JP2008088154A - New alicyclic compound, method for producing the same and polymer composition - Google Patents
New alicyclic compound, method for producing the same and polymer composition Download PDFInfo
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- JP2008088154A JP2008088154A JP2007088562A JP2007088562A JP2008088154A JP 2008088154 A JP2008088154 A JP 2008088154A JP 2007088562 A JP2007088562 A JP 2007088562A JP 2007088562 A JP2007088562 A JP 2007088562A JP 2008088154 A JP2008088154 A JP 2008088154A
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- Prior art keywords
- alicyclic
- general formula
- compound
- formula
- following general
- Prior art date
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- 150000001334 alicyclic compounds Chemical class 0.000 title claims abstract description 24
- 229920000642 polymer Polymers 0.000 title claims description 29
- 239000000203 mixture Substances 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- -1 monoterpene compound Chemical class 0.000 claims abstract description 63
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 58
- 229930003658 monoterpene Natural products 0.000 claims abstract description 20
- 235000002577 monoterpenes Nutrition 0.000 claims abstract description 20
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 13
- 125000000524 functional group Chemical group 0.000 claims abstract description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 26
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 229920002554 vinyl polymer Polymers 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 230000003287 optical effect Effects 0.000 abstract description 4
- 239000012776 electronic material Substances 0.000 abstract description 2
- 230000000704 physical effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 67
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 23
- 239000002904 solvent Substances 0.000 description 23
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 20
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 18
- 150000008064 anhydrides Chemical class 0.000 description 17
- 150000003949 imides Chemical class 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 15
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- 230000005587 bubbling Effects 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 229910001873 dinitrogen Inorganic materials 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- YHQGMYUVUMAZJR-UHFFFAOYSA-N α-terpinene Chemical compound CC(C)C1=CC=C(C)CC1 YHQGMYUVUMAZJR-UHFFFAOYSA-N 0.000 description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 150000003613 toluenes Chemical class 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000008065 acid anhydrides Chemical class 0.000 description 6
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 229920002799 BoPET Polymers 0.000 description 5
- 0 C*N(C(C12C34C(C5)[C@@](C)CC1C5C23)=O)C4=O Chemical compound C*N(C(C12C34C(C5)[C@@](C)CC1C5C23)=O)C4=O 0.000 description 5
- 238000005698 Diels-Alder reaction Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 description 4
- WSTYNZDAOAEEKG-UHFFFAOYSA-N Mayol Natural products CC1=C(O)C(=O)C=C2C(CCC3(C4CC(C(CC4(CCC33C)C)=O)C)C)(C)C3=CC=C21 WSTYNZDAOAEEKG-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000007112 amidation reaction Methods 0.000 description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 4
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000012719 thermal polymerization Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 244000028419 Styrax benzoin Species 0.000 description 3
- 235000000126 Styrax benzoin Nutrition 0.000 description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 description 3
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 235000019382 gum benzoic Nutrition 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000006358 imidation reaction Methods 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- GRWFGVWFFZKLTI-IUCAKERBSA-N (-)-α-pinene Chemical compound CC1=CC[C@@H]2C(C)(C)[C@H]1C2 GRWFGVWFFZKLTI-IUCAKERBSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-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
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
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- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- UMLWXYJZDNNBTD-UHFFFAOYSA-N alpha-dimethylaminoacetophenone Natural products CN(C)CC(=O)C1=CC=CC=C1 UMLWXYJZDNNBTD-UHFFFAOYSA-N 0.000 description 2
- 230000009435 amidation Effects 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 229960002130 benzoin Drugs 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- PVEOYINWKBTPIZ-UHFFFAOYSA-N but-3-enoic acid Chemical compound OC(=O)CC=C PVEOYINWKBTPIZ-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- TXXHDPDFNKHHGW-UHFFFAOYSA-N muconic acid Chemical compound OC(=O)C=CC=CC(O)=O TXXHDPDFNKHHGW-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 2
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- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 description 1
- LRTOHSLOFCWHRF-UHFFFAOYSA-N 1-methyl-1h-indene Chemical compound C1=CC=C2C(C)C=CC2=C1 LRTOHSLOFCWHRF-UHFFFAOYSA-N 0.000 description 1
- PEHHIFQTECNPHG-UHFFFAOYSA-N 1-tert-butylperoxy-2-methylcyclohexane Chemical compound CC1CCCCC1OOC(C)(C)C PEHHIFQTECNPHG-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Indole Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、新規脂環式化合物、新規脂環式化合物の製造方法および重合体組成物に関する。より詳細には、天然原料(モノテルペン化合物)を用いた新規脂環式化合物、新規脂環式化合物の製造方法、ならびに該モノマーを重合してなる重合体組成物に関する。 The present invention relates to a novel alicyclic compound, a method for producing a novel alicyclic compound, and a polymer composition. More specifically, the present invention relates to a novel alicyclic compound using a natural raw material (monoterpene compound), a method for producing the novel alicyclic compound, and a polymer composition obtained by polymerizing the monomer.
脂環構造を有する重合性モノマーは、特に電子材料や光学材料の分野で賞用されており、これら材料の各種性能(耐熱性や強度、透明性、耐湿性等)を一層向上させるべく、種々の分子構造が検討されている。例えば特許文献1に係る特定の脂環イミドアクリレートは、耐熱性等に優れた重合体組成物を与えるとされている。しかし、従来の脂環系重合性モノマーは、脂環構造が石油系原料に由来するものであり、原油価格の変動に伴う製品コストの高騰や、環境負荷、資源枯渇といった問題があった。
本発明は、天然物由来の原料を用いた新規な脂環式化合物を提供することを主な目的とする。 The main object of the present invention is to provide a novel alicyclic compound using a natural product-derived raw material.
本発明者は、天然原料由来の脂環式化合物について鋭意検討を重ねた結果、モノテルペン化合物に由来する脂環骨格を有する脂環式化合物が新規であり、当該化合物を合成する方法を見出し、本発明を完成するに到った。 As a result of intensive studies on alicyclic compounds derived from natural raw materials, the present inventor has found an alicyclic compound having an alicyclic skeleton derived from a monoterpene compound, and has found a method for synthesizing the compound. The present invention has been completed.
即ち本発明は、下記一般式(1)で示す脂環式化合物; That is, the present invention provides an alicyclic compound represented by the following general formula (1);
下記工程(I)と工程(II)を経由することを特徴とする、下記一般式(1)で示す脂環式化合物の製造方法; A process for producing an alicyclic compound represented by the following general formula (1), characterized by passing through the following steps (I) and (II);
(式中、R1は、下記一般式(2)で示す官能基を、またR2はモノテルペン化合物に由来する脂環骨格を表す。) (In the formula, R 1 represents a functional group represented by the following general formula (2), and R 2 represents an alicyclic skeleton derived from a monoterpene compound.)
[工程(I)]
下記一般式(4−1)で示される脂環式ジカルボン酸または下記一般式(4−2)で示される脂環式ジカルボン酸無水物に、下記一般式(5)で示されるモノアミン化合物を反応させて、下記一般式(6)で示される脂環式マレイミド化合物を製造する工程。
[Process (I)]
The monoamine compound represented by the following general formula (5) is reacted with the alicyclic dicarboxylic acid represented by the following general formula (4-1) or the alicyclic dicarboxylic acid anhydride represented by the following general formula (4-2). A step of producing an alicyclic maleimide compound represented by the following general formula (6).
(式(4−1)および(4−2)中、R2は前記同様である。) (In formulas (4-1) and (4-2), R 2 is the same as described above.)
(式(5)中、R3、R4、nは前記同様である。また、R6は水酸基またはハロゲン原子を表す。) (In Formula (5), R 3 , R 4 , and n are the same as described above. R 6 represents a hydroxyl group or a halogen atom.)
(式(6)中、R2、R3、R4、n、R6は前記同様である。) (In formula (6), R 2 , R 3 , R 4 , n, and R 6 are the same as above.)
[工程(II)]
一般式(6)で表される該脂環式マレイミド化合物に、下記一般式(7)で示すビニル化合物を反応させる工程。
[Process (II)]
A step of reacting the alicyclic maleimide compound represented by the general formula (6) with a vinyl compound represented by the following general formula (7).
(式(7)中、mおよびR5は前記同様である) (In formula (7), m and R 5 are the same as above)
および、前記脂環式化合物を重合してなる重合体組成物に関する。 The present invention also relates to a polymer composition obtained by polymerizing the alicyclic compound.
本発明の脂環式化合物は、天然原料(モノテルペン化合物)を用いたものであるため、従来の石油系原料を用いた脂環式化合物と比べて、環境負荷等の問題が小さい。また、このものは、アルキル基が結合した嵩高いビシクロ骨格、または、長鎖アルキル基が結合したシクロ骨格を有しており、従来の脂環式化合物とは異なる有利な効果(例えば、その重合体の、高耐熱性、低吸水性、低透湿性など)が期待される。 Since the alicyclic compound of the present invention uses natural raw materials (monoterpene compounds), problems such as environmental burden are small compared to conventional alicyclic compounds using petroleum-based raw materials. In addition, this compound has a bulky bicyclo skeleton to which an alkyl group is bonded or a cyclo skeleton to which a long chain alkyl group is bonded, and has an advantageous effect different from that of a conventional alicyclic compound (for example, its heavy weight). High heat resistance, low water absorption, low moisture permeability, etc.) are expected.
また、本発明の脂環式化合物を重合してなる重合体組成物は、各種の工学材料、例えば光学材料〔光ディスク記録媒体用オーバーコート剤、ハードコート剤、溝材、レンズ等〕や、電子材料〔層間絶縁膜、レジスト、ダイボンド剤、ダイオード・水晶振動子等の接着剤、ダイオード等の素子、モールド部材、ダイボンドフィルム、ソルダーレジスト等〕としても有用であることが期待される。また、該重合体組成物は、塗料用バインダー、印刷インキ用バインダー、接着剤、粘着剤、歯科材料、製紙用薬品等の他、各種成形品としても有用であると期待され、例えばレンズ〔フレネルレンズ、レンチキュラーレンズ、プリズムシート等〕においても有用であることが期待される。 In addition, the polymer composition obtained by polymerizing the alicyclic compound of the present invention includes various engineering materials such as optical materials (overcoat agents for optical disk recording media, hard coat agents, groove materials, lenses, etc.), electronic It is also expected to be useful as a material (interlayer insulating film, resist, die bond agent, adhesive such as a diode / crystal resonator, element such as a diode, mold member, die bond film, solder resist, etc.). The polymer composition is also expected to be useful as various molded products in addition to paint binders, printing ink binders, adhesives, pressure-sensitive adhesives, dental materials, papermaking chemicals, and the like. For example, lenses [Fresnel Lens, lenticular lens, prism sheet, and the like].
本発明に係る脂環式化合物(以下、脂環イミドアクリレートという)は、下記一般式(1)で示される。 The alicyclic compound (hereinafter referred to as alicyclic imide acrylate) according to the present invention is represented by the following general formula (1).
前記一般式(1)で示す脂環式化合物のR2(モノテルペン化合物に由来する脂環骨格)は特に限定されないが、該脂環式化合物は、具体的には下記一般式(3−1)、(3−2)、(3−3)および(3−4)から選ばれる1種で示される構造であるのが好ましい。なお、一般式(3−1)の脂環骨格はα−テルピネンに、一般式(3−2)のそれはα−フェランドレンに、一般式(3−3)のそれはミルセンに、一般式(3−4)のそれはアロオメシンに由来する。 R 2 of the alicyclic compound represented by the general formula (1) (an alicyclic skeleton derived from the monoterpene compound) is not particularly limited, but the alicyclic compound specifically includes the following general formula (3-1) ), (3-2), (3-3) and (3-4) are preferred. The alicyclic skeleton of the general formula (3-1) is α-terpinene, that of the general formula (3-2) is α-ferrandrene, that of the general formula (3-3) is myrcene, and the general formula (3 It is derived from aloomesin in -4).
(各式中、R1は前記一般式(2)で示す官能基を表す。なお、破線部はその炭素−炭素結合が不飽和結合であってもよいことを表す。) (In each formula, R 1 represents the functional group represented by the general formula (2). The broken line portion represents that the carbon-carbon bond may be an unsaturated bond.)
前記一般式(1)で示す脂環イミドアクリレートの製造方法は特に限定されないが、例えば、下記工程(I)と工程(II)を経由することにより製造することができる。 Although the manufacturing method of alicyclic imide acrylate shown by the said General formula (1) is not specifically limited, For example, it can manufacture by passing through the following process (I) and process (II).
[工程(I)]
下記一般式(4−1)で示される脂環式ジカルボン酸または下記一般式(4−2)で示される脂環式ジカルボン酸無水物(以下、両者を脂環式ジカルボン酸(無水物)と略すことがある)に、下記一般式(5)で示されるモノアミン化合物を反応させて、下記一般式(6)で示される脂環式マレイミド化合物を製造する工程。
[Process (I)]
The alicyclic dicarboxylic acid represented by the following general formula (4-1) or the alicyclic dicarboxylic acid anhydride represented by the following general formula (4-2) (hereinafter referred to as alicyclic dicarboxylic acid (anhydride)) A step of producing a cycloaliphatic maleimide compound represented by the following general formula (6) by reacting a monoamine compound represented by the following general formula (5) with the monoamine compound represented by the following general formula (5).
(式(4−1)および(4−2)中、R2はモノテルペン化合物に由来する脂環骨格を表す。) (In formulas (4-1) and (4-2), R 2 represents an alicyclic skeleton derived from a monoterpene compound.)
(式(5)中、R3およびR4はそれぞれ水素原子またはメチル基を、nは1〜6の整数を、R6は水酸基またはハロゲン原子を表す。) (In Formula (5), R 3 and R 4 each represent a hydrogen atom or a methyl group, n represents an integer of 1 to 6, and R 6 represents a hydroxyl group or a halogen atom.)
(式(6)中、R2、R3、R4、n、R6は前記同様である。) (In formula (6), R 2 , R 3 , R 4 , n, and R 6 are the same as above.)
[工程(II)]
前記一般式(6)で表される脂環式マレイミド化合物に、下記一般式(7)で示すビニル化合物を反応させる工程。
[Process (II)]
A step of reacting the alicyclic maleimide compound represented by the general formula (6) with a vinyl compound represented by the following general formula (7).
(式(7)中、mは0〜12の整数を、R5は水素原子またはメチル基を表す。) (In Formula (7), m represents an integer of 0 to 12, and R 5 represents a hydrogen atom or a methyl group.)
[工程(I)について]
前記一般式(4−1)または(4−2)で示す脂環式ジカルボン酸(無水物)は、例えば、各種公知のモノテルペン化合物と、マレイン酸(無水物)(マレイン酸またはマレイン酸無水物をいう)とを、各種公知の方法でディールス・アルダー反応させることにより得ることができる。他にも、一般式(4−1)の脂環式ジカルボン酸は、該モノテルペン化合物とマレイン酸ジアルキルエステルとのディールス・アルダー反応物を、更に各種公知の方法で加水分解することによっても得ることができる。また、一般式(4−2)で示す脂環式ジカルボン酸無水物は、該脂環式ジカルボン酸を各種公知の方法で脱水縮合することにより得ることもできる。なお、該脂環式ジカルボン酸(無水物)としては、後述のアミド化ないしイミド化反応が容易に進行しやすくなることから、脂環式ジカルボン酸無水物が好ましい。
[About step (I)]
The alicyclic dicarboxylic acid (anhydride) represented by the general formula (4-1) or (4-2) includes, for example, various known monoterpene compounds and maleic acid (anhydride) (maleic acid or maleic anhydride). Can be obtained by Diels-Alder reaction by various known methods. In addition, the alicyclic dicarboxylic acid of the general formula (4-1) can also be obtained by hydrolyzing the Diels-Alder reaction product of the monoterpene compound and the dialkyl maleate with various known methods. be able to. Moreover, the alicyclic dicarboxylic acid anhydride represented by the general formula (4-2) can also be obtained by dehydrating and condensing the alicyclic dicarboxylic acid by various known methods. The alicyclic dicarboxylic acid (anhydride) is preferably an alicyclic dicarboxylic acid anhydride because an amidation or imidation reaction described later easily proceeds.
該モノテルペン化合物としては、具体的には、分子内に共役二重結合を有するモノテルペン化合物を用いることができ、好ましくは、α-テルピネン(下記一般式(8−1))、α−フェランドレン(下記一般式(8−2))等の環式モノテルペン化合物や、ミルセン(下記一般式(8−3))、アロオメシン(下記一般式(8−4))等の非環式モノテルペン化合物を用いることができる。
ここに、α-テルピネンを用いた脂環イミドアクリレートは前記一般式(3−1)に、α−フェランドレンを用いた脂環イミドアクリレートは前記一般式(3−2)に、ミルセンを用いた脂環イミドアクリレートは前記一般式(3−3)に、アロオメシンを用いた脂環イミドアクリレートは前記一般式(3−4)または(3−5)(両者は異性体の関係にある)に対応する。
なお、該モノテルペン化合物はいずれも、高純度の市販品(通常85%以上)がそのまま利用できる。また、本発明で用いるモノテルペン化合物には、他の環式または非環式のモノテルペン化合物(例えばβ−フェランドレン、β-テルピネン、γ-テルピネン、α−ピネン、オシメン等)が残分として含まれていてもよい。
As the monoterpene compound, specifically, a monoterpene compound having a conjugated double bond in the molecule can be used, preferably α-terpinene (the following general formula (8-1)), α-ferran Cyclic monoterpene compounds such as drain (the following general formula (8-2)) and acyclic monoterpenes such as myrcene (the following general formula (8-3)) and aloomesin (the following general formula (8-4)) Compounds can be used.
Here, alicyclic imide acrylate using α-terpinene was used in the general formula (3-1), and alicyclic imide acrylate using α-ferrandrene was used in the general formula (3-2). The alicyclic imide acrylate corresponds to the general formula (3-3), and the alicyclic imide acrylate using aloomesin corresponds to the general formula (3-4) or (3-5) (both are in an isomer relationship). To do.
In addition, as for this monoterpene compound, the high purity commercial item (usually 85% or more) can be utilized as it is. The monoterpene compound used in the present invention includes other cyclic or acyclic monoterpene compounds (for example, β-ferrandrene, β-terpinene, γ-terpinene, α-pinene, osymene, etc.) as a residue. It may be included.
ディールス・アルダー反応は特に限定されず、各種公知の方法を利用できる。具体的には、例えば、前記モノテルペン化合物1モルと、これに対し通常0.8〜1.2モル程度となるマレイン酸(無水物)とを、通常室温〜200℃程度の温度で、通常3〜12時間程度反応させればよい。なお、脂環式ジカルボン酸(無水物)の着色を考慮して、反応容器は密閉構造とし、更に窒素等の不活性ガスでパージするのが好ましい。また、反応の際には、各種公知の溶媒〔ベンゼン、トルエン、キシレン、n−ペンタン、n−ヘキサン、n−ペンタン、シクロペンタン、酢酸メチル、酢酸エチル、酢酸イソブチル等〕から選ばれる1種を単独で、または組み合わせて用いることができる。こうして得られた脂環式ジカルボン酸(無水物)は、各種の精製手段〔減圧蒸留、水蒸気蒸留、溶媒抽出、再結晶、シリカゲルカラムクロマトグラフィー等〕で精製することもできる。 The Diels-Alder reaction is not particularly limited, and various known methods can be used. Specifically, for example, 1 mol of the monoterpene compound and maleic acid (anhydride), which is usually about 0.8 to 1.2 mol, are usually used at a temperature of about room temperature to about 200 ° C. What is necessary is just to make it react for about 3 to 12 hours. In consideration of the coloring of the alicyclic dicarboxylic acid (anhydride), it is preferable that the reaction vessel has a sealed structure and further purged with an inert gas such as nitrogen. In the reaction, one kind selected from various known solvents [benzene, toluene, xylene, n-pentane, n-hexane, n-pentane, cyclopentane, methyl acetate, ethyl acetate, isobutyl acetate, etc.] They can be used alone or in combination. The alicyclic dicarboxylic acid (anhydride) thus obtained can be purified by various purification means [vacuum distillation, steam distillation, solvent extraction, recrystallization, silica gel column chromatography, etc.].
また、得られた脂環式ジカルボン酸(無水物)が、分子中の脂環骨格(R2)に炭素−炭素不飽和結合を含む場合には、該脂環式ジカルボン酸(無水物)を水素化反応に供して、当該炭素−炭素不飽和結合を飽和結合にすることもできる。水素化反応は特に制限されず、各種公知の方法を利用できる。具体的には、例えば、前記脂環式ジカルボン酸(無水物)を、各種公知の金属触媒〔安定化ニッケルやパラジウム、パラジウムカーボン、白金等〕と、必要に応じてTHF等の溶媒との存在下で、通常9.8MPa以下(好ましくは0.98〜9.8MPa)の水素圧、室温〜300℃程度の温度、3〜24時間程度の条件で水素化反応させればよい。 Further, when the obtained alicyclic dicarboxylic acid (anhydride) contains a carbon-carbon unsaturated bond in the alicyclic skeleton (R 2 ) in the molecule, the alicyclic dicarboxylic acid (anhydride) is The carbon-carbon unsaturated bond can be converted to a saturated bond by subjecting it to a hydrogenation reaction. The hydrogenation reaction is not particularly limited, and various known methods can be used. Specifically, for example, the alicyclic dicarboxylic acid (anhydride) is present in various known metal catalysts (stabilized nickel, palladium, palladium carbon, platinum, etc.) and, if necessary, a solvent such as THF. The hydrogenation reaction may be carried out under conditions of a hydrogen pressure of usually 9.8 MPa or less (preferably 0.98 to 9.8 MPa), a temperature of room temperature to about 300 ° C., and a time of about 3 to 24 hours.
前記一般式(5)で示すモノアミン化合物としては、前記一般式(5)中のR6の種類に応じて、各種公知のものを用いることができる。具体的には、例えば、R6が水酸基の場合には、各種公知のモノアミノアルコール類〔エタノールアミン、プロパノールアミン、ブタノールアミン等〕を例示できる。また、R6がハロゲン原子(フッ素、塩素、臭素等)の場合には、各種公知のハロゲン化アルキルアミン類〔2−クロロエチルアミン、2−ブロモエチルアミン、1−アミノ−2−プロピルクロライド等〕を例示できる。これらの中でも、入手容易で安価な点より、前記モノアミノアルコール類、特にエタノールアミンが好ましい。 As the monoamine compound represented by the general formula (5), various known compounds can be used depending on the type of R 6 in the general formula (5). Specifically, for example, when R 6 is a hydroxyl group, various known monoamino alcohols [ethanolamine, propanolamine, butanolamine and the like] can be exemplified. When R 6 is a halogen atom (fluorine, chlorine, bromine, etc.), various known halogenated alkylamines [2-chloroethylamine, 2-bromoethylamine, 1-amino-2-propyl chloride, etc.] It can be illustrated. Among these, the monoamino alcohols, particularly ethanolamine is preferable from the viewpoint of availability and inexpensiveness.
前記脂環式ジカルボン酸(無水物)と前記モノアミン化合物との反応は、各種公知のアミド化・イミド化反応による。具体的には、例えば、前記脂環式ジカルボン酸(無水物)1モルと、これに対し通常0.5〜3モル程度となる前記モノアミン化合物とを、通常は水と共沸する溶媒(トルエン等)の存在下、通常10℃〜70℃程度の温度で、通常1〜12時間程度アミド化反応を行い、更に、通常80℃〜180℃程度の温度で、通常3〜20時間程度イミド化反応(脱水閉環反応)させればよい。 The reaction between the alicyclic dicarboxylic acid (anhydride) and the monoamine compound is based on various known amidation and imidation reactions. Specifically, for example, 1 mol of the alicyclic dicarboxylic acid (anhydride) and the monoamine compound, which is usually about 0.5 to 3 mol, are usually a solvent (toluene) azeotroped with water. Etc.) in the presence of an amidation reaction, usually at a temperature of about 10 ° C. to 70 ° C., usually for about 1 to 12 hours, and further at a temperature of about 80 ° C. to 180 ° C., usually for about 3 to 20 hours. What is necessary is just to make it react (dehydration ring closure reaction).
なお、アミド化反応時には、反応を促進する目的で、各種公知の酸又は塩基触媒を用いてもよい。具体的には、例えば、各種公知の有機スルホン酸〔アルキルスルホン酸、p−トルエンスルホン酸、ベンゼンスルホン酸等〕、無機酸〔硫酸、亜リン酸等〕、塩基性化合物〔ピリジン、トリメチルアミン、トリエチルアミン等〕等を、前記脂環式ジカルボン酸(無水物)1モルに対して通常0.0005〜0.05モル程度用いることができる。 In the amidation reaction, various known acid or base catalysts may be used for the purpose of promoting the reaction. Specifically, for example, various known organic sulfonic acids [alkylsulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, etc.], inorganic acids [sulfuric acid, phosphorous acid, etc.], basic compounds [pyridine, trimethylamine, triethylamine, etc.] Etc.] can usually be used in an amount of about 0.0005 to 0.05 mol with respect to 1 mol of the alicyclic dicarboxylic acid (anhydride).
また、イミド化反応時には、50℃〜100℃程度の低温域で反応を行う目的で、各種公知の触媒を用いてもよい。具体的には、例えば、ジシクロヘキシルカルボジイミドや無水酢酸などの脱水剤と、ピリジン、トリエチルアミン、酢酸ナトリウムなどの塩基性化合物の組み合わせたものを利用できる。なお、当該塩基性化合物の使用量は、脱水剤1モルに対し、通常1〜5モル程度である。 In the imidation reaction, various known catalysts may be used for the purpose of performing the reaction in a low temperature range of about 50 ° C to 100 ° C. Specifically, for example, a combination of a dehydrating agent such as dicyclohexylcarbodiimide or acetic anhydride and a basic compound such as pyridine, triethylamine or sodium acetate can be used. In addition, the usage-amount of the said basic compound is about 1-5 mol normally with respect to 1 mol of dehydrating agents.
また、両反応時には、必要に応じて各種の重合禁止措置をとることができる。具体的には、例えば、重合禁止剤(フェノール類、ジチオカルバミン酸塩類、フェノチアジン類等)を、前記脂環式ジカルボン酸(無水物)1モルに対して通常0.0001〜0.01モル%程度用いたり、反応系を空気や酸素でバブリングしたりすることができる。 In both reactions, various polymerization prohibition measures can be taken as necessary. Specifically, for example, a polymerization inhibitor (phenols, dithiocarbamates, phenothiazines, etc.) is usually about 0.0001 to 0.01 mol% with respect to 1 mol of the alicyclic dicarboxylic acid (anhydride). It can be used or the reaction system can be bubbled with air or oxygen.
こうして得られた、前記一般式(6)で示す脂環式マレイミド化合物は、前記精製手段で精製してもよい。また、該脂環式マレイミド化合物が、分子中の脂環骨格に炭素−炭素不飽和結合を含む場合には、この段階においても前記同様に水素化反応を適用してもよい。 The alicyclic maleimide compound represented by the general formula (6) thus obtained may be purified by the purification means. Further, when the alicyclic maleimide compound contains a carbon-carbon unsaturated bond in the alicyclic skeleton in the molecule, a hydrogenation reaction may be applied at this stage as described above.
[工程(II)について]
該脂環式マレイミド化合物に、前記一般式(7)で示すビニル化合物を反応させる方法は、前記一般式(6)中のR6の種類により異なる。例えば、R6が水酸基である場合には、当該脂環式マレイミド化合物と前記ビニル化合物とをエステル化反応させればよい。また、R6がハロゲン原子である場合には、当該脂環式マレイミド化合物と前記ビニル化合物とを各種公知の方法で置換反応させればよい。
[About Process (II)]
The method of reacting the alicyclic maleimide compound with the vinyl compound represented by the general formula (7) differs depending on the type of R 6 in the general formula (6). For example, when R 6 is a hydroxyl group, the alicyclic maleimide compound and the vinyl compound may be esterified. When R 6 is a halogen atom, the alicyclic maleimide compound and the vinyl compound may be subjected to a substitution reaction by various known methods.
該ビニル化合物の具体例としては、例えばアクリル酸、メタクリル酸、3−ブテン酸、4−ペンテン酸等が挙げられる。 Specific examples of the vinyl compound include acrylic acid, methacrylic acid, 3-butenoic acid, 4-pentenoic acid and the like.
前記エステル化反応は特に限定されず、各種公知の方法を利用できる。具体的には、例えば、前記脂環式マレイミド化合物1モルと、これに対し通常0.5〜20モル程度となる前記ビニル化合物とを、通常20℃〜150℃程度の温度で、通常2〜20時間程度反応させればよい。なお、反応時には、水と共沸する芳香族系溶媒(好ましくはトルエン)を用い、水を反応系から除去しながら反応を行うのが好ましい。また、必要に応じて各種公知のエステル化触媒、例えば酸触媒〔p−トルエンスルホン酸、硫酸等〕、金属酸化物・水酸化物〔水酸化リチウム、酸化カルシウム、酸化マグネシウム等〕を、前記マレイミド化合物1モルに対し、通常0.001〜0.2モル程度用いることができる。また、必要に応じて前記重合禁止措置を適用することもできる。重合禁止剤の使用量は、該脂環式マレイミド化合物1モルに対して通常0.0001〜0.01モル%程度である。 The esterification reaction is not particularly limited, and various known methods can be used. Specifically, for example, 1 mol of the alicyclic maleimide compound and the vinyl compound which is usually about 0.5 to 20 mol are usually 2 to 20 ° C. What is necessary is just to make it react for about 20 hours. In the reaction, it is preferable to use an aromatic solvent (preferably toluene) azeotroped with water and perform the reaction while removing water from the reaction system. If necessary, various known esterification catalysts such as acid catalysts (p-toluenesulfonic acid, sulfuric acid, etc.), metal oxides / hydroxides (lithium hydroxide, calcium oxide, magnesium oxide, etc.) Usually, about 0.001 to 0.2 mol can be used with respect to 1 mol of the compound. Moreover, the said superposition | polymerization prohibition measure can also be applied as needed. The usage-amount of a polymerization inhibitor is about 0.0001-0.01 mol% normally with respect to 1 mol of this alicyclic maleimide compound.
前記置換反応は特に限定されず、各種公知の方法を利用できる。具体的には、例えば前記脂環式マレイミド化合物1モルと、これに対し通常0.8〜2モル程度の前記ビニル化合物と、該ビニル化合物と同モル程度の塩基性触媒(例えば水酸化ナトリウム水溶液)と、必要に応じて各種溶媒とからなる溶液に、1モル程度の前記脂環式マレイミド化合物(通常、トルエンとメタノールとからなる混合溶媒で溶解したもの)を通常30分〜2時間かけて滴下し、通常20℃〜150℃程度、通常2〜20時間程度置換反応させればよい。 The substitution reaction is not particularly limited, and various known methods can be used. Specifically, for example, 1 mol of the alicyclic maleimide compound, usually about 0.8 to 2 mol of the vinyl compound, and a basic catalyst of the same mol as the vinyl compound (for example, sodium hydroxide aqueous solution) And about 1 mol of the alicyclic maleimide compound (usually dissolved in a mixed solvent consisting of toluene and methanol) in a solution consisting of various solvents as necessary over a period of usually 30 minutes to 2 hours. The reaction may be carried out by dropping, and the substitution reaction is usually about 20 ° C to 150 ° C, usually about 2 to 20 hours.
なお、前記脂環式マレイミド化合物が、前記一般式(6)のR2中に炭素−炭素不飽和結合を有する場合には、前記重合禁止措置を適用することができる。重合禁止剤の使用量は、該脂環式マレイミド化合物1モルに対して通常0.0001〜0.01モル%程度である。 Note that the alicyclic maleimide compound, carbon in R 2 in the general formula (6) - when carbon unsaturated bond, can be applied to the polymerization inhibiting action. The usage-amount of a polymerization inhibitor is about 0.0001-0.01 mol% normally with respect to 1 mol of this alicyclic maleimide compound.
こうして得られた、前記一般式(1)で示す脂環イミドアクリレートは、通常はそのままでも高純度であるが、前記精製手段で精製することにより、純度をより高めることができる。また、該脂環イミドアクリレートが、分子中の脂環骨格に炭素−炭素不飽和結合を含む場合には、前記同様水素化反応を適用してもよい。水素化した脂環イミドアクリレートを用いた重合体は耐熱性が良く、また軟化点が高いなどの特徴を有する。 The thus obtained alicyclic imide acrylate represented by the general formula (1) is usually highly pure as it is, but the purity can be further improved by purifying it by the purification means. Further, when the alicyclic imide acrylate contains a carbon-carbon unsaturated bond in the alicyclic skeleton in the molecule, a hydrogenation reaction may be applied as described above. A polymer using a hydrogenated alicyclic imide acrylate has characteristics such as good heat resistance and a high softening point.
本発明に係る脂環イミドアクリレートは、分子中に重合性二重結合を有するので、単独で重合させ、若しくは他の重合性モノマーと共重合させることにより、各種の、油性ないし水性の重合体組成物とすることができる。 Since the alicyclic imide acrylate according to the present invention has a polymerizable double bond in the molecule, various oily or aqueous polymer compositions can be obtained by polymerizing alone or copolymerizing with other polymerizable monomers. It can be a thing.
他の重合性モノマーとしては、例えば、アクリル酸アルキルエステル〔(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸ヒドロキシエチル、(メタ)アクリル酸イソボルニル等〕、芳香族系モノマー〔スチレン、α−メチルスチレン、ビニルトルエン、インデン、メチルインデン等〕、アニオン性ビニルモノマーやその中和塩〔(メタ)アクリル酸、クロトン酸、マレイン酸、イタコン酸、フマル酸、ムコン酸、シトラコン酸、ビニルスルホン酸、スチレンスルホン酸、(メタ)アリルスルホン酸、2−アクリルアミド−2−メチルプロパンスルホン酸等や、これらの中和塩〕、第三級アミノ基含有ビニルモノマー〔アリルアミン、N,N−ジメチルアミノエチル(メタ)アクリレート、N,N−ジエチルアミノエチル(メタ)アクリレート、N,N−ジメチルアミノプロピル(メタ)アクリルアミド、N,N−ジエチルアミノプロピル(メタ)アクリルアミド等〕、該第三級アミノ基含有ビニルモノマーを四級化剤〔メチルクロライド、ベンジルクロライド、ジメチル硫酸、エピクロルヒドリン等〕で第四級化してなるカチオン性ビニルモノマー、多官能ビニルモノマー〔ジビニルベンゼン、トリプロピレングリコールジアクリレート、テトラエチレングリコールジアクリレート、トリメチロールプロパントリアクリレート、ジトリメチロールプロパンテトラアクリレート、ビスフェノールAテトラエチレングリコールジアクリレート、ヘキサメチレングリコールジアクリレート、1,9−ノナンジオールジアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールヘキサアクリレート、N−ビニルピロリドン、(メタ)アクリルアミドN−ビニルホルムアミド、4−ヒドロキシブチルビニルエーテル、ジエチレングリコールジビニルエーテル等〕、酢酸ビニルなどのモノマーが挙げられ、これらは1種を単独で、あるいは2種以上を組み合わせて用いることができる。 Other polymerizable monomers include, for example, alkyl acrylate esters [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, hydroxyethyl (meth) acrylate, isobornyl (meth) acrylate Etc.], aromatic monomers (styrene, α-methylstyrene, vinyltoluene, indene, methylindene, etc.), anionic vinyl monomers and neutralized salts thereof ((meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, Fumaric acid, muconic acid, citraconic acid, vinyl sulfonic acid, styrene sulfonic acid, (meth) allyl sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, etc., and neutralized salts thereof], containing tertiary amino group Vinyl monomer [allylamine, N, N-dimethylaminoethyl (meth) acrylate , N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, etc.], and the tertiary amino group-containing vinyl monomer is quaternized. Cationic vinyl monomers, polyfunctional vinyl monomers (divinylbenzene, tripropylene glycol diacrylate, tetraethylene glycol diacrylate, trimethylolpropane) that are quaternized with an agent (methyl chloride, benzyl chloride, dimethyl sulfate, epichlorohydrin, etc.) Triacrylate, ditrimethylolpropane tetraacrylate, bisphenol A tetraethylene glycol diacrylate, hexamethylene glycol diacrylate, 1,9-nonanediol diacrylate , Pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, N-vinyl pyrrolidone, (meth) acrylamide N-vinylformamide, 4-hydroxybutyl vinyl ether, diethylene glycol divinyl ether, etc.], and vinyl acetate. One species can be used alone, or two or more species can be used in combination.
なお、本発明の脂環イミドアクリレートと前記その他のモノマーを共重合させる場合において、両者の重量比は、得られる重合体組成物の用途に応じて適宜決定することができるが、例えば前者:後者で80:20〜10:90程度である。 In the case where the alicyclic imide acrylate of the present invention is copolymerized with the other monomer, the weight ratio between the two can be appropriately determined according to the use of the obtained polymer composition. For example, the former: the latter Is about 80:20 to 10:90.
重合方法は特に制限されず、例えば活性エネルギー線(紫外線や電子線)を照射したり(光重合)、加熱したりする方法(加熱重合)を採用できる。また、重合は、前記溶媒の存在下または不存在下で行うこともできる。 The polymerization method is not particularly limited, and for example, a method of irradiating active energy rays (ultraviolet rays or electron beams) (photopolymerization) or heating (heat polymerization) can be employed. The polymerization can also be performed in the presence or absence of the solvent.
光重合の際には、各種公知の光重合開始剤を用いることができる。具体的には、例えば、アセトフェノン類〔アセトフェノン、2,2−ジメトキシ−2−フェニルアセトフェノン、2,2−ジエトキシ−2−フェニルアセトフェノン、1,1−ジクロロアセトフェノン、1−ヒドロキシシクロヘキシルフェニルケトン、2−メチル−1−[4−(メチルチオ)フェニル]−2−モルフォリノ−プロパン−1−オンおよびN,N−ジメチルアミノアセトフェノン等〕、ベンゾフェノン類〔ベンゾフェノン、メチルベンゾフェノン、4,4’−ジクロロベンゾフェノン、4,4’−ビスジエチルアミノベンゾフェノン、ミヒラーズケトンおよび4−ベンゾイル−4’−メチルジフェニルサルファイド等〕、チオキサントン類〔2,4−ジメチルチオキサントン、2,4−ジエチルチオキサントン、2−クロロチオキサントンおよび2,4−ジイソプロピルチオキサントン等のチオキサントン〕、アントラキノン類〔2−メチルアントラキノン、1−クロロアントラキノンおよび2−アミルアントラキノン等〕、ベンゾイン類〔ベンゾイン、ベンゾインメチルエーテルおよびベンゾインプロピルエーテル等〕が挙げられ、これらは1種を単独で、あるいは2種以上を組み合わせて用いることができる。また、必要に応じてN,N−ジメチルアミノ安息香酸エチルエステル、N,N−ジメチルアミノ安息香酸イソアミルエステル、トリエチルアミンおよびトリエタノールアミン等の光増感剤を併用することもできる。なお、該光重合開始剤や該光増感剤の使用量はいずれも、重合体組成物の固形分重量に対し、通常0.01〜10重量%程度である。 In the photopolymerization, various known photopolymerization initiators can be used. Specifically, for example, acetophenones [acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2- Methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one and N, N-dimethylaminoacetophenone, etc.], benzophenones [benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4 , 4′-bisdiethylaminobenzophenone, Michler's ketone, 4-benzoyl-4′-methyldiphenyl sulfide, etc.], thioxanthones [2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxone] Thioxanthones such as N-tone and 2,4-diisopropylthioxanthone], anthraquinones [such as 2-methylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone], benzoins [such as benzoin, benzoin methyl ether and benzoin propyl ether] These can be used singly or in combination of two or more. Further, if necessary, photosensitizers such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethylamine and triethanolamine can be used in combination. In addition, both the usage-amount of this photoinitiator and this photosensitizer are about 0.01 to 10 weight% normally with respect to the solid content weight of a polymer composition.
また熱重合の際には、各種公知の熱重合開始剤を用いることができる。具体的には、例えば、有機過酸化物〔1,1−ビス(t−ブチルパーオキシ)2−メチルシクロヘキサン、1,1−ビス(t−ヘキシルパーオキシ)−3,3,5−トリメチルシクロヘキサン、1,1−ビス(t−ヘキシルパーオキシ)シクロヘキサン、1,1−ビス(t−ブチルパーオキシ)−3,3,5−トリメチルシクロヘキサン、1,1−ビス(t−ブチルパーオキシ)シクロヘキサン等〕、アゾ系化合物〔1,1’−アゾビス(シクロヘキサン−1−カルボニトリル)、2−(カルバモイルアゾ)イソブチロニトリル、2−フェニルアゾ−4−メトキシ−2,4−ジメチルバレロニトリル、アゾジ−t−オクタンおよびアゾジ−t−ブタン等〕が挙げられ、これらは1種を単独で、あるいは2種以上を組み合わせて用いることができる。なお、前記有機過酸化物は還元剤と組み合わせることによりレドックス系開始剤としてもよい。該熱重合開始剤の使用量は、重合体組成物の固形分重量に対して、通常0.01〜10重量%程度である。 In the thermal polymerization, various known thermal polymerization initiators can be used. Specifically, for example, organic peroxide [1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane Etc.], azo compounds [1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, azodi -T-octane and azodi-t-butane, etc.], and these can be used alone or in combination of two or more. That. In addition, the said organic peroxide is good also as a redox-type initiator by combining with a reducing agent. The usage-amount of this thermal-polymerization initiator is about 0.01 to 10 weight% normally with respect to the solid content weight of a polymer composition.
その他、重合反応時には前記重合禁止剤や重合禁止措置を適用することもできる。 In addition, the polymerization inhibitor and the polymerization prohibition measure can be applied during the polymerization reaction.
本発明の重合体組成物には、その用途に応じて各種添加剤を適用することができる。具体的には、例えば、耐熱性、密着性、硬度などの特性を向上する目的で無機充填剤〔シリカ粉末、アルミナ、ジルコン、ケイ酸カルシウム、炭酸カルシウム等〕を適用できるほか、着色剤〔フタロシアニン・ブルー、フタロシアニングリーン、アイオジン・グリーン、ジスアゾイエロー、クリスタルバイオレット、酸化チタン、カーボンブラック、ナフタレンブラック等〕、難燃剤〔三酸化アンチモン、リン酸エステル、赤リンおよびメラミン樹脂をはじめとする含窒素化合物等〕、消泡剤〔シリコーン系、フッ素系、高分子系等〕、密着性付与剤〔イミダゾール類、チアゾール類、トリアゾール類、シランカップリング剤等〕、応力緩和剤〔シリコーンオイル、シリコーンゴム粉末等〕、光安定剤〔ヒンダードアミン系化合物等〕、帯電防止剤、レベリング剤などを用いることができる。また、前記溶媒を希釈溶剤として用いることもできる。 Various additives can be applied to the polymer composition of the present invention depending on its use. Specifically, for example, inorganic fillers (silica powder, alumina, zircon, calcium silicate, calcium carbonate, etc.) can be applied for the purpose of improving properties such as heat resistance, adhesion, and hardness, and colorants (phthalocyanine).・ Blue, phthalocyanine green, iodine green, disazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black, etc.], flame retardants (antimony trioxide, phosphate esters, red phosphorus, melamine resins and other nitrogen-containing compounds) Etc.], antifoaming agents (silicone-based, fluorine-based, polymer-based, etc.), adhesion-imparting agents (imidazoles, thiazoles, triazoles, silane coupling agents, etc.), stress relieving agents (silicone oil, silicone rubber powder) Etc.), light stabilizers (hindered amine compounds, etc.), charging Or the like can be used stop, leveling agents. Moreover, the said solvent can also be used as a dilution solvent.
なお、各重合反応は各種溶媒、例えば、アルコール系溶媒(メタノール、エタノール等)、芳香族系溶媒(ベンゼン、トルエン、キシレン等)、ケトン系溶媒(アセトン、メチルエチルケトン等)、エーテル系溶媒(THF等)の存在下または不存在下で行うことできる。 Each polymerization reaction can be carried out in various solvents such as alcohol solvents (methanol, ethanol, etc.), aromatic solvents (benzene, toluene, xylene, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), ether solvents (THF, etc.). ) In the presence or absence.
また、活性エネルギー線としては、例えば、紫外線や電子線が挙げられる。紫外線の光源としては、例えば低圧水銀灯、高圧水銀灯、メタルハライドランプ、キセノンランプ、無電極放電ランプおよびカーボンアークランプ等が挙げられる。また、電子線源としては、
例えばコックロフトワルトシン型、バンデグラフ型または共振変圧器型の照射装置が挙げ
られる。
Moreover, as an active energy ray, an ultraviolet-ray and an electron beam are mentioned, for example. Examples of the ultraviolet light source include a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, an electrodeless discharge lamp, and a carbon arc lamp. As an electron beam source,
For example, a Cockloft-Waltsin type, a bandegraph type or a resonant transformer type irradiation device may be mentioned.
以下に、実施例を挙げて本発明を更に具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、スペクトル測定には次の装置を使用した。
1H−NMR、13C−NMR:BRUKERARX300(ブルカーバイオスピン社製)
IR:AVATAR360(ThermoNicolet社製)
ガスクロマトグラフィー(GC):5890SERIES II(HEWLETT社製)
Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to these examples. In addition, the following apparatus was used for the spectrum measurement.
1 H-NMR, 13 C-NMR: BRUKERARX300 (manufactured by Bruker BioSpin)
IR: AVATAR 3 60 (ThermoNicolet Co., Ltd.)
Gas chromatography (GC): 5890 SERIES II (made by HEWLETT)
実施例1
温度計、滴下ロート、窒素ガス導入口、攪拌機を備えた反応容器に、無水マレイン酸179.9gと脱水トルエン350mLを仕込み、系内を窒素置換した。次いで、無水マレイン酸を50℃で溶解し、攪拌下にα−テルピネン(和光純薬(株)製、純度90%)277.8gを、系内の温度が60℃程度になるように水浴で発熱を抑えながら滴下した。滴下終了後、系内の温度が下がりはじめたら、60℃で加熱攪拌しながらディールス・アルダー反応を6時間行った。反応終了後、溶媒および未反応原料を減圧留去・除去して固体を採取し、これを減圧乾燥することにより、脂環式ジカルボン酸無水物(以下、α−テルピネン酸無水物という)を417.1g得た。なお、このものの純度(GC法による測定値をいう。以下、同様)は96.9%であった。
Example 1
A reaction vessel equipped with a thermometer, a dropping funnel, a nitrogen gas inlet, and a stirrer was charged with 179.9 g of maleic anhydride and 350 mL of dehydrated toluene, and the system was purged with nitrogen. Next, maleic anhydride was dissolved at 50 ° C., and 277.8 g of α-terpinene (manufactured by Wako Pure Chemical Industries, Ltd., purity 90%) was stirred in a water bath so that the temperature in the system was about 60 ° C. The solution was added dropwise while suppressing the exotherm. When the temperature in the system began to drop after completion of the dropwise addition, Diels-Alder reaction was performed for 6 hours while heating and stirring at 60 ° C. After completion of the reaction, the solvent and unreacted raw material were removed by distillation under reduced pressure to collect a solid, which was dried under reduced pressure to obtain alicyclic dicarboxylic acid anhydride (hereinafter referred to as α-terpinenic acid anhydride) 417. 0.1 g was obtained. In addition, the purity (referred to as a measured value by the GC method, hereinafter the same) of this product was 96.9%.
次に、ディーンスターク分水器(ジムロート冷却管)、温度計、滴下ロート、窒素ガス導入口、攪拌機を備えた反応容器に、前記α−テルピネン酸無水物180.0g、脱水トルエン200mLを仕込み、系内を窒素置換した。次いで、室温で系内を攪拌しつつ、エタノールアミン45.3gを滴下した。滴下終了後、反応系を106〜110℃まで昇温して、ディーンスターク分水器により水を系内から留去しながら、イミド化反応を20時間行った。その際、共沸除去したトルエンおよびエタノールアミンを系内に補充しながらイミド化反応を行った。反応終了後、溶媒を減圧留去してから、n−ヘキサンを加えて再結晶を行った。次いで、得られた結晶を減圧乾燥することにより、脂環式マレイミド化合物207.0gを得た。このものの純度は97.2%であった。 Next, a reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), thermometer, dropping funnel, nitrogen gas inlet, and stirrer was charged with 180.0 g of the α-terpinenic acid anhydride and 200 mL of dehydrated toluene, The system was replaced with nitrogen. Next, 45.3 g of ethanolamine was added dropwise while stirring the system at room temperature. After completion of the dropwise addition, the reaction system was heated to 106 to 110 ° C., and an imidization reaction was performed for 20 hours while distilling water from the system with a Dean-Stark water separator. At that time, imidization reaction was performed while replenishing toluene and ethanolamine azeotropically removed into the system. After completion of the reaction, the solvent was distilled off under reduced pressure, and n-hexane was added for recrystallization. Subsequently, the obtained crystal was dried under reduced pressure to obtain 207.0 g of an alicyclic maleimide compound. The purity of this product was 97.2%.
次に、ディーンスターク分水器(ジムロート冷却管)、温度計、滴下ロート、空気バブリング用導入管、攪拌機を備えた反応容器に、当該脂環式マレイミド化合物150.0g、ヒドロキノン1.85g、トルエン300mLを仕込み、p−トルエンスルホン酸3.70g、アクリル酸185.1gを添加して攪拌した。次いで、反応系を空気でバブリングしながら106〜110℃まで昇温して、ディーンスターク分水器で水を系内から留去しながらエステル化反応を21時間行った。その際、反応の進行はGCで追跡した。また、反応を促進させ、完結させる目的でp−トルエンスルホン酸を系内に添加しながら反応を行った。次いで、反応溶液を室温まで冷却し、分液ロートを用いてイオン交換水、炭酸水素ナトリウム水溶液での洗浄を3回繰り返し、更に減圧下にトルエンを留去し、脂環イミドアクリレート(A−1)(以下、化合物A−1という)128.7gを得た。なお、このものの純度は92.4%であった。 Next, 150.0 g of the alicyclic maleimide compound, 1.85 g of hydroquinone, toluene in a reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), a thermometer, a dropping funnel, an air bubbling introduction tube, and a stirrer. 300 mL was charged, and 3.70 g of p-toluenesulfonic acid and 185.1 g of acrylic acid were added and stirred. Next, the temperature of the reaction system was raised to 106 to 110 ° C. while bubbling with air, and the esterification reaction was carried out for 21 hours while water was distilled away from the system using a Dean-Stark water separator. At that time, the progress of the reaction was followed by GC. In addition, the reaction was carried out while adding p-toluenesulfonic acid into the system for the purpose of promoting and completing the reaction. Next, the reaction solution was cooled to room temperature, washed with ion-exchanged water and an aqueous sodium hydrogen carbonate solution three times using a separatory funnel, and further toluene was distilled off under reduced pressure to obtain an alicyclic imide acrylate (A-1 ) (Hereinafter referred to as Compound A-1) 128.7 g. The purity of this product was 92.4%.
1 H−NMR(300MHz、溶媒CDCl 3 、δ(ppm)):6.36、6.10、5.86、4.20、3.71、2.93、2.54、1.47、1.27、1.09、0.97
13 C−NMR(300MHz、溶媒CDCl 3 、δ(ppm)):177.10、165.61、135.09、135.36、131.20、128.00、127.89、60.93、50.09、46.23、43.50、36.85、34.18、29.52、22.80、18.30、16.78
IR(neat):2960、1726、1702、1692、1400、1182cm−1 1 H-NMR (300 MHz, solvent CDCl 3 , δ (ppm)) : 6.36, 6.10, 5.86, 4.20, 3.71, 2.93, 2.54, 1.47, 1 .27, 1.09, 0.97
13 C-NMR (300 MHz, solvent CDCl 3 , δ (ppm)): 177.10, 165.61, 135.09, 135.36, 131.20, 128.00, 127.89, 60.93, 50 .09, 46.23, 43.50, 36.85, 34.18, 29.52, 22.80, 18.30, 16.78
IR (neat) : 2960, 1726, 1702, 1692, 1400, 1182 cm −1
実施例2
温度計、水素バルーンを備えた反応容器に、実施例1で得られたα−テルピネン酸無水物180.0g、パラジウムカーボン18.0g、脱水THF200mLを仕込み、攪拌下に、50℃で30時間水素化反応を行った。反応終了後、反応系を室温まで冷却し、濾過によりパラジウムカーボンを除去した後、減圧下にTHFを留去した。次いで、得られた固体を減圧乾燥して、水素化α−テルピネン酸無水物163.4gを得た。
なお、このものの純度は98.6%であった。
Example 2
A reaction vessel equipped with a thermometer and a hydrogen balloon was charged with 180.0 g of α-terpinenic acid anhydride obtained in Example 1, 18.0 g of palladium carbon, and 200 mL of dehydrated THF, and hydrogenated at 50 ° C. for 30 hours with stirring. The reaction was carried out. After completion of the reaction, the reaction system was cooled to room temperature, palladium carbon was removed by filtration, and then THF was distilled off under reduced pressure. Subsequently, the obtained solid was dried under reduced pressure to obtain 163.4 g of hydrogenated α-terpinenic acid anhydride.
The purity of this product was 98.6%.
次に、ディーンスターク分水器(ジムロート冷却管)、温度計、滴下ロート、窒素ガス導入口、攪拌機を備えた反応容器に、前記水素化α−テルピネン酸無水物118.9g、脱水トルエン200mLを仕込み、系内を窒素置換した。その後、室温において、攪拌状態の反応系に、エタノールアミン30.7gを滴下した。滴下終了後、系内の発熱が落ち着いたら、反応系を106〜110℃まで昇温して、ディーンスターク分水器で水を系内から留去しながらイミド化反応を8時間行った。その際、水と共に留去したトルエンおよびエタノールアミンを系内に補充しながら反応を行った。反応終了後、溶媒を減圧下に留去し、次いでn−ヘキサンを加えて再結晶を行った。その後、得られた結晶を減圧乾燥することにより、脂環式マレイミド化合物119.6gを得た。なお、このものの純度は98.9%であった。 Next, 118.9 g of the hydrogenated α-terpinenic acid anhydride and 200 mL of dehydrated toluene were placed in a reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), thermometer, dropping funnel, nitrogen gas inlet, and stirrer. The system was purged with nitrogen. Thereafter, 30.7 g of ethanolamine was added dropwise to the stirred reaction system at room temperature. When the heat generation in the system settled after completion of the dropwise addition, the reaction system was heated to 106 to 110 ° C., and an imidization reaction was carried out for 8 hours while distilling water from the system with a Dean-Stark water separator. At that time, the reaction was carried out while replenishing toluene and ethanolamine distilled off together with water. After completion of the reaction, the solvent was distilled off under reduced pressure, and then n-hexane was added for recrystallization. Thereafter, the obtained crystal was dried under reduced pressure to obtain 119.6 g of an alicyclic maleimide compound. The purity of this product was 98.9%.
次に、ディーンスターク分水器(ジムロート冷却管)、温度計、滴下ロート、空気バブリング用導入管、攪拌機を備えた反応容器に、当該脂環式マレイミド化合物119.5g、ヒドロキノン0.56g、トルエン400mLを仕込み、p−トルエンスルホン酸8.14g、アクリル酸146.4gを添加して攪拌した。次いで、反応系を空気でバブリングしながら106〜110℃まで昇温し、ディーンスターク分水器で水を系内から留去しながらエステル化反応を7時間行った。次いで、反応溶液を室温まで冷却し、分液ロートを用いてイオン交換水、炭酸水素ナトリウム水溶液での洗浄を3回繰り返し、更に減圧下にトルエンを留去し、脂環イミドアクリレート(A−2)(以下、化合物A−2という)109.1gを得た。なお、このものの純度は97.0%であった。 Next, 119.5 g of the alicyclic maleimide compound, 0.56 g of hydroquinone, toluene are added to a reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), a thermometer, a dropping funnel, an introduction tube for air bubbling, and a stirrer. 400 mL was charged, and 8.14 g of p-toluenesulfonic acid and 146.4 g of acrylic acid were added and stirred. Next, the reaction system was heated to 106 to 110 ° C. while bubbling with air, and the esterification reaction was carried out for 7 hours while distilling water from the system with a Dean-Stark water separator. Next, the reaction solution was cooled to room temperature, washed with ion-exchanged water and an aqueous sodium hydrogen carbonate solution three times using a separatory funnel, and further toluene was distilled off under reduced pressure to obtain an alicyclic imide acrylate (A-2 ) (Hereinafter referred to as Compound A-2) 109.1 g was obtained. The purity of this product was 97.0%.
1 H−NMR(300MHz、溶媒CDCl 3 、δ(ppm)):6.39、6.10、5.83、4.32、3.83、2.94、2.54、1.47、1.13、0.97、0.81
13 C−NMR(300MHz、溶媒CDCl 3 、δ(ppm)):178.19、131.33、131.06、128.05、127.86、61.08、59.57、48.77、44.82、37.13、33.92、31.07、28.99、26.36、25.26、22.93、17.30、16.91
IR(neat):2949、1726、1702、1692、1396、1182cm−1 1 H-NMR (300 MHz, solvent CDCl 3 , δ (ppm)) : 6.39, 6.10, 5.83, 4.32, 3.83, 2.94, 2.54, 1.47, 1 .13, 0.97, 0.81
13 C-NMR (300 MHz, solvent CDCl 3 , δ (ppm)) : 178.19, 131.33, 131.06, 128.05, 127.86, 61.08, 59.57, 48.77, 44 .82, 37.13, 33.92, 31.07, 28.99, 26.36, 25.26, 22.93, 17.30, 16.91
IR (neat) : 2949, 1726, 1702, 1692, 1396, 1182 cm −1
実施例3
温度計、滴下ロート、窒素ガス導入口、攪拌機を備えた反応容器に、無水マレイン酸309.8gと脱水トルエン250mLを仕込み、系内を窒素置換した。次いで、無水マレイン酸を50℃で溶解し、攪拌下にミルセン(アルドリッチ製、純度90%)503.4gを、系内の温度が60℃程度になるように水浴で発熱を抑えながら滴下した。滴下終了後、系内の温度が下がりはじめたら、60℃で加熱攪拌しながらディールス・アルダー反応を3時間行った。反応終了後、副生物を濾過で分離後、溶媒および未反応原料を減圧留去・除去して淡黄色液体を採取し、これを減圧乾燥することにより、脂環式ジカルボン酸無水物(以下、ミルセン酸無水物という)を646.9g得た。なお、このものの純度は90.2%であった。
Example 3
A reaction vessel equipped with a thermometer, a dropping funnel, a nitrogen gas inlet, and a stirrer was charged with 309.8 g of maleic anhydride and 250 mL of dehydrated toluene, and the system was purged with nitrogen. Next, maleic anhydride was dissolved at 50 ° C., and 503.4 g of myrcene (manufactured by Aldrich, purity 90%) was added dropwise with stirring while suppressing heat generation in a water bath so that the temperature in the system was about 60 ° C. When the temperature in the system began to drop after completion of the dropwise addition, Diels-Alder reaction was carried out for 3 hours while heating and stirring at 60 ° C. After completion of the reaction, by-products are separated by filtration, the solvent and unreacted raw material are distilled off under reduced pressure to remove a pale yellow liquid, and this is dried under reduced pressure to obtain an alicyclic dicarboxylic acid anhydride (hereinafter, 646.9 g of myrsenic anhydride was obtained. The purity of this product was 90.2%.
次に、ディーンスターク分水器(ジムロート冷却管)、温度計、滴下ロート、窒素ガス導入口、攪拌機を備えた反応容器に、前記ミルセン酸無水物175.0g、脱水トルエン200mLを仕込み、系内を窒素置換した。次いで、室温で系内を攪拌しつつ、エタノールアミン45.6gを滴下した。滴下終了後、反応系を106〜110℃まで昇温して、ディーンスターク分水器により水を系内から留去しながら、イミド化反応を12時間行った。反応終了後、溶媒を減圧留去してから、得られた淡黄色粘性固体を減圧乾燥することにより、脂環式マレイミド化合物189.4gを得た。このものの純度は88.0%であった。 Next, 175.0 g of myrsenic anhydride and 200 mL of dehydrated toluene were charged into a reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), thermometer, dropping funnel, nitrogen gas inlet, and stirrer. Was replaced with nitrogen. Next, 45.6 g of ethanolamine was added dropwise while stirring the system at room temperature. After completion of the dropwise addition, the reaction system was heated to 106 to 110 ° C., and an imidization reaction was performed for 12 hours while water was distilled away from the system using a Dean-Stark water separator. After completion of the reaction, the solvent was distilled off under reduced pressure, and the obtained pale yellow viscous solid was dried under reduced pressure to obtain 189.4 g of an alicyclic maleimide compound. The purity of this product was 88.0%.
次に、ディーンスターク分水器(ジムロート冷却管)、温度計、滴下ロート、空気バブリング用導入管、攪拌機を備えた反応容器に、当該脂環式マレイミド化合物160.0g、ヒドロキノン1.73g、トルエン200mLを仕込み、p−トルエンスルホン酸9.66g、アクリル酸173.7gを添加して攪拌した。次いで、反応系を空気でバブリングしながら106〜110℃まで昇温し、ディーンスターク分水器で水を系内から留去しながらエステル化反応を21時間行った。その際、反応の進行はGCで追跡した。次いで、反応溶液を室温まで冷却し、分液ロートを用いてイオン交換水、炭酸水素ナトリウム水溶液での洗浄を3回繰り返し、更に減圧下にトルエンを留去し、脂環イミドアクリレート(A−3)(以下、化合物A−3という)132.5gを得た。なお、このものの純度は89.0%であった。 Next, 160.0 g of the alicyclic maleimide compound, 1.73 g of hydroquinone, toluene are added to a reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), a thermometer, a dropping funnel, an air bubbling introduction tube, and a stirrer. 200 mL was charged, and 9.66 g of p-toluenesulfonic acid and 173.7 g of acrylic acid were added and stirred. Next, the reaction system was heated to 106-110 ° C. while bubbling with air, and the esterification reaction was carried out for 21 hours while water was distilled off from the system using a Dean-Stark water separator. At that time, the progress of the reaction was followed by GC. Next, the reaction solution was cooled to room temperature, washed with ion-exchanged water and an aqueous sodium hydrogen carbonate solution three times using a separatory funnel, and further toluene was distilled off under reduced pressure to obtain an alicyclic imide acrylate (A-3). ) (Hereinafter referred to as Compound A-3) 132.5 g was obtained. The purity of this product was 89.0%.
1 H−NMR(300MHz、溶媒CDCl 3 、δ(ppm)):6.40、6.06、5.82、5.56、5.02、4.28、3.77、3.06、2.52、2.22、1.67、1.58、1.27、1.01、0.94、0.76
13 C−NMR(300MHz、溶媒CDCl 3 、δ(ppm)):179.76、165.70、140.30、131.30、127.87、123.49、119.73、60.98、39.24、37.26、27.49、25.91、24.04、19.32、17.65
IR(neat):2929、1701、1398、1182cm−1 1 H-NMR (300 MHz, solvent CDCl 3 , δ (ppm)) : 6.40, 6.06, 5.82, 5.56, 5.02, 4.28, 3.77, 3.06, 2 .52, 2.22, 1.67, 1.58, 1.27, 1.01, 0.94, 0.76
13 C-NMR (300 MHz, solvent CDCl 3 , δ (ppm)): 179.76, 165.70, 140.30, 131.30, 127.87, 123.49, 119.73, 60.98, 39 .24, 37.26, 27.49, 25.91, 24.04, 19.32, 17.65
IR (neat) : 2929, 1701, 1398, 1182 cm −1
実施例4
温度計、水素バルーンを備えた反応容器に、実施例3で得られたミルセン酸無水物200.0g、パラジウムカーボン15.0g、脱水THF200mLを仕込み、攪拌下に、50℃で72時間水素化反応を行った。反応終了後、反応系を室温まで冷却し、濾過によりパラジウムカーボンを除去した後、減圧下にTHFを留去した。次いで、得られた固体を減圧乾燥して、水素化ミルセン酸無水物198.0gを得た。なお、このものの純度は90.6%であった。
Example 4
A reaction vessel equipped with a thermometer and a hydrogen balloon was charged with 200.0 g of myrsenic anhydride obtained in Example 3, 15.0 g of palladium carbon, and 200 mL of dehydrated THF, and the hydrogenation reaction was performed at 50 ° C. for 72 hours with stirring. Went. After completion of the reaction, the reaction system was cooled to room temperature, palladium carbon was removed by filtration, and then THF was distilled off under reduced pressure. Next, the obtained solid was dried under reduced pressure to obtain 198.0 g of hydrogenated myrsenic anhydride. The purity of this product was 90.6%.
次に、ディーンスターク分水器(ジムロート冷却管)、温度計、滴下ロート、窒素ガス導入口、攪拌機を備えた反応容器に、前記水素化ミルセン酸無水物198.0g、脱水トルエン200mLを仕込み、系内を窒素置換した。その後、室温において、攪拌状態の反応系に、エタノールアミン52.5gを滴下した。滴下終了後、系内の発熱が落ち着いたら、反応系を106〜110℃まで昇温し、ディーンスターク分水器で水を系内から留去しながらイミド化反応を6時間行った。反応終了後、室温に戻し、窒素ガス導入口を空気バブリング用導入管に取り替え、ヒドロキノン2.19g、p−トルエンスルホン酸11.41g、アクリル酸218.9gを添加して攪拌した。次いで、反応系を空気でバブリングしながら106〜110℃まで昇温し、ディーンスターク分水器で水を系内から留去しながらエステル化反応を12時間行った。次いで、反応溶液を室温まで冷却し、分液ロートを用いてイオン交換水、炭酸水素ナトリウム水溶液での洗浄を3回繰り返し、更に減圧下にトルエンを留去し、脂環イミドアクリレート(A−4)(以下、化合物A−4という)206.0gを得た。なお、このものの純度は85.6%であった。 Next, in a reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), a thermometer, a dropping funnel, a nitrogen gas inlet, and a stirrer, 198.0 g of the hydrogenated myrsenic acid anhydride and 200 mL of dehydrated toluene were charged. The system was replaced with nitrogen. Thereafter, 52.5 g of ethanolamine was added dropwise to the stirred reaction system at room temperature. When the heat generation in the system was settled after the completion of the dropping, the reaction system was heated to 106 to 110 ° C., and an imidization reaction was carried out for 6 hours while distilling water from the system with a Dean-Stark water separator. After completion of the reaction, the temperature was returned to room temperature, the nitrogen gas inlet was replaced with an air bubbling inlet, 2.19 g of hydroquinone, 11.41 g of p-toluenesulfonic acid, and 218.9 g of acrylic acid were added and stirred. Next, the temperature of the reaction system was raised to 106 to 110 ° C. while bubbling with air, and the esterification reaction was carried out for 12 hours while distilling water from the system with a Dean-Stark water separator. Next, the reaction solution was cooled to room temperature, washed with ion-exchanged water and an aqueous sodium hydrogen carbonate solution three times using a separatory funnel, and further toluene was distilled off under reduced pressure to obtain an alicyclic imide acrylate (A-4). ) (Hereinafter referred to as Compound A-4) 206.0 g. The purity of this product was 85.6%.
1 H−NMR(300MHz、溶媒CDCl 3 、δ(ppm)):6.34、6.07、5.82、4.33、3.81、2.87、2.22、1.67、1.58、1.27、1.22、1.15、0.86
13 C−NMR(300MHz、溶媒CDCl 3 、δ(ppm)):179.86、165.68、132.20、127.85、60.96、39.70、36.89、34.01、28.73、27.83、24.26、22.52
IR(neat):2927、1708、1397、1182cm−1 1 H-NMR (300 MHz, solvent CDCl 3 , δ (ppm)): 6.34, 6.07, 5.82, 4.33, 3.81, 2.87, 2.22, 1.67, 1 .58, 1.27, 1.22, 1.15, 0.86
13 C-NMR (300 MHz, solvent CDCl 3 , δ (ppm)): 179.86, 165.68, 132.20, 127.85, 60.96, 39.70, 36.89, 34.01, 28 .73, 27.83, 24.26, 22.52
IR (neat) : 2927, 1708, 1397, 1182 cm −1
比較例1
ディーンスターク分水器(ジムロート冷却管)、温度計、滴下ロート、窒素ガス導入口、攪拌機を備えた反応容器にテトラヒドロ無水フタル酸(商品名「リカシッドTH」、新日本理化(株)製)200.0g、脱水トルエンを185.0gを仕込み、系内を窒素置換した。次いで、反応容器を室温で攪拌しつつエタノールアミン80.3gを滴下した。滴下終了後、還流温度(110℃)まで加熱し、水をトルエンで共沸除去しつつ6時間反応を行うことにより、環イミド化合物を得た。このものは純度99.1%であった(GC法による)。
Comparative Example 1
Tetrahydrophthalic anhydride (trade name “Ricacid TH”, manufactured by Shin Nippon Rika Co., Ltd.) 200 in a reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), thermometer, dropping funnel, nitrogen gas inlet, and stirrer 0.0 g and 185.0 g of dehydrated toluene were charged, and the system was purged with nitrogen. Next, 80.3 g of ethanolamine was added dropwise while stirring the reaction vessel at room temperature. After completion of the dropwise addition, the mixture was heated to the reflux temperature (110 ° C.) and reacted for 6 hours while removing water azeotropically with toluene to obtain a cyclic imide compound. This had a purity of 99.1% (according to GC method).
次いで、上記の反応溶液を室温まで戻し、窒素ガス導入口を空気バブリング用導入管に変更し、メトキノン2.57g、p−トルエンスルホン酸15g、アクリル酸185.9gを添加し攪拌した。系内で空気をバブリングしながら、還流温度(106〜110℃)まで加熱昇温し、ディーンスターク分水器で水を系内から留去しながら反応を16時間行った。次いで、反応溶液を40℃以下まで冷却し、分液ロートを用いてイオン交換水、炭酸水素ナトリウム水溶液での洗浄を繰り返し、減圧濃縮でトルエンを留去し、脂環イミドアクリレートB(以下、化合物Bという)を得た。このものは純度93.1%であった(GC法による)。なお、当該化合物Bの各スペクトル測定値および構造は、以下のようになる。 Next, the reaction solution was returned to room temperature, the nitrogen gas inlet was changed to an air bubbling inlet tube, 2.57 g of methoquinone, 15 g of p-toluenesulfonic acid, and 185.9 g of acrylic acid were added and stirred. While bubbling air in the system, the temperature was raised to the reflux temperature (106 to 110 ° C.), and the reaction was carried out for 16 hours while water was distilled from the system with a Dean-Stark water separator. Next, the reaction solution is cooled to 40 ° C. or lower, washed repeatedly with ion-exchanged water and aqueous sodium hydrogen carbonate solution using a separatory funnel, and toluene was distilled off by concentration under reduced pressure to obtain alicyclic imide acrylate B (hereinafter referred to as compound B)). This had a purity of 93.1% (by the GC method). In addition, each spectrum measurement value and structure of the compound B are as follows.
1 H−NMR(300MHz、溶媒CDCl 3 、δ(ppm)):5.87、6.37、6.06、4.26、3.79、3.10、2.56、2.20
IR(neat):1653、1703、1725、1182、1401cm-1 1 H-NMR (300 MHz, solvent CDCl 3 , δ (ppm)): 5.87, 6.37, 6.06, 4.26, 3.79, 3.10, 2.56, 2.20
IR (neat): 1653, 1703, 1725, 1182, 1401 cm −1
比較例2
ディーンスターク分水器(ジムロート冷却管)、温度計、滴下ロート、窒素ガス導入口、攪拌機を備えた反応容器に無水コハク酸(和光純薬(株)製)150.0g、脱水トルエンを150.0g仕込み、系内を窒素置換した。次いで、反応容器を室温で攪拌しつつエタノールアミン89.7gを滴下した。滴下終了後、還流温度(110℃)まで加熱し、水をトルエンで共沸除去しつつ3時間反応を行い、イミド化合物を得た。このものは純度97.0%であった(GC法による)。
Comparative Example 2
In a reaction vessel equipped with a Dean-Stark water separator (Dimroth condenser), thermometer, dropping funnel, nitrogen gas inlet, and stirrer, 150.0 g of succinic anhydride (Wako Pure Chemical Industries, Ltd.) and 150. dehydrated toluene. 0 g was charged and the inside of the system was replaced with nitrogen. Next, 89.7 g of ethanolamine was added dropwise while stirring the reaction vessel at room temperature. After completion of the dropwise addition, the mixture was heated to the reflux temperature (110 ° C.) and reacted for 3 hours while removing water azeotropically with toluene to obtain an imide compound. This had a purity of 97.0% (according to GC method).
次いで、上記の反応溶液を室温まで戻し、窒素ガス導入口を空気バブリング用導入管に変え、メトキノン3.0g、p−トルエンスルホン酸30.0g、アクリル酸378.0gを添加し攪拌した。次いで、系内を空気でバブリングしながら還流温度(106〜110℃)まで加熱昇温し、ディーンスターク分水器で水を系内から留去しながら反応を16時間行った。次いで、反応溶液を40℃以下まで冷却し、分液ロートを用いてイオン交換水、炭酸水素ナトリウム水溶液での洗浄を繰り返し、減圧濃縮でトルエンを留去し、イミドアクリレートC(以下、化合物Cという)を得た。このものは純度87.0%であった(GC法による)。なお、当該化合物Cの各スペクトル測定値および構造は、以下のようになる。 Next, the reaction solution was returned to room temperature, the nitrogen gas inlet was changed to an air bubbling inlet tube, 3.0 g of methoquinone, 30.0 g of p-toluenesulfonic acid, and 378.0 g of acrylic acid were added and stirred. Next, the system was heated to reflux temperature (106 to 110 ° C.) while bubbling with air, and the reaction was carried out for 16 hours while water was distilled from the system with a Dean-Stark water separator. Next, the reaction solution is cooled to 40 ° C. or lower, repeatedly washed with ion-exchanged water and an aqueous sodium hydrogen carbonate solution using a separatory funnel, and toluene is distilled off by concentration under reduced pressure to obtain imidoacrylate C (hereinafter referred to as Compound C). ) This had a purity of 87.0% (according to GC method). In addition, each spectrum measurement value and structure of the compound C are as follows.
1 H−NMR(300MHz、溶媒CDCl 3 、δ(ppm)):6.78、6.36、5.87、4.32、3.84、2.72
IR(neat):1700、1401、1184、1112cm-1 1 H-NMR (300 MHz, solvent CDCl 3 , δ (ppm)): 6.78, 6.36, 5.87, 4.32, 3.84, 2.72
IR (neat): 1700, 1401, 1184, 1112 cm −1
以下、比較用の化合物D〜Gを示す。 Hereinafter, Comparative Compounds D to G are shown.
化合物D(商品名「アロニックスM140」、東亞合成(株)製) Compound D (trade name “Aronix M140”, manufactured by Toagosei Co., Ltd.)
実施例5
前記化合物A−1を50部、トルエン50部、アゾビスイソブチロニトリルを0.9部(該Aに対して3mol%)を混合し、熱重合用組成物Aを調製した。次いでこれを、窒素雰囲気下、80℃、5時間の条件で重合させた。次いで、得られた各重合物を、ヘキサンを用いて再沈精製して未反応の化合物を除去し、更に減圧乾燥することによって(1333Pa、80℃、5時間)、重合体A−1を得た。当該重合体A−1は、下記耐熱性試験に供した。
Example 5
50 parts of the compound A-1, 50 parts of toluene, and 0.9 part of azobisisobutyronitrile (3 mol% with respect to A) were mixed to prepare a composition A for thermal polymerization. Subsequently, this was polymerized under conditions of 80 ° C. and 5 hours in a nitrogen atmosphere. Subsequently, each polymer obtained was purified by reprecipitation using hexane to remove unreacted compounds, and further dried under reduced pressure (1333 Pa, 80 ° C., 5 hours) to obtain a polymer A-1. It was. The polymer A-1 was subjected to the following heat resistance test.
実施例6〜8
実施例5と同様の方法で、前記化合物A−2〜A−4についても重合体A−2〜A−4を作製し、それぞれを下記耐熱性試験に供した。
Examples 6-8
Polymers A-2 to A-4 were prepared for the compounds A-2 to A-4 in the same manner as in Example 5, and each was subjected to the following heat resistance test.
(耐熱性の評価)
前記重合体A−1〜A−4について、市販の熱重量測定装置(TG−DTA)および示差走査熱量分析装置(DSC)(製品名「2000S システムWS002」、マック・サイエンス社製)を用いて、熱分解開始温度およびTgを求めた。なお、測定条件、および数値の算出法は以下の通りである。結果を表1に示す。
(Evaluation of heat resistance)
About the said polymers A-1 to A-4, using a commercially available thermogravimetric measuring device (TG-DTA) and a differential scanning calorimeter (DSC) (product name "2000S system WS002", manufactured by Mac Science). The thermal decomposition onset temperature and Tg were determined. The measurement conditions and the numerical value calculation method are as follows. The results are shown in Table 1.
・TG−DTA:室温から10℃/minで昇温して800℃までサンプルを加熱した際にチャート上に出現した屈曲点における温度を、熱分解開始温度とした。
・DSC:−50℃から10℃/minで昇温して200℃までサンプルを加熱した後、再度−50℃まで冷却し、再び200℃まで加熱した際に得られる、2サイクル目の曲線から、接線法により屈曲点を算出して、Tgとした。
TG-DTA: The temperature at the bending point that appeared on the chart when the sample was heated from room temperature at 10 ° C./min and heated to 800 ° C. was defined as the thermal decomposition start temperature.
DSC: From the second cycle curve obtained when the sample was heated from -50 ° C. at 10 ° C./min to 200 ° C., then cooled again to −50 ° C., and again heated to 200 ° C. The inflection point was calculated by the tangent method and set as Tg.
実施例9
前記化合物A−3を80部、ウレタンアクリレート(商品名「アロニックスM−1600」、東亞合成(株)製)20部を60℃で混合し、更に1−ヒドロキシシクロヘキシルフェニルケトン(商品名「イルガキュア184」、チバ・スペシャリティ・ケミカルズ(株)製)3部を60℃で添加して混合することにより、光重合用組成物A’を得た。次いでこれを、ガラス板上に載置したPETフィルムに膜厚が硬化後に約200μmとなるように塗布した。次いで、当該PETフィルムをガラス板に載せたまま、HO2−L21型水銀ランプを設置した紫外線照射装置(製品名「UB022−5B」、アイグラフィックス株式会社製)に10回通過させて紫外線重合を行い、重合体(硬化被膜)A’−3を得た。
Example 9
80 parts of the compound A-3 and 20 parts of urethane acrylate (trade name “Aronix M-1600”, manufactured by Toagosei Co., Ltd.) were mixed at 60 ° C., and further 1-hydroxycyclohexyl phenyl ketone (trade name “Irgacure 184”). 3 parts of Ciba Specialty Chemicals Co., Ltd.) was added at 60 ° C. and mixed to obtain composition A ′ for photopolymerization. Subsequently, this was apply | coated to PET film mounted on the glass plate so that a film thickness might be set to about 200 micrometers after hardening. Next, while the PET film is placed on a glass plate, it is passed 10 times through an ultraviolet irradiation device (product name “UB022-5B”, manufactured by Eye Graphics Co., Ltd.) equipped with a HO2-L21 type mercury lamp to carry out ultraviolet polymerization. And polymer (cured coating) A′-3 was obtained.
なお、紫外線照射装置は、ランプ高さが10cm、コンベアスピード10m/min、紫外線照射強度が130mJ/cm2である。なお、硬化の完了は、紫外線照射のパス後、被膜の表面を指でこすり、タック(粘着性)がなくなった時点をもって判断した。 The ultraviolet irradiation device has a lamp height of 10 cm, a conveyor speed of 10 m / min, and an ultraviolet irradiation intensity of 130 mJ / cm 2 . The completion of the curing was judged when the surface of the coating was rubbed with a finger after the ultraviolet irradiation pass and tack (adhesiveness) disappeared.
実施例10
実施例9において、前記化合物A−3の代わりにA−4を用いた他は同様にして光重合用組成物A’−4を調製し、各組成物を前記同様の工程で紫外線重合させ、重合体(硬化被膜)A’−4を得た。
Example 10
In Example 9, a photopolymerizable composition A′-4 was prepared in the same manner except that A-4 was used instead of the compound A-3, and each composition was subjected to ultraviolet polymerization in the same process as described above. Polymer (cured film) A′-4 was obtained.
比較例3〜5
実施例9において、前記化合物A−3の代わりに前記化合物B〜Dを用いた他は同様にして光重合用組成物B’〜D’を調製し、各組成物を前記同様の工程で紫外線重合させ、重合体(硬化被膜)B’〜D’を得た。
Comparative Examples 3-5
In Example 9, photopolymerizable compositions B ′ to D ′ were prepared in the same manner except that the compounds B to D were used in place of the compound A-3, and each composition was subjected to ultraviolet rays in the same manner as described above. Polymerization was performed to obtain polymers (cured coatings) B ′ to D ′.
(吸水性の評価)
重合体(硬化被膜)A’−3を有するPETフィルムを縦45mm×横6mmの短冊状に切り取り、PETフィルムから剥がした硬化被膜を試験片とした。この試験片を120℃で24時間乾燥してその重量(W0)を測り、次いでこれを40℃の水浴に24時間浸した後に水分を十分ふき取ってその重量(W1)を測り、その重量変化(W1−W0)/W0×100を硬化被膜の吸水率(%)として評価した。また、前記重合体(硬化被膜)A’−3、A’−4、ならびに重合体(硬化被膜)B’、C’およびD’についても同様にして吸水率を評価した。結果を表2に示す。
(Evaluation of water absorption)
A PET film having a polymer (cured film) A′-3 was cut into strips of 45 mm in length × 6 mm in width and peeled off from the PET film was used as a test piece. The test piece was dried at 120 ° C. for 24 hours and weighed (W 0 ), then immersed in a 40 ° C. water bath for 24 hours and then thoroughly wiped to measure its weight (W 1 ). The change (W 1 −W 0 ) / W 0 × 100 was evaluated as the water absorption rate (%) of the cured coating. Further, the water absorption rate of the polymers (cured coatings) A′-3 and A′-4 and the polymers (cured coatings) B ′, C ′ and D ′ were evaluated in the same manner. The results are shown in Table 2.
実施例11〜12、比較例6〜8
前記光重合用組成物A’−3の1gをメチルエチルケトンで希釈し、30重量%の溶液とした。次いで、バーコーターNo.12を用いて、当該溶液を膜厚が硬化後に約3μmとなるようにPETフィルムに塗工し、80℃で1分間乾燥した後、前記同様の方法で紫外線重合させ、重合体(硬化被膜)A’’−3を作成した。次いで、該重合体A’’−3について、鉛筆硬度(JIS−K−5400)、およびTgを評価した。また、前記光重合用組成物A’−4ならびにB’〜D’についても同様にして重合体A’’−4ならびにB’’〜D’’を作成し、鉛筆硬度を評価した。結果を表3に示す。
Examples 11-12, Comparative Examples 6-8
1 g of the photopolymerization composition A′-3 was diluted with methyl ethyl ketone to obtain a 30% by weight solution. Next, bar coater No. 12 was applied to a PET film so that the film thickness was about 3 μm after curing, dried at 80 ° C. for 1 minute, and then UV-polymerized in the same manner as described above to obtain a polymer (cured film). A ″ -3 was created. The polymer A ″ -3 was then evaluated for pencil hardness (JIS-K-5400) and Tg. Further, for the photopolymerization compositions A′-4 and B ′ to D ′, polymers A ″ -4 and B ″ to D ″ were similarly prepared, and pencil hardness was evaluated. The results are shown in Table 3.
Claims (6)
[工程(I)]
下記一般式(4−1)で示される脂環式ジカルボン酸または下記一般式(4−2)で示される脂環式ジカルボン酸無水物に、
下記一般式(5)で示されるモノアミン化合物を反応させて、下記一般式(6)で示される脂環式マレイミド化合物を製造する工程。
[工程(II)]
前記一般式(6)で表される脂環式マレイミド化合物に、下記一般式(7)で示すビニル化合物を反応させる工程。
[Process (I)]
To the alicyclic dicarboxylic acid represented by the following general formula (4-1) or the alicyclic dicarboxylic acid anhydride represented by the following general formula (4-2),
A step of reacting a monoamine compound represented by the following general formula (5) to produce an alicyclic maleimide compound represented by the following general formula (6).
[Process (II)]
A step of reacting the alicyclic maleimide compound represented by the general formula (6) with a vinyl compound represented by the following general formula (7).
A polymer composition obtained by polymerizing the composition for polymerization according to claim 5.
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