
って急速混合し、直らに鋳型に注入し、賦型した後、型
内で硬化さける方法が用いられることになる。この場合
上ツマ−の組成は両液で同じであることは必ずしも必要
でなく、モノマーの機能によって適宜変更することが出
来る。Therefore, as shown in the previous example, two solutions were prepared in advance: a solution consisting mainly of the monomer and the catalyst component (solution A), and a solution consisting mainly of the monomer and the activator component (solution B). A method is used in which the mixture is rapidly mixed using a static mixer, poured directly into a mold, shaped, and then hardened within the mold. In this case, the composition of the upper layer does not necessarily need to be the same for both liquids, and can be changed as appropriate depending on the function of the monomer.
例えば、上記極性上ツマ−を共重合して、手合開始調節
剤としての機能を用いる場合、溶液（Ｂ）に多く添加り
−る場合も可能である。また、側鎖含有メタセシス重合
性モノマーも、触媒成分や活性化剤との相互作用が懸念
される場合には、溶液（Ａ）または溶液（８）のいずれ
か一方にのみ添加しておくことも可能である。For example, when the above-mentioned polar polymer is copolymerized and used to function as a polymerization initiation regulator, it is also possible to add a large amount to the solution (B). Additionally, if there is a concern about interaction with the catalyst component or activator, the side chain-containing metathesis-polymerizable monomer may be added to either solution (A) or solution (8). It is possible.
もう一つの単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Ｖ「用す
るルイスペース或いはかかるルイスペースを有するメタ
ごシス重合上ツマ−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Ｊる方法、１なわち、
レジン・インジェクションの方式もとることが出来る。Another method for obtaining a monopolymer molded product is to add Lewis space using V as a regulator for delaying the initiation of metathesis polymerization or a metathesis polymerization agent containing such Lewis space to initiate polymerization. A method for delaying the flow of a pre-generated premix into a mold, 1.
A resin injection method can also be used.
この場合は、型内にガラス繊維マツＩ−などを予め布置
しておくことにより、ｍ組強化成型物を得るのに有利で
ある。In this case, by placing glass fiber pine I- or the like in the mold in advance, it is advantageous to obtain an m-set reinforced molded product.
特に前述の如く、本発明の側鎖含有メタセシス中合性モ
ノマーは低粘度モノマー液を要求するプレミックス法に
好適であることは前述の通りである。。In particular, as described above, the side chain-containing metathesis-neutralizing monomer of the present invention is suitable for the premix method which requires a low-viscosity monomer liquid. .
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
スデン、レニウム、タンタル、モリブデンなどのハライ
ドなどの塩基が用いられるか、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。As the catalyst component in the metathesis polymerization catalyst system, bases such as halides such as tungsden, rhenium, tantalum, and molybdenum are used, and tungsten compounds are particularly preferred. Such tungsten compounds include tungsten halide.
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、タングステンへキリクロライド、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１Ｎ！２塩なども用いることが出来る。Tungsten oxyhalide is preferable, and more specifically, tungsten helichloride, tungsten oxychloride, etc. are preferable. Also, organic ammonium tungsten 1N! 2 salts can also be used.
かかるタングステン化合物は、直接モノマーに添加Ｊる
と、直らにカチオン徂合 ゛を開始１゛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化合物は
不活性溶媒例えばベンビン、１〜ルエン、クロロベンビ
ン等に予め懸濁し、少笛のアルコール系化合物または７
１ノ一ル系化合物を添加覆ることににって可溶化さＵて
使用するのが好ましい。It is known that such tungsten compounds, when added directly to monomers, immediately start cation association, which is not preferable. Therefore, such a tungsten compound is pre-suspended in an inert solvent such as benbin, 1-toluene, chlorobenbin, etc., and mixed with a small amount of alcoholic compound or 7
It is preferable to use it after it is solubilized by adding a monol compound.
さらに、上述した如き、好ましく″ない手合を予防する
ためにタングステン化合物１ ’Ｅルに苅し、約１・〜
５モルのルイス塩基またはキレ−１〜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ヒブルアレトン
、ア（？１−酢酸アルキルエステル類、テトラヒドロフ
ラン、ベンゾニ１〜リルなどをあげることかできる。極
性モノマーを用いる場合には前述の如く、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なる。Furthermore, in order to prevent undesirable effects such as those mentioned above, a tungsten compound is added to the
Preferably, 5 moles of a Lewis base or a cleavage agent are added. Examples of such additives include ahibularetone, a(?1-acetic acid alkyl esters, tetrahydrofuran, benzoni-1-lyl, etc.). When a polar monomer is used, as described above, it may itself be a Lewis base. In some cases, the above-mentioned compounds may have the same effect even without the addition of the above-mentioned compounds.
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（）る活性化剤成分は、
周期律表第■〜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、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、１〜リオクヂルアルミ
ニウム、ジオクチルアルミニウムアイオタイド、テ１〜
ラブチル錫などをあげることができる。これら活性化剤
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Ｊ、す、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 activator component () in the metathesis polymerization catalyst system is
Organometallic compounds mainly consisting of alkylated products of metals from Groups ■ to ■ of the periodic table are preferred, particularly tetraalkyltin, alkylaluminum compounds, and alkylaluminium halide compounds, and specifically, diethylaluminum chloride, ethyl dichloride, etc. Aluminum, 1 ~ Liocdyl aluminum, dioctyl aluminum iotide, Te 1 ~
You can give things such as Labuchil tin. Another solution (corresponding to solution B) is formed by dissolving these organometallic compounds as activator components in the raw material monomer.
本発明にｄ−３いては、基本的に前記溶液Ａおよび溶液
Ｂ８混合Ｊ″ることによって、架橋重合体成型物を１７
にとができるが、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、成型用鋳型に充分流れ込まない
間に硬化が起こることがあり、度々問題となる場合が多
く、前述の如くそのために活性調節剤を用いることが好
ましい。In d-3 of the present invention, the cross-linked polymer molded product is basically prepared by mixing the solution A and the solution B8.
However, if the above composition remains as it is, the polymerization reaction will start very quickly, so hardening may occur before it has sufficiently flowed into the mold, which often causes problems, as mentioned above. For this purpose, it is preferable to use an activity modifier.
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、エステル類、二Ｉ〜リル類などが用
いられる。具体例としては安息香酸エヂル、ブチルニー
デル、ジグライムなどをあげることが出来る。かかる調
節剤は一般的に、有機金属化合物の話性化剤の成分の溶
液の側に添加して用いられる。前述と同様にルイスペー
ス基を有するＥノン−を使用する場合には、それに調節
剤のＩＱ目をかねさＵることが出来る。As such regulators, Lewis bases are generally used, and among them, ethers, esters, di-I-lyls, etc. are used. Specific examples include edyl benzoate, butyl needle, diglyme, and the like. Such modifiers are generally used by being added to the solution of the components of the organometallic compound speech-enhancing agent. In the same manner as described above, when Enon- containing a Lewis space group is used, the IQ value of the regulator can be added to it.
メタセシス千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
のイーｊ近でありＪ：た、活性化剤成分はアルキルアル
ミニウム類を用いる場合には、上記原料単量体に対する
アルミニウム化合物の比率は、−しル基準で約１００対
１〜約２０００対１、好ましくは約２００対１〜約５０
０対１の付近が用いられる。The amount of the metathesis catalyst system to be 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
When an alkyl aluminum is used as the activator component, the ratio of the aluminum compound to the raw material monomer is about 100:1 to about 2000:1 on a -1 basis. , preferably about 200 to 1 to about 50
A value around 0:1 is used.
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。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.
本発明による架（ｎ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、ざらに各種
添加剤を配合することができる。かかる添加剤としては
、充填剤、顔料、酸化防止剤、光安定剤、難燃化剤、高
分子改良剤などがおる。このＪ：うな添加剤は、本発明
の架橋重合体が成型されて後は添加することが不可能で
あるから、添加覆る場合には予め前記した原料溶液に添
加しておく必要がある。In order to improve or maintain its properties in practical use, various additives may be added to the crosslinked polymer molded product of the present invention. Examples of such additives include fillers, , pigments, antioxidants, light stabilizers, flame retardants, polymer modifiers, etc. These J: additives cannot be added after the crosslinked polymer of the present invention is molded. Therefore, when adding it, it is necessary to add it to the above-mentioned raw material solution in advance.
その最ら容易な方法としては、前記溶液Ａ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、活性化剤成分と実用上さしつかえある程度
には反応Ｕ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、ぞの反応がぎりえないが共存し
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、成型用−［−ルビ中に、充填しておくこ
とも、可能である。The easiest method is to use the solution A 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 activator component in the liquid to a practical extent, and It must be something that does not inhibit polymerization.
No. If the reaction cannot be avoided, but polymerization will not be substantially inhibited even if they coexist, it may be possible to mix it with the monomer to prepare a third liquid and use it immediately before polymerization. I can do it. In addition, in the case of a solid filler,
If both components are mixed and the shape is such that the voids can be sufficiently filled just before starting the polymerization reaction or during polymerization, it is possible to fill it in the molding molding. be.
添加剤としての補強祠又は充填剤は、曲げ−しジュラス
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、つＡラストナイト等を
あげることが出来る。これらを、いわゆるシランガブラ
ーなどににって表面処理したものも好適に使用できる。Reinforcing grains or fillers as additives are effective in improving bending stiffness. Examples of such materials include glass fiber, mica, carbon black, and last night. Those surface-treated with so-called silane gobbler 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７１ノール系又はア
ミン径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、１トラキス［メチレン（３，
５−ジ−ｔ−ブチルー４−ヒドロキシシンナメ−１・）
１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 71-nol type or amine diameter antioxidant to the solution in advance. Specific examples of these antioxidants include 2.6-
t-Butyl-p-cresol, N,N'-diphenyl-
p-phenylenediamine, 1-trakis[methylene (3,
5-di-t-butyl-4-hydroxycinname-1.)
1 methane etc.
本発明の重合体成型物は、側鎖○有メタセシス重合性モ
ノマーを共重合することにＪ：つて内部可塑化し耐衝撃
性を改善した点に特徴を有している。The polymer molded product of the present invention is characterized by internal plasticization and improved impact resistance by copolymerizing a metathesis-polymerizable monomer with a side chain.
この様に、共重合による可塑化を利用することにＪ：っ
て、固型ゴムの添加の場合にりも広範な耐衝撃性を持っ
た成型物を得られるようになったものであるが、固型エ
ラストマーも或いはより低分子量の液状ゴムも本発明の
特徴を損なわない範囲で少量、一般に５重量％以下の量
、さらに一般には３重量％以下を併用して用いることが
出来る。かかる目的に用いられるエラストマーとしては
、スチレン−ブタジェン−スチレン１〜リブロツクゴム
。In this way, by utilizing plasticization through copolymerization, it has become possible to obtain molded products with a wider range of impact resistance than when solid rubber is added. A solid elastomer or a lower molecular weight liquid rubber can be used in combination in small amounts, generally not more than 5% by weight, more generally not more than 3% by weight, as long as the characteristics of the present invention are not impaired. Elastomers used for this purpose include styrene-butadiene-styrene 1 to ribbed rubber.
スチレン−イソプレン−スチレン１〜リブロツクゴム、
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−ジェンターポリマー。Styrene-Isoprene-Styrene 1 ~ Riblock rubber,
Polybutadiene, polyisoprene, butyl rubber, ethylene propylene-genterpolymer.
ニトリルゴムなどをあげることが出来る。Examples include nitrile rubber.
本発明の小合体成型物は、前記した如く、手合と成型と
を同時に行うことによって製造される。The small integrated molded product of the present invention is manufactured by simultaneously carrying out the handling and molding as described above.
かかる成型法としては重油の如く、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
ｕしめるレジンインジェクション方式、触媒系を２つに
分（）た溶液Ａと溶液１３をヘッド部で衝突混合ししめ
てそのまま型に流し込むＲＩ〜１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Ｊ
ることが可能て゛ある。Such molding methods include a resin injection method in which a premix of a catalyst system and a monomer mixture, such as heavy oil, is mixed in advance and poured into a mold, and a resin injection method in which the catalyst system is divided into two parts (solution A and solution 13) into a head. It is possible to use the RI~1 method, in which the mixture is mixed by impact at a section and then poured into a mold as it is. In either case, the injection pressure into the mold can be relatively low, so an inexpensive mold can be used.
It is possible.
また、型内の重合反応が開始されると反応熱にＪ、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づ
る。ポリウレタン−ＲＴＭの場合と異なり、モールドか
ら離脱は容易であり、１２１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 is started, the temperature inside the mold rises rapidly due to the reaction heat, and the polymerization reaction ends in a short time. Unlike polyurethane-RTM, release from the mold is easy and often does not require a separate mold release agent.
成型物は、表面に酸化層が出来ることにＪ、って１、ポ
ギシャポリウレタンなどの一般に使用される塗料へのＩ
ｆｆＪ着１１は、良好である。。Molded products may have an oxidized layer on their surface.
ffJ arrival 11 is in good condition. .
かくして得られた成型物は、従来のものに比して内部可
塑化によって耐衝撃性、即ち可撓性が改良されており、
自動車等を含めた各種運搬機器の部（Ａ、電気、電子機
器のハウジングなど、大型の成型物を含めて広範な用途
に使用出来る。The molded product thus obtained has improved impact resistance, that is, flexibility, due to internal plasticization compared to conventional products.
It can be used in a wide range of applications, including large molded parts such as parts of various transportation equipment including automobiles (A, housings of electrical and electronic equipment, etc.).
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１〜２６．比較例
［原料上ツマ−の調製］
市販のＤＣＰを減圧下、窒素気流中で蒸留精製し、凝固
点３３．４°Ｃを示す精製ジシクロペンタジェンを得た
。ガスクロマ１〜グラフによる純度測定では９９％以上
の純度を示した。Examples 1-26. Comparative Example [Preparation of Raw Materials] Commercially available DCP was purified by distillation under reduced pressure in a nitrogen stream to obtain purified dicyclopentadiene having a freezing point of 33.4°C. Purity measurement using Gas Chroma 1 graph showed a purity of 99% or more.
一方市販ジシクロペンタジェンを熱解離ざＶシクロペン
タジェンを得、これにアクリル酸ブチルを反応ｕしめる
方法により５−７トキシカルポニルノル小ルネン（ＢＣ
Ｎ）を合成した。ざらにマレイン酸ジブデルニスデルを
反応Ｉしめる方法にＪ、リノ°ディック酸ジブデルニス
デル（ＮＤＢ）を、メタアクリル酸２−エチルヘキシル
を反応せしめる方法によって５−メチル−５（２−エチ
ルヘキシル）カルボニルノルボルネン（（）ｆ［ＩｃＮ
）を合１戊した。On the other hand, commercially available dicyclopentadiene was thermally dissociated to obtain V-cyclopentadiene, which was then reacted with butyl acrylate to obtain 5-7-toxycarponylnorsolenene (BC).
N) was synthesized. 5-Methyl-5(2-ethylhexyl)carbonylnorbornene (()f [IcN
) were combined.
きらにアクリル酸２−エチルヘキシルを反応μしめる方
法により５（２−エチルヘキシル）カルボニルノルボル
ネン（ＥＩＩＣＮ）を、マレイン酸ジ（２−エチルヘキ
シル）を反応ｕしめる方法ににリプディック酸ジ（２−
エチルヘキシル）エステル（ＮＢＥＩ＋）を合成した。5(2-ethylhexyl)carbonylnorbornene (EIICN) was prepared by a method of reaction with 2-ethylhexyl acrylate, and lipdic acid di(2-ethylhexyl) was prepared by a method of reaction of di(2-ethylhexyl) maleate.
Ethylhexyl) ester (NBEI+) was synthesized.
これらの化合物はガスクロマ１〜グラフによる純度分析
で９９％以上であった。The purity of these compounds was determined to be 99% or more by gas chroma 1-graph analysis.
［触媒成分溶液の調製］
六塩化タングステン２０ｇを乾燥トルエン７０〃認に窒
素気流中下で添加し、次いでノニルノ１ノール２１ｇお
よび１−ルエン１６〃認よりなる溶液を添加して０．５
Ｈのタングステン含有触媒溶液を調製し、この溶液に対
し、窒素ガスを一晩パージして、六塩化タングステンと
ノニルフ、Ｌノールとの反応によって）Ｉｌｌ′ｌ製８
れた塩化水素ガスを除去して、重合川触媒とした。[Preparation of catalyst component solution] 20 g of tungsten hexachloride was added to 70 g of dry toluene under a nitrogen stream, and then a solution consisting of 21 g of nonyl-1-nol and 16 g of 1-toluene was added to give 0.5 g of tungsten hexachloride.
A tungsten-containing catalyst solution of H was prepared and the solution was purged with nitrogen gas overnight to react with tungsten hexachloride and nonilf, L-nor).
The resulting hydrogen chloride gas was removed to obtain a polymerization catalyst.
かかる溶液１０ｍｊ、 ７ｔチ）ｔ、ｔ７１？ ｈ／１
．０ ｍ１２！ｌｉ量１本）捏合１勿５００ ｔｔｔを
混合し、タングスデン含量０．００１Ｍ溶液Ａ溶液製し
た。Such solution 10 mj, 7t h)t, t71? h/1
．． 0 m12! A solution A having a tungsden content of 0.001M was prepared by mixing 500 ttt of li (1 bottle) and kneading.
［活性化剤成分溶液の調製］
トリオクヂルアルミニウム８５に対しジオクチルアルミ
ニウムアイオダイド１５．ジグライム３００のモル割合
て調製し、混合単量体５００＋１を混合してアルミニウ
ム分として、０．００３Ｈの溶液Ｂを調製した。[Preparation of activator component solution] Dioctylaluminum iodide 15% to 85% trioctylaluminum. Diglyme was prepared at a molar ratio of 300, and mixed monomer 500+1 was mixed to prepare a solution B having an aluminum content of 0.003H.
かかる溶液中の単量体混合物中の前記カルボン酸ニスデ
ル類おにσ共重合成分との使用モル比を次表に示した。The molar ratio of the Nisder carboxylic acid to the σ copolymer component in the monomer mixture in the solution is shown in the following table.
かかる上記の溶液を触媒成分溶液（溶液Ａ＞１００認、
活性化剤成分溶液（溶液Ｂ）１０１１認を所定の温度と
しだ後充分窒素でｃ１３きかえたシリンジ内に取り出し
た゛。かかるシリンジから液を一定速度で両方を同時に
攪拌機つぎガラスフラスコ内に急速攪拌かに押し出し、
急速混合した後攪拌機をあげ熱雷体を押入し、液のシリ
ンジからの注入が終わった時点から１００ ’Ｃに到達
した時間（手合時間）を測定した。The above solution was converted into a catalyst component solution (solution A > 100,
After bringing the activator component solution (solution B) 1011 to a predetermined temperature, it was taken out into a syringe that had been thoroughly replaced with nitrogen. The liquid from the syringe is simultaneously forced out at a constant rate into a stirrer and then into a glass flask with rapid stirring.
After rapid mixing, the stirrer was turned on, a thermal lightning rod was inserted, and the time from the time when the injection of the liquid from the syringe was completed to the time when the temperature reached 100'C (hand time) 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、Ｔ Ｍ Ａ法−鉗浸入モードで軟化点を測定
した。また膨潤率を別のリンプルで測定した。結果を表
２にまとめた。Further, the solidified crosslinked resin was taken out, cut into sections, and the softening point was measured in a nitrogen stream using the TMA method - forceps penetration mode. The swelling rate was also measured using another rimpull. The results are summarized in Table 2.
ざらに核実施例の液核Ａ、Ｂを１０Ｉｎｉづつシリンジ
に取り出し、それを機械的に一定速度で押出しノズル内
に導き、そこで衝突混合して型内に流し込める超小型Ｒ
ＩＭＩＸＩにか〜りて成型した所、褐色のタフな３ｍｍ
厚の板状物が成型出来た。この板を用いてノツチ付アイ
ゾツト強度を測定し同表に併記した。An ultra-compact R that can take out liquid nuclei A and B of the Rough Nucleus Example into a syringe, mechanically guide them at a constant speed into an extrusion nozzle, mix them by collision there, and pour them into a mold.
The part molded by IMIXI is a brown tough 3mm.
A thick plate-like object could be formed. The notched isot strength was measured using this plate and is also listed in the same table.
混合時温度と手合時間からこれらの化合物の添加量が僧
づに従い反応開始温度が高くなりまた反応１時間が良く
なる傾向を示し、比較例に比して大型の成型物を１ｑる
のに有利となる。かつｊｑられた樹脂は軟化点の低い柔
軟でタフな成型物が１ｑられており、ノツチ付アイゾツ
トの耐衝撃性の測定結果から−し比較例に比して人ｒｌ
Ｊに改善されていることが判る。Based on the mixing temperature and handling time, as the amount of these compounds added increases, the reaction start temperature becomes higher and the reaction time tends to be shorter, which is advantageous for producing large molded products by 1 q compared to the comparative example. becomes. Moreover, the molded resin is flexible and tough with a low softening point, and from the results of measuring the impact resistance of the notched Izot, it has a lower softening point than the comparative example.
It can be seen that it has been improved to J.
実施例２７〜３０
無水ノ“ディック酸とブチルアミンをアセ１〜ニトリル
を１〜ルエン中加熱還流により１５２水反応せしめる方
法によりブチルノーディック酸イミド（ＢＮＩ）を合成
した、反応混合物から減圧上蒸留精製した。Examples 27-30 Butyl nodic acid imide (BNI) was synthesized by a method in which anhydrous nodic acid and butylamine were reacted with 152 water by heating and refluxing 1 to nitrile in 1 to toluene, and purified by distillation on reduced pressure from the reaction mixture. did.
また無水ノーディック酸と２−エチルヘキシルアミンと
の同様の反応により２−エチルへキシルノ”ディック酸
イミド（Ｂ１１旧）を合成した。In addition, 2-ethylhexylnodic acid imide (old B11) was synthesized by a similar reaction between nodic anhydride and 2-ethylhexylamine.
これらの化合物がガスクロマ１ヘゲ°ラフによる純度分
析では９９％以上であった。Purity analysis of these compounds using Gas Chroma 1 Hage Rough showed that the purity was 99% or more.
構造はＭＳ、ＩＲおよびＮＭＲから確認した。The structure was confirmed by MS, IR and NMR.
重合は表３に示すような単量体の混合比で混合物を実施
例１と同様に実施した。結果を表４に示した。Polymerization was carried out in the same manner as in Example 1 using a mixture of monomers at the mixing ratio shown in Table 3. The results are shown in Table 4.
表 ３
表 ４
混合ｎ：’ｊ １ｇ度と手合時間からこれらの化合物の
添加量が贈りに従い反応開始温度が高くなりまた反応１
１．１間が長くなる傾向を示し、比較例に比して大型の
成型物を１′ｌるのに有利となる。かつ得られた樹脂は
柔軟でタフな成型物が１！７られており、ノツブイ・」
アイゾツトの耐衝撃性の測定結果からも比較例に比して
改善されていることが判る。Table 3 Table 4 Mixing n:'j From 1 g degree and mixing time, the reaction initiation temperature becomes higher and reaction 1 increases as the amount of these compounds added increases.
There is a tendency for the distance between 1.1 and 1.1 mm to become longer, which is advantageous in making a large molded product 1'l longer than in the comparative example. Moreover, the obtained resin is molded into a flexible and tough product.
The results of measuring the impact resistance of Izotz also show that it is improved compared to the comparative example.
実施例３１
市販のジシクロペンタジェンを熱解離させたシクロペン
タジェンとアリルブチルエーテルをオー１〜クレープ中
反応せしめる方向によりブチル（５−ノルボルネニルメ
チル）エーテル（ＢＮＥ）を合成した。この化合物は０
．２ｍｍ１１ｇ減圧下４４℃の留分にす１ｑられ、ガス
クロマトグラフによる純度分析では９９％以上であった
。なおＭ４造は〜１ｓ、ＮＭＲおよびＩＲより確認した
。Example 31 Butyl (5-norbornenylmethyl) ether (BNE) was synthesized by reacting cyclopentadiene obtained by thermally dissociating commercially available dicyclopentadiene with allyl butyl ether in a crepe. This compound is 0
．． 2 mm, 11 g, and 1 q were distilled into a distillate at 44° C. under reduced pressure, and the purity analysis by gas chromatography showed that it was 99% or more. The M4 structure was confirmed by NMR and IR for ~1s.
ＤＣＰとの共重合は、ＤＣＰ ９０モル％、 ＢＮＥ
１０モル％の混合物を実施例１と同様に実施し、重合開
始温度５０’Ｃで、７秒間で１００℃を上回り最高到達
温度は１８７℃であった。比較例に比し、混合時温度が
高くなり、重合時間が長くなることからＢＮＥを添加す
ることにより比較例よりも大型の成型物を１ｑるのに有
利となる。またＴＨＡによる軟化点測定では７８°Ｃで
ありざらにノツチ付アイゾツトによる耐衝撃性の測定値
は４ｅ＋＜ｇ −ｃｍ／ｃｍであった。このことにす１
ｑられた樹脂は軟化点の低い柔軟で耐衝撃性のり−ぐれ
た乙のであることが判る。For copolymerization with DCP, DCP 90 mol%, BNE
A 10 mol % mixture was carried out in the same manner as in Example 1, and the polymerization initiation temperature was 50'C, exceeding 100C in 7 seconds, and the highest temperature reached was 187C. Compared to the comparative example, the mixing temperature is higher and the polymerization time is longer, so adding BNE is advantageous in producing larger molded products of 1 q than in the comparative example. Further, the softening point was measured by THA at 78°C, and the impact resistance measured by rough notched Izot was 4e+<g-cm/cm. I agree with this 1
It can be seen that the prepared resin is flexible with a low softening point and has excellent impact resistance.
実施例３２
市販のジシクロペンタジニ［ンと１−Δクテンを１７０
°Ｃでオー１〜クレープ中で反応ｕしめる方法により５
−へキシルノルボルネン（ＩＩＮＢ）を合成した。Example 32 Commercially available dicyclopentazine and 1-Δctene were mixed at 170%
By the method of reaction u in a crepe from 1 to 5 at °C.
-hexylnorbornene (IINB) was synthesized.
コノ化合物ハ０．７ｍｍ１１ｇ減圧下、ＧＯ’Ｃの留分
より１ｑられガスクロマトグラフィーににる純度分析で
は９９％以上の純度でおった。なお構造はＮＭＲ，ＭＳ
により確認した。0.7 mm of 11 g of the Kono compound was extracted from the GO'C fraction under reduced pressure, and the purity analysis by gas chromatography showed that the purity was 99% or more. The structure is NMR, MS
Confirmed by.
ＤＣＰとの共重合はＤＣＰ ８０モル％、 ＩＩＮＢ
２０モル％の混合物を実施例１と同様に実施し手合開始
温度３５°Ｃで混合後３２秒で１００°Ｃに達示、最高
到達温度は１７３°Ｃであった。−ｒＭＡにＪ、る軟化
点測定では８３°Ｃを示し、ざらにノツヂイ号アイゾツ
トによる耐衝撃性の測定値は７．５Ｋ（Ｊ・ｃ ｍ ／
ｃ ｍてあった。このこと−；り比較例に比しｆｕＪ
Ｂｉｒ ＝性が向上しでいることか判る。Copolymerization with DCP is DCP 80 mol%, IINB
A 20 mol% mixture was prepared in the same manner as in Example 1, and the starting temperature was 35°C, and the temperature reached 100°C in 32 seconds after mixing, and the maximum temperature reached was 173°C. The softening point measured by -rMA was 83°C, and the impact resistance measured by Zarani No Tsuji Izotsu was 7.5K (J cm /
There was a cm. This means that compared to the comparative example, fuJ
Bir = You can see that your sexuality has improved.
Claims (3)
よび回転を阻害されない原子を５個以上有する１価の鎖
状有機基を少なくとも１個有する単量体をメタセシス重
合性モノマー中の３〜５０モル％含有する原料単量体を
メタセシス重合触媒系の存在下バルク重合せしめること
によって得られた内部可塑化された重合体成型物。(1) A monomer having at least one metathesis polymerizable group in the molecule and at least one monovalent chain organic group having 5 or more atoms whose rotation is not inhibited is added to the metathesis polymerizable monomer. An internally plasticized polymer molded product obtained by bulk polymerizing raw material monomers containing mol % in the presence of a metathesis polymerization catalyst system.
系の存在下バルク重合せしめて重合体成型物を得る方法
において、原料単量体として、分子中にメタセシス重合
性基を少なくとも１個および回転を阻害されない原子を
５個以上有する１価の鎖状有機基を少なくとも１個有す
る単量体をメタセシス重合性モノマー中の３〜５０モル
％含有する原料単量体を使用することを特徴とする内部
可塑化された重合体成型物の製造方法。(2) In a method for bulk polymerizing metathesis polymerizable monomers in the presence of a metathesis polymerization catalyst system to obtain a molded polymer, the raw monomer contains at least one metathesis polymerizable group in the molecule and does not inhibit rotation. Internal plasticization characterized by using a raw material monomer containing 3 to 50 mol% of a monomer having at least one monovalent chain organic group having 5 or more atoms in the metathesis polymerizable monomer. A method for producing a polymer molded article.
セシス重合性モノマーの反応性溶液（溶液Ａ） ｂ）メタセシス重合触媒系の活性化剤成分を含むメタセ
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、前記
溶液Ａおよび溶液Ｂのメタセシス重合性モノマーは、両
液を合せた組成が分子中にメタセシス重合性基を少なく
とも１個および回転を阻害されない原子を５個以上有す
る１価の鎖状有機基を少なくとも１個有する単量体をメ
タセシス重合性モノマー中の３〜５０モル％含有する原
料単量体であることを特徴とする反応性溶液の組合せ。(3) a) A reactive solution of a metathesis polymerizable monomer containing a catalyst component of a metathesis polymerization catalyst system (solution A) b) A reactive solution of a metathesis polymerizable monomer containing an activator component of a metathesis polymerization catalyst system (solution B) ) In the combination of reactive solutions consisting of at least A combination of reactive solutions characterized in that the raw material monomers contain 3 to 50 mol % of a monomer having at least one monovalent chain organic group in the metathesis polymerizable monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62092099A JPH0778115B2 (en) | 1987-04-16 | 1987-04-16 | Method for producing crosslinked polymer molding and combination of reactive solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62092099A JPH0778115B2 (en) | 1987-04-16 | 1987-04-16 | Method for producing crosslinked polymer molding and combination of reactive solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63258920A true JPS63258920A (en) | 1988-10-26 |
| JPH0778115B2 JPH0778115B2 (en) | 1995-08-23 |
Family
ID=14044999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62092099A Expired - Lifetime JPH0778115B2 (en) | 1987-04-16 | 1987-04-16 | Method for producing crosslinked polymer molding and combination of reactive solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0778115B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5561271B2 (en) * | 2009-03-26 | 2014-07-30 | 日本ゼオン株式会社 | Resin composition, resin film and electronic component |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53103000A (en) * | 1977-02-21 | 1978-09-07 | Showa Denko Kk | Improved process for producing ring-opening polymer |
-
1987
- 1987-04-16 JP JP62092099A patent/JPH0778115B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53103000A (en) * | 1977-02-21 | 1978-09-07 | Showa Denko Kk | Improved process for producing ring-opening polymer |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5561271B2 (en) * | 2009-03-26 | 2014-07-30 | 日本ゼオン株式会社 | Resin composition, resin film and electronic component |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0778115B2 (en) | 1995-08-23 |
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