JPS63234017A - Production of monomer for ring opening polymerization - Google Patents
Production of monomer for ring opening polymerizationInfo
- Publication number
- JPS63234017A JPS63234017A JP6567187A JP6567187A JPS63234017A JP S63234017 A JPS63234017 A JP S63234017A JP 6567187 A JP6567187 A JP 6567187A JP 6567187 A JP6567187 A JP 6567187A JP S63234017 A JPS63234017 A JP S63234017A
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- heat
- norbornene
- product
- polymerization
- 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
- 239000000178 monomer Substances 0.000 title claims abstract description 32
- 238000007151 ring opening polymerisation reaction Methods 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 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 34
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 abstract description 15
- 239000011347 resin Substances 0.000 abstract description 15
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 14
- 238000010107 reaction injection moulding Methods 0.000 abstract description 11
- 238000010438 heat treatment Methods 0.000 abstract description 7
- 239000003963 antioxidant agent Substances 0.000 abstract description 4
- 230000003078 antioxidant effect Effects 0.000 abstract description 3
- 238000000746 purification Methods 0.000 abstract description 3
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 24
- 239000000203 mixture Substances 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 101150087322 DCPS gene Proteins 0.000 description 11
- 101100386724 Schizosaccharomyces pombe (strain 972 / ATCC 24843) nhm1 gene Proteins 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 238000005649 metathesis reaction Methods 0.000 description 10
- 239000012535 impurity Substances 0.000 description 9
- 239000013256 coordination polymer Substances 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 7
- 238000007710 freezing Methods 0.000 description 6
- 230000008014 freezing Effects 0.000 description 6
- 230000037048 polymerization activity Effects 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- -1 tungsten halide Chemical class 0.000 description 5
- 239000012190 activator Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000012662 bulk polymerization Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002848 norbornenes Chemical class 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004634 thermosetting polymer Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-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
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- JWIVXACJSSFIHH-UHFFFAOYSA-N 4-prop-1-en-2-ylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(C(=C)C)C2 JWIVXACJSSFIHH-UHFFFAOYSA-N 0.000 description 1
- BSFWGXOMEGLIPL-UHFFFAOYSA-N 4-prop-1-enylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(C=CC)C2 BSFWGXOMEGLIPL-UHFFFAOYSA-N 0.000 description 1
- YSWATWCBYRBYBO-UHFFFAOYSA-N 5-butylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCC)CC1C=C2 YSWATWCBYRBYBO-UHFFFAOYSA-N 0.000 description 1
- VVKPRHOUENDOED-UHFFFAOYSA-N 5-dodecylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCCCCCCCCCC)CC1C=C2 VVKPRHOUENDOED-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
- QHJIJNGGGLNBNJ-UHFFFAOYSA-N 5-ethylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CC)CC1C=C2 QHJIJNGGGLNBNJ-UHFFFAOYSA-N 0.000 description 1
- WMWDGZLDLRCDRG-UHFFFAOYSA-N 5-hexylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCCCC)CC1C=C2 WMWDGZLDLRCDRG-UHFFFAOYSA-N 0.000 description 1
- PCBPVYHMZBWMAZ-UHFFFAOYSA-N 5-methylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C)CC1C=C2 PCBPVYHMZBWMAZ-UHFFFAOYSA-N 0.000 description 1
- GOLQZWYZZWIBCA-UHFFFAOYSA-N 5-octylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(CCCCCCCC)CC1C=C2 GOLQZWYZZWIBCA-UHFFFAOYSA-N 0.000 description 1
- LJKQIQSBHFNMDV-UHFFFAOYSA-N 7-thiabicyclo[4.1.0]hepta-2,4-dien-6-ol Chemical class C1=CC=CC2(O)C1S2 LJKQIQSBHFNMDV-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- URYAFVKLYSEINW-UHFFFAOYSA-N Chlorfenethol Chemical compound C=1C=C(Cl)C=CC=1C(O)(C)C1=CC=C(Cl)C=C1 URYAFVKLYSEINW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000003967 crop rotation Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000001993 dienes Chemical class 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
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- UCQHUEOREKHIBP-UHFFFAOYSA-N heptacyclo[9.6.1.14,7.113,16.02,10.03,8.012,17]icosa-5,14-diene Chemical compound C1C(C23)C4C(C=C5)CC5C4C1C3CC1C2C2C=CC1C2 UCQHUEOREKHIBP-UHFFFAOYSA-N 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GDSGXRQXKTWBOS-UHFFFAOYSA-N n,n-di(tridecyl)tridecan-1-amine Chemical compound CCCCCCCCCCCCCN(CCCCCCCCCCCCC)CCCCCCCCCCCCC GDSGXRQXKTWBOS-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明はジシクロペンタジェン類から高い重合活性を有
する開環重合用モノマーを製造する方法に関し、さらに
詳細には、ジシクロペンタジェン類を熱処理することに
より、特別に精製することなく高活性で、しかも反応射
出成形に利用した場合、高い熱変形温度および改良され
た曲げ弾性率を有する熱硬化性樹脂を与える開環重合用
モノマーの製造法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing a monomer for ring-opening polymerization having high polymerization activity from dicyclopentadiene, and more particularly, to a method for producing a monomer for ring-opening polymerization having high polymerization activity from dicyclopentadiene. The present invention relates to a method for producing monomers for ring-opening polymerization which thereby yield thermosetting resins with high activity without special purification and which, when used in reaction injection molding, have a high heat distortion temperature and an improved flexural modulus. .
従来の技術
近年、ジシクロペンタジェンやメチルテトラシクロデセ
ンなどのノルボルネン系七ノで−を反応射出成形法によ
り、メタセシス触媒系を用いて。Prior art In recent years, norbornene derivatives such as dicyclopentadiene and methyltetracyclodecene have been synthesized by reaction injection molding using metathesis catalyst systems.
金型内で開環重合させ熱硬化性ポリマーを製造する方法
が注目されている。A method of manufacturing a thermosetting polymer by ring-opening polymerization in a mold is attracting attention.
例えば、特開昭58−129013号には、反応射出成
形法CRIM法)により、メタセシス触媒系を使用する
熱硬化性ジシクロペンタジェン(D CP)ホモポリマ
ーの製造方法が開示されており、好ましい実施態様では
、該ホモポリマーは、ハロゲン化タングステン、オキシ
ハロゲン化タングステンのようなメタセシス触媒系の触
媒成分とモノマー(D CP)との混合物からなる一方
の溶液と、ハロゲン化アルキルアルミニウムのようなメ
タセシス触媒活性剤とモノマー(DCP)とからなるも
う一方の溶液の二種類の溶液を反応射出成形(RIM)
機中で合わせ、次いで、成形金型中に注入することによ
って製造される。For example, JP-A-58-129013 discloses a method for producing thermosetting dicyclopentadiene (D CP) homopolymer using a metathesis catalyst system by reaction injection molding method (CRIM method), which is a preferred method. In embodiments, the homopolymer is mixed with a solution consisting of a mixture of a monomer (DCP) and a catalyst component of a metathesis catalyst system, such as tungsten halide, tungsten oxyhalide, and a metathesis catalyst system, such as an alkyl aluminum halide. Reaction injection molding (RIM) of two solutions, one consisting of a catalyst activator and the other consisting of a monomer (DCP)
It is manufactured by combining in a machine and then pouring into a mold.
特開昭59−51911号には、RIM法においてメタ
セシス触媒系を使用する方法によるノルボルネン環を含
む環状オレフィンの塊状による開卵重合法が開示されて
おり、この塊状重合法においては、ポットライフを延長
するため共触媒(活性剤)としてアルコキシアルキルア
ルミニウムハライドやアリールオキシアルキルアルミニ
ウムハライド共触媒の使用が提案されている。JP-A No. 59-51911 discloses an opening polymerization method using a mass of cyclic olefin containing a norbornene ring using a metathesis catalyst system in the RIM method. In this bulk polymerization method, the pot life is reduced. The use of alkoxyalkylaluminum halides and aryloxyalkylaluminium halide cocatalysts as cocatalysts (activators) has been proposed to extend the process.
しかし、従来のRIM法では、出発原料として石版のD
CP類をそのまま使用すると、その中に含まれている少
量の不純物のために重合が妨げられるので重合活性が十
分ではない、そのために、例えば純度が96〜97%の
重版のDCPをさらにM製し、低沸点溜升などの不純物
を除去しなければならなかった(特開昭58−1290
13号)。However, in the conventional RIM method, the lithographic D
If CPs are used as they are, the small amount of impurities contained therein will hinder the polymerization and the polymerization activity will not be sufficient. Therefore, for example, reprinted DCP with a purity of 96 to 97% may be further added to M. However, it was necessary to remove impurities such as low-boiling distillates (Japanese Patent Application Laid-Open No. 1290-1980)
No. 13).
そして、DCPEを精製するために蒸留を繰り返し、純
度を上げることが行なわれてきた。しかし、この方法で
はDCPの回収率が低下し、また、たとえ高純度に精製
した場合でも、しばしば反応射出成形における重合反応
条件に対して不活性になることがあった。In order to purify DCPE, distillation has been repeated to increase its purity. However, this method lowers the recovery rate of DCP, and even when purified to a high degree of purity, it often becomes inert to the polymerization reaction conditions in reaction injection molding.
最近、重版のDCPを蒸留し、さらに重合妨害物となる
不純物を除去するためにモレ午ニラーシーブやアルミナ
、シリカゲルなどの吸着剤で処理する方法が提案された
(米国特許第4,584.425号)、シかし、この方
法では蒸留性能が不十分であるため、多量の初留4分や
釜残物を残す必要があり、高純度のDCPの収率が低い
という欠点があるうえ、吸着剤による処理工程の増加や
廃吸着剤の廃棄処理など工業的には不利な点がある。Recently, a method has been proposed in which the reprinted DCP is distilled and further treated with adsorbents such as sieves, alumina, and silica gel to remove impurities that interfere with polymerization (U.S. Pat. No. 4,584,425). ), however, this method has insufficient distillation performance, requiring a large amount of initial distillation and residue to be left behind, resulting in a low yield of high-purity DCP. There are disadvantages from an industrial perspective, such as an increase in the number of processing steps using adsorbents and disposal of waste adsorbents.
しかも、これらの開示された方法による開環重合体は、
耐衝撃性、高弾性率、i+を熱性などのごときエンジニ
アリングプラスチックに要求される諸物性において比較
的良好な性能を有しているが、昨今の厳しい要求性能か
らみると未だ必ずしも充分とはいいがたい0例えば、こ
れらの方法によって得られるDCPホモポリマーのガラ
ス転移温度は5通常約90℃前後であり、#熱性が要求
される分野の材料としてはやや不足である。Moreover, the ring-opened polymers produced by these disclosed methods are
Although it has relatively good performance in various physical properties required for engineering plastics such as impact resistance, high modulus of elasticity, and thermal properties of i+, it is still not necessarily sufficient considering the recent strict performance requirements. For example, the glass transition temperature of the DCP homopolymer obtained by these methods is usually around 90° C., which is somewhat insufficient as a material for fields requiring thermal properties.
ところで、この場合、使用するノルボルネン系モノマー
が多環体になるにつれ、つまりモノマー中の環状構造単
位が多くなるにつれ、得られるポリマーの熱変形温度は
上昇する。しかし、高純度の多環モノマーは入手が困難
であり、しかもそれらは固体であることが多いためRI
M法による金型への注入操作が困難となる。Incidentally, in this case, as the norbornene monomer used becomes polycyclic, that is, as the number of cyclic structural units in the monomer increases, the heat distortion temperature of the resulting polymer increases. However, it is difficult to obtain high-purity polycyclic monomers, and since they are often solid, RI
Injection into a mold using the M method becomes difficult.
特開昭61−179214号には、ポリマー生成物のガ
ラス転移温度(T g)を高め、熱変形温度を改良する
ため、DCPなどのノルボルネン系モノマーと例えばト
リメチロールプロパン−トリス−(5−ノルボルネン−
2−カルボキシレート)のように1重合中に開裂して架
橋の数を増すような2 (11以上の反応性二重合結合
を有するコモノマーなどとの共重合法が開示されている
。しかしながら、この方法では入手困難な特殊なコモノ
マーを使用する必要があり、経済性の面で難点がある。JP-A-61-179214 discloses that in order to increase the glass transition temperature (Tg) and improve the heat distortion temperature of a polymer product, a norbornene monomer such as DCP and, for example, trimethylolpropane-tris-(5-norbornene −
A copolymerization method with a comonomer having 11 or more reactive double bonds, such as 2-carboxylate), which increases the number of crosslinks by cleavage during one polymerization, has been disclosed. This method requires the use of special comonomers that are difficult to obtain, and is economically disadvantageous.
発明が解決しようとする問題点
本発明者らは、前記問題点を克服すべく鋭意研究を積み
重ねた結果、ジシクロペンタジェン類の熱処理によって
得られる生成物を単独で、または該生成物とフルボルネ
ン系モノマーとを混合したものが、高い重合活性を有し
て、おり、しかもこれらを所定形状の金型内で、メタセ
シス触媒系の存在下に開環重合せしめることにより、高
いガラス転移点を有し、かつ曲げ弾性率の改良された熱
硬化性樹脂の得られることを見出し、その知見に基づい
て本発明を完成するに至った。Problems to be Solved by the Invention As a result of extensive research in order to overcome the above problems, the present inventors have discovered that the products obtained by heat treatment of dicyclopentadines can be used alone or in combination with fulbornene. A mixture of these monomers has high polymerization activity, and by ring-opening polymerization of these in a mold with a predetermined shape in the presence of a metathesis catalyst system, it has a high glass transition point. However, the present inventors have discovered that a thermosetting resin with improved flexural modulus can be obtained, and based on this knowledge, they have completed the present invention.
問題点を解決するための手段
すなわち、本発明の要旨は、ジシクロペンタジェン類を
120〜250℃で熱処理し1次いで必要に応じてノル
ボルネン系モノマーを混合することを特徴とする開環重
合用モノマーの製造法にある。A means for solving the problems, that is, the gist of the present invention is to provide a method for ring-opening polymerization, which is characterized in that dicyclopentadiene is heat-treated at 120 to 250°C, and then, if necessary, a norbornene monomer is mixed therein. It is in the method of manufacturing monomers.
以下、本発明の構成要素について詳述する。Hereinafter, the constituent elements of the present invention will be explained in detail.
(ジシクロペンタジェン類)
本発明において用いられる原料のジシクロペンタジェン
類は、通常、その純度が90重量%以上、好ましくは9
5重量%以上のものであれば、必ずしも予め精製する必
要はなく、その熱処理物は°高活性であり良好な開環重
合体を与える。(Dicyclopentadines) The raw material dicyclopentadines used in the present invention usually has a purity of 90% by weight or more, preferably 9% by weight or more.
If it is 5% by weight or more, it is not necessarily necessary to purify it in advance, and the heat-treated product is highly active and yields a good ring-opened polymer.
ジシクロペンタジェン類は、通常、不純物として低沸点
不純物および高沸点不純物を含み、前者の具体例として
は、例えば炭素数4〜6の炭化水素、シクロペンタジェ
ンとブタジェン、イソプレン、ピペリレンなどの鎖状共
役ジオレフィンとの共二量体化物(ビニルノルボルネン
、イソプロペニルノルボルネン、プロペニルノルボルネ
ンなど)などが挙げら、また後者の例としては、例えば
シクロペンタジェンの3量体、シクロペンタジェンとイ
ソプレンの共二量体化物(メチルビシクロノナジェン)
などが挙げられる。この中で、炭素数4〜6の炭化水素
は反応射出成形の成形不良を引き起すため、従来は十分
に除去しなければならなかったが1本発明においては、
純度が98%以下であっても充分な重合活性を有する。Dicyclopentadines usually contain low-boiling point impurities and high-boiling point impurities as impurities, and specific examples of the former include hydrocarbons having 4 to 6 carbon atoms, chains such as cyclopentadiene and butadiene, isoprene, piperylene, etc. Examples of the latter include co-dimers with conjugated diolefins (vinylnorbornene, isopropenylnorbornene, propenylnorbornene, etc.); Codimerized product (methylbicyclononadene)
Examples include. Among these, hydrocarbons having 4 to 6 carbon atoms cause molding defects in reaction injection molding, so conventionally they had to be sufficiently removed, but in the present invention,
Even if the purity is 98% or less, it has sufficient polymerization activity.
本発明で用いるジシクロペンタジェン類は、ジシクロペ
ンタジェン(D CP)やそのメチル置換体およびエチ
ル置換体などのアルキル置検体である。原料のDCPは
、エンド異性体、エキソ異性体またはこれらの混合物で
ある。The dicyclopentadiene used in the present invention is an alkyl substituted analyte such as dicyclopentadiene (DCP) or its methyl substituted product or ethyl substituted product. The starting DCP is an endo isomer, an exo isomer or a mixture thereof.
(ジシクロペンタジェン類の熱処理)
熱処理の条件としては、ジシクロペンタジェン類を窒素
ガスなどの不活性ガス雰囲気下、120〜250℃、好
ましくは150〜220℃の温度で、0.5〜20時間
、好ましくは1−10時間加熱する方法が挙げられる。(Heat treatment of dicyclopentadines) The conditions for heat treatment are that dicyclopentadines are treated in an atmosphere of an inert gas such as nitrogen gas at a temperature of 120 to 250°C, preferably 150 to 220°C, and a temperature of 0.5 to A method of heating for 20 hours, preferably 1 to 10 hours is mentioned.
処理の反応形式は、バッチ式、連続式のいずれでもよい
、また、処理に際して、ベンゼン、トルエン、キシレン
などのごとき反応に不活性な溶剤を共存させることがで
きるが、この場合には処理後に溶剤を除去する操作が必
要となるため、できるだけ溶剤を使用せずに処理するこ
とが好ましい。The reaction format of the treatment may be either batch or continuous.Also, during the treatment, a solvent inert to the reaction such as benzene, toluene, xylene, etc. may be coexisting, but in this case, the solvent may be removed after the treatment. Since this requires an operation to remove , it is preferable to perform the treatment without using a solvent as much as possible.
また、S処理は酸化防止剤の存在下に行なうことが好ま
しい、酸化防止剤としてはフェノール系のものが良く、
例えば、4.4−ジオキシジフェニル、ヒドロキノン拳
モノベンジルエーテル2、4−ジメチル−6−t−ブチ
ルフェノール、2、6−ジーt−ブチルフェノール、2
.6−ジ−7ミルヒドロキノン、2.6−ジーt−ブチ
ル−P−クレゾール、4−ヒドロキシメチル−2。In addition, it is preferable that the S treatment be carried out in the presence of an antioxidant, and phenolic antioxidants are preferred.
For example, 4,4-dioxydiphenyl, hydroquinone monobenzyl ether 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butylphenol, 2
.. 6-di-7milhydroquinone, 2,6-di-t-butyl-P-cresol, 4-hydroxymethyl-2.
6−ジーt−ブチルフェノール、4,4′−メチレン−
ビス−(6−t−ブチル−O−クレゾール)、ブチル化
ヒドロキシ7ニソール、フェノール縮合物,ブチレン化
フェノール、ジアルキル・フェノール・スルフィド、高
分゛子量多価フェノール、ビスフェノールなどが挙げら
れる.t−ブチルカテコール、ヒドロキノン、レゾルシ
ン、ピロガロールなどのキノン系も使用することができ
る.酸化防止剤の使用量は通常、DCP類に対して10
N10,OOOppm,好ましくは100〜l・OO
OPPmである。6-di-t-butylphenol, 4,4'-methylene-
Examples include bis-(6-t-butyl-O-cresol), butylated hydroxy 7-nisole, phenol condensates, butylenated phenols, dialkyl phenol sulfides, high molecular weight polyhydric phenols, and bisphenols. Quinones such as t-butylcatechol, hydroquinone, resorcinol, and pyrogallol can also be used. The amount of antioxidant used is usually 10% for DCPs.
N10, OOOppm, preferably 100~l・OO
It is OPPm.
得られた生成物は,そのままで開環重合による熱硬化性
樹脂の製造原料として使用可能であるが、必要により未
反応のDCP類または低沸点不純物を蒸留により除去し
てもよい。The obtained product can be used as it is as a raw material for producing a thermosetting resin by ring-opening polymerization, but if necessary, unreacted DCPs or low-boiling impurities may be removed by distillation.
DCP類の熱処理によって得られる生成物は。The products obtained by heat treatment of DCPs are:
ワックス状もしくは油状のものである.ワックス状のも
のは,凝固点が通常100℃以下,好ましくは60℃以
下のものであり、油状のものは、30℃における粘度が
通常200センチポイズ(c p s)以下,#?まし
くは100cps以下のもあである.これらの生成物は
,未反応のDCP類とDCP類の熱反応物とを含んでい
るが,本発明においてはDCP類の熱反応物を5重量%
以上、さらには10重量%以上含有するものが好ましい
。It is waxy or oily. The waxy type usually has a freezing point of 100°C or lower, preferably 60°C or lower, and the oily type usually has a viscosity of 200 centipoise (c p s) or lower at 30°C, #? Preferably, the power is less than 100 cps. These products contain unreacted DCPs and thermally reacted products of DCPs, but in the present invention, the thermally reacted products of DCPs are contained in an amount of 5% by weight.
Those containing 10% by weight or more are preferable.
(ノルボルネン第七ツマ−)
本願発明において,必要に応じてDCP類の熱処理生成
物と混合して使用されるノルボルネン第七ツマ−は、置
換および未置換のノルボルネン。(Norbornene No. 7) In the present invention, norbornene No. 7, which is used in combination with the heat-treated product of DCPs as needed, is substituted or unsubstituted norbornene.
ジシクロペンタジェン、ジヒドロジシクロペンタジェン
、トリシクロペンタジェン、テトラシクロペンタジェン
、テトラシクロドデセンなどであり、具体例として,ジ
シクロペンタジェン、メチルテトラシクロドデセン、2
−ノルボルネン、5−メチル−2−ノルボルネン、5,
6−シメチルー2−ノルボルネン、5−エチル−2−ノ
ルボルネン、5−ブチル−2−ノルボルネン、5−へキ
シル−2−ノルボルネン、5−オクチル−2−ノルボル
ネン、5−ドデシル−2−ノルボネン等が挙げられる。Dicyclopentadiene, dihydrodicyclopentadiene, tricyclopentadiene, tetracyclopentadiene, tetracyclododecene, etc. Specific examples include dicyclopentadiene, methyltetracyclododecene, 2
-norbornene, 5-methyl-2-norbornene, 5,
Examples include 6-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-dodecyl-2-norbornene, etc. It will be done.
(DCP類の熱処理生成物とノルボルネン系モノマーと
の混合)
DCP類の熱処理によって得られるワックス状もしくは
油状の生成物は単独でも開環重合用モノマーとして用い
ることができるが、必要によりノルボルネン系モノマー
と混合して用いることかでさる。その場合、熱処理生成
物とノルボルネン系モノマーとの混合比率は目的に応じ
て適宜選択すればよいが、通常は前者が100〜10重
量%、好ましくは100〜20重量%で後者がO〜90
重i%、好ましくは0〜80重量%であり、混合物中に
は熱処理生成物中に含まれるDCP類の熱反応物が5重
量%以上、さらには10重量%以上存在することが好ま
しい、熱処理生成物の割合が減少するにつれ、得られる
熱硬化性4#詣のガラス転移温度および曲げ弾性率が低
下する。(Mixing the heat-treated product of DCPs and norbornene monomer) The waxy or oily product obtained by heat-treating DCPs can be used alone as a monomer for ring-opening polymerization, but if necessary, it may be mixed with a norbornene monomer. It is possible to use them in combination. In that case, the mixing ratio of the heat-treated product and the norbornene monomer may be appropriately selected depending on the purpose, but usually the former is 100 to 10% by weight, preferably 100 to 20% by weight, and the latter is O to 90% by weight.
% by weight, preferably 0 to 80% by weight, and it is preferable that the thermally reacted product of DCPs contained in the heat-treated product is present in the mixture at 5% by weight or more, more preferably 10% by weight or more. As the proportion of the product decreases, the glass transition temperature and flexural modulus of the resulting thermosetting 4# resin decrease.
両者の混合物の性状には特に制限はないが、30℃好ま
しくは10℃で液状を呈するものであることが金型への
注入などの操作上有利である。Although there are no particular limitations on the properties of the mixture, it is advantageous for operations such as injection into a mold to be liquid at 30°C, preferably 10°C.
30℃における液状物の粘度は通常500cps以下で
あり、なかでも200cps以下、特に100cps以
下のものが好ましい。The viscosity of the liquid at 30° C. is usually 500 cps or less, preferably 200 cps or less, particularly 100 cps or less.
なお、熱処理生成物あるいは混合物に、エラストマーや
DCPII脂などの高分子改質剤、フィラー等を添加す
ることにより凝固点を低下させることが可箋であり、こ
の場合には高分子改質剤やフィラーを含む混合物が上記
温度で液状であればよい。In addition, it is possible to lower the freezing point by adding a polymer modifier such as an elastomer or DCPII resin, or a filler to the heat-treated product or mixture. It is sufficient if the mixture containing the above is liquid at the above temperature.
熱処理生成物とノルボルネン系モノマーとの混合は、パ
ワーミキサー、スタテックミキサー、衝突混合機などの
混合機等を用いて容易に行なうことができるが、熱処理
生成物がワックス状の場合には、熱処理終了後の溶融状
態でノルボルネン系モノマーと混合する方法が能率的で
ある。The heat-treated product and the norbornene monomer can be easily mixed using a mixer such as a power mixer, static mixer, or collision mixer. However, if the heat-treated product is wax-like, the heat-treated An efficient method is to mix the molten state with the norbornene monomer after completion of the process.
(その他の任意成分)
本発明の開環重合用モノマーには、充填剤、酸化防止剤
、顔料、着色剤、高分子改質剤など種々の添加剤を配合
することができ、それにより得られる開環重合体の特性
を改質することができる。(Other optional components) Various additives such as fillers, antioxidants, pigments, colorants, and polymer modifiers can be blended into the monomer for ring-opening polymerization of the present invention, and the resulting The properties of ring-opened polymers can be modified.
充填剤にはガラス、カーボンブラック、タルク、炭酸カ
ルシウム、雲母などの無機質充填剤がある。Fillers include inorganic fillers such as glass, carbon black, talc, calcium carbonate, and mica.
高分子改質剤には、エラストマーや熱重合DCP樹脂な
どがある0例えば、エラストマーを配合すると熱硬化性
樹脂の衝撃強度を高めることができ、熱重合DCP樹脂
を配合すると曲げ弾性率をさらに改良することができる
。高分子改質剤は七ツマー反応溶液に溶解させて配合す
る。Polymer modifiers include elastomers and thermopolymerized DCP resins.For example, blending an elastomer can increase the impact strength of a thermosetting resin, and blending a thermopolymerized DCP resin can further improve the flexural modulus. can do. The polymer modifier is dissolved and blended into the seven-mer reaction solution.
エラストマーとしては、天然ゴム、ポリブタジェン、ポ
リイソプレン、スチレン−ブタジェン−スチレンブロッ
ク共重合体、スチレン−イソプレン−スチレンブロック
共を合体、エチレンニアtrピレンージェンターポリマ
ーなどがある。これらの使用割合は通常0.1〜20重
量%である。Examples of the elastomer include natural rubber, polybutadiene, polyisoprene, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block combination, ethylene nia tr-pyrene terpolymer, and the like. The proportion of these used is usually 0.1 to 20% by weight.
(開環重合用モノマーの重合方法)
本発明の開環重合用モノマーは、公知のメタセシス触媒
および活性剤を用いて重合させることができる。(Polymerization method of monomer for ring-opening polymerization) The monomer for ring-opening polymerization of the present invention can be polymerized using a known metathesis catalyst and activator.
すなわち、本発明の熱処理生成物−たは該生成物とノル
ボルネン系モノマーとの混合物を所定形状の金型内に導
入し、金型中でメタセシス触媒系の存在下に塊状重合せ
しめる重合方法により、熱硬化性S+詣を製造すること
ができる。実質的に塊状重合であればよく、少量の不活
性溶剤が存在していてもかまわない、メタセシス触媒系
は、いずれも七ツマ−に溶解して用いる方が好ましいが
、生成物の性質を本質的に損なわない範囲であれば少量
の溶剤に懸濁または溶解させて用いてもよい。That is, by a polymerization method in which the heat-treated product of the present invention or a mixture of the product and a norbornene monomer is introduced into a mold of a predetermined shape and bulk polymerized in the mold in the presence of a metathesis catalyst system, Thermosetting S+ can be manufactured. Substantially bulk polymerization is sufficient, and the presence of a small amount of inert solvent is acceptable.It is preferable to use the metathesis catalyst system by dissolving it in a 7-mer solution. It may be used by suspending or dissolving it in a small amount of solvent as long as it does not adversely affect the product's performance.
好ましい熱硬化性樹脂の製造法では、前記熱処理生成物
または該生成物とノルボルネン系モノマーとの混合物を
二液に分けて別の容器に入れ、一方にはメタセシス触媒
を、他方には活性剤を添加し、二種類の安定な反応溶液
を調製する。この二種類の反応溶液を混合し1次いで高
温下に保持された成形金型中に注入し、そこで塊状によ
る開4重合を開始し、熱硬化性樹脂を得る。In a preferred method for producing a thermosetting resin, the heat-treated product or a mixture of the product and a norbornene monomer is divided into two liquids and placed in separate containers, one containing a metathesis catalyst and the other containing an activator. to prepare two stable reaction solutions. These two types of reaction solutions are mixed and then poured into a mold kept at a high temperature, where open tetrapolymerization in bulk is initiated to obtain a thermosetting resin.
本発明の開環重合用モノマーの重合においては、従来か
らRIM成形装置として公知の衝突混合装置を、二種類
の反応溶液を混合するために使用することができる。こ
の場合、二種類の反応溶液を納めた容器は別々の流れの
供給源となる。二種類の流れをRIMa&のミキシング
・ヘッドで瞬間的に混合させ、次いで、高温の成形金型
中に注入し、そこで即座に塊状重合させて熱硬化性樹脂
を得る。In the polymerization of the monomer for ring-opening polymerization of the present invention, an impingement mixer conventionally known as a RIM molding device can be used to mix the two reaction solutions. In this case, the vessels containing the two reaction solutions become sources of separate streams. The two streams are instantaneously mixed in a RIMa& mixing head and then injected into a hot mold where they undergo instant bulk polymerization to obtain a thermoset resin.
このように、衝突混合装置を使用できるが、そのような
混合手段に限定されるわけではなく、室温におけるポッ
トライフが1時間もあるような場合には、ミキサー中で
二種類の反応溶液の混合が完了してから、予備加熱した
金型中へ1回もしくは数回にわたって射出あるいは注入
してもよい(例えば特開昭59−51911号参照)、
この方式の場合には、衝突混合装置に比較して、装置を
小型化することができ、また低圧で操作可能という利点
を有する。As described above, an impingement mixing device can be used, but is not limited to such a mixing means, and when the pot life at room temperature is as long as 1 hour, mixing of two reaction solutions in a mixer is possible. After completion of the injection, injection or injection into the preheated mold may be performed once or several times (see, for example, Japanese Patent Application Laid-Open No. 59-51911).
This method has the advantage that the device can be made smaller and can be operated at lower pressure than an impingement mixing device.
また、重合方法としては、前記二種類の反応溶液を使用
する場合に限定されない、当業者であれば容易に理解し
うるように1例えば第三番目の容器に反応液と添加剤を
入れて第三の流れとして使用するなど各種の変形が可能
である。In addition, the polymerization method is not limited to the case where the above two types of reaction solutions are used, but as can be easily understood by those skilled in the art, for example, the reaction solution and additives are placed in a third container and the Various modifications are possible, such as using it as a third flow.
金型温度は50℃以上、好ましくは60〜200℃、特
に好ましくは90〜130℃である。金型圧力は通常0
.1〜100Kg/Cm″の範囲内である。The mold temperature is 50°C or higher, preferably 60-200°C, particularly preferably 90-130°C. Mold pressure is usually 0
.. It is within the range of 1 to 100 Kg/Cm''.
重合時間は適宜選択すればよいが、通常は約20分より
短かく、好ましくは5分以下であるが。The polymerization time may be selected as appropriate, but is usually shorter than about 20 minutes, preferably 5 minutes or less.
それより長くてもよい。It may be longer.
なお2重合反応成分類は窒素ガスなどの不活性ガス雰囲
気下で貯蔵し、また操作しなければならない、成形金型
は不活性ガスでシールしてもよいが、しなくてもかまわ
ない。Note that the bipolymerization reaction components must be stored and operated under an inert gas atmosphere such as nitrogen gas, and the mold may or may not be sealed with an inert gas.
このように、本発明の製造法による七ツマ−は通常のR
IM法で重合させることが可能であり、DCP類を高度
に精製することが必ずしも必要でないため、モノマーコ
ストを低く抑えることができる利点がある。In this way, the seven-spot produced by the production method of the present invention is a normal R
Since it is possible to polymerize by the IM method and it is not necessarily necessary to highly purify DCPs, there is an advantage that the monomer cost can be kept low.
(熱硬化性樹脂の性状)
本発明の七ツマ−を使用して得られる塊状重合体は、冷
却すると硬質な固体となる熱硬化性樹脂である。ガラス
転移点(Tg)は95℃以上、好ましくは100℃以上
であり、高い熱変形温度を有する。(Properties of Thermosetting Resin) The bulk polymer obtained using the seven polymers of the present invention is a thermosetting resin that becomes a hard solid when cooled. The glass transition point (Tg) is 95°C or higher, preferably 100°C or higher, and has a high heat distortion temperature.
実施例
以下に実施例および参考例を挙げて本発明をさらに具体
的に説明するが1本発明はこれら実施例のみに限定され
るものではない、なお1部、比および%はすべ重量基準
である。EXAMPLES The present invention will be described in more detail with reference to examples and reference examples below, but the present invention is not limited to these examples only. All parts, ratios, and percentages are based on total weight. be.
実施例1
500ppmの2.6−ジ−ターシャリ−ブチルフェノ
ール(BIT)を含む純度98.5%のジシクロペンタ
ジェン(D CP)を1皇のオートクレーブに700g
仕込み、十分窒素置換したのち、170℃に昇温し、4
時間反応させて油状物を得た。この油状物の粘度は30
℃で10cpsであり1組成は、未反応DCPが75%
、シクロペンタジェン(c p)の三量体以上の成分が
25、%であった・
実施例2
反応条件を180℃で4時間とする以外は参考例1と全
く同様の操作でワックス状生成物を得た。このワックス
状生成゛物は、凝固点が50℃であり(55℃での粘度
は30cpsである。)、未反応DCPが40%、CP
三景体以上の成分が60%の組成のものであった。Example 1 700 g of 98.5% pure dicyclopentadiene (D CP) containing 500 ppm of 2,6-di-tert-butylphenol (BIT) was placed in a large autoclave.
After the preparation and sufficient nitrogen replacement, the temperature was raised to 170℃, and
An oily substance was obtained after reacting for a period of time. The viscosity of this oil is 30
10 cps at °C and one composition has 75% unreacted DCP.
, the trimer or higher component of cyclopentadiene (cp) was 25%.Example 2 A waxy product was produced in the same manner as in Reference Example 1, except that the reaction conditions were 180°C for 4 hours. I got something. This waxy product has a freezing point of 50°C (viscosity at 55°C is 30 cps), 40% unreacted DCP, CP
The composition was 60% composed of Sankeitai or higher components.
このようにして得たワックス状生成物にざらにDCPを
添加混合し、その混合比率を変えた場合の各凝固点を第
1表に示す。Table 1 shows the solidification points obtained when DCP was roughly added and mixed to the waxy product thus obtained and the mixing ratio was varied.
第1表
実施例3
500ppmのBHTを含む純度94.5%のDCP(
CPダイマーであって、不純物としてプi4ペニルノル
ボルネソ3.2%、インプロペニルツルボ、、 A−0
、7%、ヒールノルボルネンO82%、その他1.4%
を含む1日本ゼオン社製)を用いること以外は実施例1
と同様にして熱処理を行ない、30℃での粘度が10c
psの油状物を得た。この油状物の組成は、未反応DC
Pが76%、CP三量体以上の成分が24%であった。Table 1 Example 3 94.5% pure DCP containing 500 ppm BHT (
CP dimer, containing 3.2% penylnorborneso and impropenylturbo as impurities, A-0
, 7%, heel norbornene O 82%, other 1.4%
Example 1 except that 1 containing Nippon Zeon Co., Ltd.) was used.
Heat treatment was performed in the same manner as above, and the viscosity at 30°C was 10c.
An oil of ps was obtained. The composition of this oil is the unreacted DC
P was 76%, and components of CP trimer or higher were 24%.
参考例1
実施例1で得た油状物を2つの容器に入れ、一方には、
油状物に対しジエチルアルミニウムクロリド(D E
A C)を33ミリモル濃度、n−プロパツールを4.
95ミリモル濃度となるようにそれぞれ添加した(A液
)。Reference Example 1 The oil obtained in Example 1 was placed in two containers, and one contained:
Diethylaluminum chloride (D E
A C) at 33 mmolar concentration and n-propatool at 4.
Each was added to a concentration of 95 mmol (solution A).
他方には、油状物に対し、トリ(トリデシル)アンモニ
ウムモリブデートを4ミリモル濃度となるように添加し
たCB液)。On the other hand, a CB solution in which tri(tridecyl)ammonium molybdate was added to the oil at a concentration of 4 mmol).
これらA、B両反応液をl:lの比率に混合した。この
混合物は、35℃で1時間粘度変化のない安定な状態を
保持した(以下、ポットライフと呼ぶ、)。Both reaction solutions A and B were mixed at a ratio of 1:1. This mixture maintained a stable state with no viscosity change for 1 hour at 35°C (hereinafter referred to as pot life).
両反応液を200X200X2mmの空間容覆を有する
、90℃に加熱された金型の中ヘギャボンプとパワーミ
キサーを用いて速やかに注入した。注入時間は約15秒
であった。注入終了30秒後に急激に発熱し反応が始ま
った。そして、金型内で計3分間反応を行なった。これ
ら一連の操作は窒素ガス雰囲気下で実施した。Both reaction solutions were quickly poured into a mold having a spatial coverage of 200×200×2 mm and heated to 90° C. using a gas pump and a power mixer. Injection time was approximately 15 seconds. 30 seconds after the end of the injection, a sudden heat was generated and the reaction started. Then, the reaction was carried out in the mold for a total of 3 minutes. These series of operations were performed under a nitrogen gas atmosphere.
このようにして得られた成形品のガラス転移点を測定し
たところ110℃であり、曲げ弾性率は21.000K
g/crn’であった。The glass transition point of the molded product thus obtained was measured to be 110°C, and the flexural modulus was 21.000K.
g/crn'.
参考例2
実施例2の第1表に示す各組成の混合物を用いて、参考
例1と全く同様にして(ただし、ワックスのみのものは
液温55℃に加熱して注入した。)、成形品を得た。こ
れらの成形品のポットライフ、ガラス転移点および曲げ
弾性率を第2表に示す。Reference Example 2 Using a mixture of each composition shown in Table 1 of Example 2, molding was carried out in exactly the same manner as in Reference Example 1 (however, the wax-only mixture was heated to a liquid temperature of 55°C and injected). I got the item. Table 2 shows the pot life, glass transition point, and flexural modulus of these molded products.
(以下余白)
#!2表
本り5℃−−輪作
本末50℃でのポットライフ
実施例4
実施例2で得たワックス状生成物50部、DCP30部
、メチルテトラサイクロドデセン20部の比率からなる
混合物を、各成分を55℃で混合して調製した。混合物
の凝固点は0℃以下であり、30℃での粘度は200P
Sであった。(Left below) #! Table 2: Pot life at 5°C - end of crop rotation at 50°C Example 4 A mixture consisting of 50 parts of the waxy product obtained in Example 2, 30 parts of DCP, and 20 parts of methyltetracyclododecene was added to each It was prepared by mixing the ingredients at 55°C. The freezing point of the mixture is below 0℃, and the viscosity at 30℃ is 200P
It was S.
この混合物を用い参考例1と同様にして重合を行ったと
ころ、得られた成形品のTgは130℃1曲げ弾性率は
27,500Kg/Cm″であった。Using this mixture, polymerization was carried out in the same manner as in Reference Example 1, and the resulting molded article had a Tg of 130° C. and a flexural modulus of 27,500 Kg/Cm''.
参考例3
実施例1で得た油状物を2つの容器に入れ、一方には、
油状物に対し、DEACを48ミリモル濃度になるよう
に添加し、他方の容器には、六塩化タングステンを7ミ
リモル濃度となるように添加した。このようにして調製
した2種類の反応液をl:lの混合比率になるように、
衝突混合型のRIM機を用い、参考例1と同様の金型、
温度条件下で射出成形した。Reference Example 3 The oil obtained in Example 1 was placed in two containers, and one contained:
DEAC was added to the oil at a concentration of 48 mmolar, and tungsten hexachloride was added to the other vessel at a concentration of 7 mmolar. The two types of reaction solutions prepared in this way were mixed at a mixing ratio of 1:1.
Using a collision mixing type RIM machine, the same mold as in Reference Example 1,
Injection molded under temperature conditions.
このようにして得られた成形品のTgは168℃であっ
た。なお、混合物の35℃におけるポットライフは約1
5秒であった。The molded article thus obtained had a Tg of 168°C. The pot life of the mixture at 35°C is approximately 1
It was 5 seconds.
参考例3
実施例3で得た油状物を用いること以外は参考例1と同
様にして成形品を得た。得られた成形品のTgは105
℃、曲げ弾性率は21,000K g/ Crn’であ
った・
実施例5
実施例3で使用した純度94.5%のDCPを用いるこ
と以外は実施例2と全く同様の操作でワックス状生成物
を得た。このワックス状の生成物は凝固点が45℃であ
り、50℃での粘度は30cpsであった。また、未反
応DCPが42%、CP三量体以上が58%の組成のも
のであった。Reference Example 3 A molded article was obtained in the same manner as in Reference Example 1 except that the oil obtained in Example 3 was used. The Tg of the obtained molded product is 105
℃, and the flexural modulus was 21,000 K g/Crn'.Example 5 A wax-like product was produced in the same manner as in Example 2 except for using the DCP with a purity of 94.5% used in Example 3. I got something. This waxy product had a freezing point of 45°C and a viscosity of 30 cps at 50°C. Furthermore, the composition was 42% unreacted DCP and 58% CP trimer or more.
このようにして得たワックス状生成物50部。50 parts of the waxy product thus obtained.
DCPを50部の比率からなる混合物を参考例1と同様
にして、成形品を得た。A molded article was obtained using a mixture containing 50 parts of DCP in the same manner as in Reference Example 1.
混合物の凝固点は3℃であり、得られた成形品のTgは
115℃、曲げ弾性率は23.500K g / c
m″であった。The freezing point of the mixture is 3℃, the Tg of the obtained molded product is 115℃, and the flexural modulus is 23.500K g/c
It was m''.
発明の効果
本発明によれば、ジシクロペンタジェン類を単に熱処理
するだけで、またはこの熱処理生成物とノルボルネン系
モノマーとを混合するだけで高度の重合活性を有する開
環重合用七ツマ−を得ることができ、不純物を含む粗D
CPの場合であっても、必ずしも蒸留等の特別な精製を
行なう必要がないので七ツマーコストを低減させること
ができる。Effects of the Invention According to the present invention, it is possible to produce a hexamer for ring-opening polymerization having a high degree of polymerization activity by simply heat-treating dicyclopentadiene or by mixing the heat-treated product with a norbornene monomer. Crude D that can be obtained and contains impurities
Even in the case of CP, it is not necessary to carry out special purification such as distillation, so the cost can be reduced.
しかも、この七ツマ−を用いることにより、従来のポリ
DCPポリマーに比較して熱変形温度および曲げ弾性率
に優れた熱硬化性樹脂を経済的に得ることができる。そ
して、この樹脂は耐熱性を要求される様々な分野に適用
可能であるという優れた効果を有する。Moreover, by using this 7-mer, it is possible to economically obtain a thermosetting resin that has superior heat deformation temperature and flexural modulus compared to conventional polyDCP polymers. This resin has the excellent effect of being applicable to various fields requiring heat resistance.
Claims (1)
、次いで必要に応じてノルボルネン系モノマーを混合す
ることを特徴とする開環重合用モノマーの製造法。A method for producing a monomer for ring-opening polymerization, which comprises heat-treating dicyclopentadiene at 120 to 250°C, and then mixing a norbornene monomer as necessary.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62065671A JPH082947B2 (en) | 1987-03-23 | 1987-03-23 | Method for producing monomer for ring-opening polymerization |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62065671A JPH082947B2 (en) | 1987-03-23 | 1987-03-23 | Method for producing monomer for ring-opening polymerization |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63234017A true JPS63234017A (en) | 1988-09-29 |
JPH082947B2 JPH082947B2 (en) | 1996-01-17 |
Family
ID=13293693
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62065671A Expired - Lifetime JPH082947B2 (en) | 1987-03-23 | 1987-03-23 | Method for producing monomer for ring-opening polymerization |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH082947B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01198621A (en) * | 1987-10-01 | 1989-08-10 | B F Goodrich Co:The | Production of resionous monomer and cycloolefin polymer composition obtained therefrom |
JPH01268718A (en) * | 1988-04-20 | 1989-10-26 | Nippon Oil Co Ltd | Production of polymer |
JPH0284428A (en) * | 1988-04-08 | 1990-03-26 | B F Goodrich Co:The | Method for heightening polymerization activity of cycloolefin monomer for bulk polymerization |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63227623A (en) * | 1987-02-26 | 1988-09-21 | 帝人メトン株式会社 | Methathesis polymer of thermally oligomerized dicyclopentadiene and its production |
-
1987
- 1987-03-23 JP JP62065671A patent/JPH082947B2/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63227623A (en) * | 1987-02-26 | 1988-09-21 | 帝人メトン株式会社 | Methathesis polymer of thermally oligomerized dicyclopentadiene and its production |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01198621A (en) * | 1987-10-01 | 1989-08-10 | B F Goodrich Co:The | Production of resionous monomer and cycloolefin polymer composition obtained therefrom |
JPH0284428A (en) * | 1988-04-08 | 1990-03-26 | B F Goodrich Co:The | Method for heightening polymerization activity of cycloolefin monomer for bulk polymerization |
JPH01268718A (en) * | 1988-04-20 | 1989-10-26 | Nippon Oil Co Ltd | Production of polymer |
Also Published As
Publication number | Publication date |
---|---|
JPH082947B2 (en) | 1996-01-17 |
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