JPS63128004A - Production of radically curable resin - Google Patents
Production of radically curable resinInfo
- Publication number
- JPS63128004A JPS63128004A JP27298786A JP27298786A JPS63128004A JP S63128004 A JPS63128004 A JP S63128004A JP 27298786 A JP27298786 A JP 27298786A JP 27298786 A JP27298786 A JP 27298786A JP S63128004 A JPS63128004 A JP S63128004A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- acid anhydride
- copolymer
- formula
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 37
- 239000011347 resin Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- -1 vinyl compound Chemical class 0.000 claims abstract description 34
- 229920001577 copolymer Polymers 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 150000002440 hydroxy compounds Chemical class 0.000 claims abstract description 18
- 239000004593 Epoxy Substances 0.000 claims abstract description 17
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 15
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 14
- 125000004018 acid anhydride group Chemical group 0.000 claims abstract description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims 2
- 239000001257 hydrogen Substances 0.000 claims 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 17
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 abstract description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 4
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 abstract description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004566 building material Substances 0.000 abstract description 2
- 238000007142 ring opening reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000003054 catalyst Substances 0.000 description 9
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920006337 unsaturated polyester resin Polymers 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LOJBIMMTQPHXBL-UHFFFAOYSA-N (1-chloro-3-hydroxypropan-2-yl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(CO)CCl LOJBIMMTQPHXBL-UHFFFAOYSA-N 0.000 description 2
- POTYORUTRLSAGZ-UHFFFAOYSA-N (3-chloro-2-hydroxypropyl) prop-2-enoate Chemical compound ClCC(O)COC(=O)C=C POTYORUTRLSAGZ-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- 239000013040 bath agent Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 125000006364 carbonyl oxy methylene group Chemical group [H]C([H])([*:2])OC([*:1])=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 1
- CXJAFLQWMOMYOW-UHFFFAOYSA-N 3-chlorofuran-2,5-dione Chemical compound ClC1=CC(=O)OC1=O CXJAFLQWMOMYOW-UHFFFAOYSA-N 0.000 description 1
- AXGOOCLYBPQWNG-UHFFFAOYSA-N 3-ethylfuran-2,5-dione Chemical compound CCC1=CC(=O)OC1=O AXGOOCLYBPQWNG-UHFFFAOYSA-N 0.000 description 1
- RDUXDNVQXJZSPY-UHFFFAOYSA-N 3-methylideneoxane-2,6-dione Chemical compound C=C1CCC(=O)OC1=O RDUXDNVQXJZSPY-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- QZYCWJVSPFQUQC-UHFFFAOYSA-N 3-phenylfuran-2,5-dione Chemical compound O=C1OC(=O)C(C=2C=CC=CC=2)=C1 QZYCWJVSPFQUQC-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
- 229910015900 BF3 Inorganic materials 0.000 description 1
- CBUORVHJUFBDTQ-UHFFFAOYSA-N C(C=C)(=O)O.ClC=CC1=CC=CC=C1 Chemical class C(C=C)(=O)O.ClC=CC1=CC=CC=C1 CBUORVHJUFBDTQ-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical group [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- AFTLIIOXEHXDOZ-UHFFFAOYSA-N buta-1,3-diene;furan-2,5-dione;styrene Chemical compound C=CC=C.O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 AFTLIIOXEHXDOZ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/14—Esterification
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、共重合体の側鎖に重合性のアクリロイル基又
はメタクリロイル基を有する、各種用途に有用なラジカ
ル硬化可能な樹脂の製造方法だ関する。[Detailed Description of the Invention] [Field of Industrial Application] The present invention is a method for producing a radically curable resin useful for various uses, which has a polymerizable acryloyl group or methacryloyl group in the side chain of the copolymer. related.
ラジカル硬化型樹脂としては、不飽和ポリエステル樹脂
、ビニルエステル樹脂が代表的であシ、ジアリルフタレ
ート樹脂も成形材料、化粧板等の用途に利用されている
。Typical radical-curable resins include unsaturated polyester resins and vinyl ester resins, and diallyl phthalate resins are also used as molding materials, decorative boards, and the like.
これらの樹脂は、それぞれの樹脂の有する特徴、特性を
生かして多様な用途において利用されており、欠くこと
のできない存在となっている。These resins are used in a variety of applications by taking advantage of the characteristics and properties of each resin, and have become indispensable.
しかしながら、その反面、技術の急激な進歩と共により
高度の性能や、新しい性質が要求されることもしばしば
あり、これらの要求に対応して樹脂の改良を図らねばな
らぬ事も多い。On the other hand, however, with rapid advances in technology, higher performance and new properties are often required, and resins often have to be improved in response to these demands.
例えは、不飽和ポリエステル樹脂は優れた耐水性、耐熱
性、耐薬品性を有し、ＦＲＰや自動車部品等の用途に広
く用いられているが、耐ｖｔｒ撃性を心安とする分野に
おいて使用するには性能的に不充分であるのが実情であ
る。For example, unsaturated polyester resin has excellent water resistance, heat resistance, and chemical resistance, and is widely used in applications such as FRP and automobile parts. The reality is that the performance is insufficient.
本発明省らは既存樹脂が抱えている諸欠点を改良してそ
の用途を拡大すると共に、熱恢化性樹脂に対する第［し
い要求性能に応えられる工うなｍ脂の開発を進めてきた
結果、不飽和ポリエステル樹脂等の前記欠点を補うこと
のできるラジカル倣化性樹脂の製造方法を見出すに至り
た。As a result of our efforts to improve the various drawbacks of existing resins and expand their uses, the Ministry of Invention and others has proceeded with the development of resins that can meet the new performance requirements for heat-curable resins. We have now discovered a method for producing radical mimicking resins that can compensate for the drawbacks of unsaturated polyester resins and the like.
〔間ｍ点を解決するための手段〕
即ち、本発明は、α、β−不飽和酸無水物、α、β−不
飽和酸無水物と共Ｉ合可能なビニル化合物、及累、メチ
ル、クロルメチル、エチル、ＣＨ２＝区ｏｏｃ４−。[Means for solving the m-point] That is, the present invention provides an α,β-unsaturated acid anhydride, a vinyl compound capable of co-merging with an α,β-unsaturated acid anhydride, and a methyl, Chloromethyl, ethyl, CH2 = ward ooc4-.
ＣＨ２＝ Ｃ（ＣＨ，）ＣＯＯＣＨ２−１ＣＨ２＝ Ｃ
ＨＣＨ２０ＣＨ２−を表わす）で示されるエポキシ化合
物とアクリル酸又はメタクリル酸とを反応して得られる
ヒドロキシ化合物と同一の構造式をもつヒドロキシ化合
物によってエステル化して共重合体の側鎖に不飽和二重
結合を尋人し、共１合体の酸無水物基が開演して生成し
たカルメキシル基の一部またはすべてを一般式％式％
示されるエポキシ化合物と反応させることを特徴とする
硬化性樹脂の製造方法を提供するにある。CH2= C(CH,)COOCH2-1CH2= C
HCH20CH2-) is esterified with a hydroxy compound having the same structural formula as the hydroxy compound obtained by reacting an epoxy compound represented by (HCH20CH2-) with acrylic acid or methacrylic acid to form an unsaturated double bond in the side chain of the copolymer. A method for producing a curable resin, which is characterized by reacting some or all of the carmexyl groups produced by the opening of the acid anhydride groups of the co-merged with an epoxy compound represented by the general formula %. is to provide.
本発明によるラジカル硬化性樹脂はジエン化合物に帰因
する耐倫撃性成分を共重合体分子中に有し、しかも分子
１４１１鎮にラジカル架橋性の不飽和二重結合を有して
いることから、従来の仮住型樹脂にはない優れた耐衝撃
性を発揮することができる。The radical curable resin according to the present invention has an impact resistance component attributable to the diene compound in the copolymer molecule, and also has an unsaturated double bond capable of radical crosslinking in the molecule 1411. It can exhibit excellent impact resistance not found in conventional temporary resins.
以下本発明についてさらに詳しく説明する。The present invention will be explained in more detail below.
本発明において用いられるα、β−不飽和酸無水物とし
ては例えば無水マレイン酸、シトラコン酸無水物、無水
２−エチルマレイン酸、無水２−フェニルマレイン酸、
無水２−クロロマレイン酸、イタコン酸無水物、２−メ
チレン−グルタル酸無水物等があげられる。Examples of the α,β-unsaturated acid anhydride used in the present invention include maleic anhydride, citraconic anhydride, 2-ethylmaleic anhydride, 2-phenylmaleic anhydride,
Examples include 2-chloromaleic anhydride, itaconic anhydride, 2-methylene-glutaric anhydride, and the like.
また、α、β−不飽和酸無水物と共重合可能なビニル化
合物としては、例えばスチレン、α−メチルスチレン、
ビニルトルエン、クロルスチレンアクリル酸エステル類
、メタクリル酸エステル類、酢酸ビニル、塩化ビニル、
アクリロニトリル等があげられこれらの１つ又は２種以
上が用いられるが、これらのうちでも脣にスチレンが好
ましい。Examples of vinyl compounds copolymerizable with α,β-unsaturated acid anhydrides include styrene, α-methylstyrene,
Vinyl toluene, chlorostyrene acrylates, methacrylates, vinyl acetate, vinyl chloride,
Acrylonitrile and the like can be mentioned, and one or more of these can be used, but among these, styrene is most preferred.
α、β−不飽和酸無水物及びビニル化合物と共重合させ
る１、３−ジエン化合物としては例えば１．３−ブタジ
ェン、イソプレン、２，３−ジメチルブタジェン、クロ
ロプレン等があげられる。Examples of the 1,3-diene compound to be copolymerized with the α,β-unsaturated acid anhydride and the vinyl compound include 1,3-butadiene, isoprene, 2,3-dimethylbutadiene, and chloroprene.
上記α、β−不飽和酸無水物、ビニル化合物及び１．３
−ジエン化合物の共重合の際の比率は、目的とする樹脂
の性能に合わせて適宜変化させることができる。The above α,β-unsaturated acid anhydride, vinyl compound and 1.3
- The ratio of the diene compound during copolymerization can be changed as appropriate depending on the desired performance of the resin.
α、β−不飽和酸無水物、ビニル化合物及び１，３−ジ
エン化合物とからなる共重合体は加圧、常圧、又は減圧
工種々の方法で製造することができる。A copolymer comprising an α,β-unsaturated acid anhydride, a vinyl compound, and a 1,3-diene compound can be produced by various methods including pressurization, normal pressure, or reduced pressure.
例えばビニル化合物を溶剤に溶かし、重合触媒を添加後
、常圧下一定温度でα、β−不飽和酸無水物及び１，３
−ジエン化合物を添加しながら反応させる方法や、α、
β−不飽和酸無水物を溶剤に溶かし重合触媒を添加後、
常圧下一定温度でビニル化合物及び１，３−ジエン化合
物を添加しながら反応させる方法等がある。For example, after dissolving a vinyl compound in a solvent and adding a polymerization catalyst, α, β-unsaturated acid anhydride and 1,3
- A method of reacting while adding a diene compound, α,
After dissolving β-unsaturated acid anhydride in a solvent and adding a polymerization catalyst,
There is a method of reacting while adding a vinyl compound and a 1,3-diene compound at a constant temperature under normal pressure.
上記共重合体を製造する除、使用する溶剤はα、β−不
飽和酸無水物、ビニル化合物、１，３−ジエン化合物を
溶解し、反応に不活性であるものであればいずれも使用
できるが、ビニル化合物自体を溶剤として用いて実質無
溶剤で反応させることしては通常一般的に用いられるラ
ジカル重合開始剤でよく例えば過酸化物、アゾ化合物等
があげられる。又、必要に応じてメルカプタン類のごと
き１合ｖｒ４ａ剤を併用することもできる。Except for producing the above copolymer, any solvent can be used as long as it dissolves the α,β-unsaturated acid anhydride, vinyl compound, and 1,3-diene compound and is inert to the reaction. However, when the vinyl compound itself is used as a solvent and the reaction is carried out substantially without solvent, commonly used radical polymerization initiators may be used, such as peroxides, azo compounds, etc. Further, if necessary, a 1-vr4a agent such as mercaptans can be used in combination.
反応温度は原料組成、触ｆｓ、短によって異なるが、通
常Ｏ〜１５０℃、好ましくは４０〜１２０℃の範囲内で
行なわれる。The reaction temperature varies depending on the raw material composition, catalytic fs, and temperature, but is usually carried out within the range of 0 to 150°C, preferably 40 to 120°C.
上記重合体の製造の除、α、β−不飽和不飽和物無水物
ニル化合物が未反応物として生成共産合体溶液中に残存
することもあるが、後述の樹脂の硬化の除に硬化体中に
組み込１れるので、符に差しつかえない。Except for the production of the above-mentioned polymer, the α,β-unsaturated anhydride compound may remain as an unreacted product in the resulting copolymer solution, but during the curing of the resin described below, the α,β-unsaturated anhydride compound may remain in the cured product. Since it is incorporated into 1, it can be used as a sign.
この様にして得られた共′ＪＩＬ合体の酸無水物基を、
ル、クロルメチル、エチル、ＣＨ２＝ＣＨＣ００ＣＨ２
−１ＣＨ２＝Ｃ（ＣＨ，）ＣＯＯＣＨ２−、ＣＨ２＝Ｃ
ＨＣＨ２０ＣＨ２−を表わす）で示されるエポキシ化合
物とアクリル酸又はメタクリル酸とを反応して得られる
ヒドロキシ化合物と同一の構造式をもつヒドロキシ化合
物に工つてエステル化する。The acid anhydride group of the co′JIL composite obtained in this way,
chloromethyl, ethyl, CH2=CHC00CH2
-1CH2=C(CH,)COOCH2-, CH2=C
The epoxy compound represented by HCH20CH2- is reacted with acrylic acid or methacrylic acid to form a hydroxy compound having the same structural formula as the hydroxy compound obtained by reacting with acrylic acid or methacrylic acid.
該ヒドロキシ化合物としては、例えは２−ヒドロキシエ
チルアクリレート、２−ヒドロキシエチルメタクリレー
ト、２−ヒドロキシプロピルアクリレート、２−ヒドロ
キシエチルメタクリレート脂３−クロル−２−ヒドロキ
シエチルアクリレート性
タクリレート、２．−ヒドロキシブチルアクリレート、
２・−ヒドロキシブチルメタクリレート、３−クロル−
２−（３−クロル−２−ヒドロキシプロピルオキシ）プ
ロピルアクリレート、３−クロル−２−（３−クロル−
２−ヒドロキシプロピルオキシ）プロピルメタクリレー
ト、１−メチル−２−ヒドロキシエチルアク＋） ｖ
−ト、１− メｆｋ−２−ヒドロキシエチルメタクリレ
ート、１−クロルメチル−２−ヒドロキシエチルアクリ
レート、１−クロルメチル−２−ヒドロキシエチルメタ
クリレート等があげられる。Examples of the hydroxy compound include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 3-chloro-2-hydroxyethyl acrylate acrylate, 2. -Hydroxybutyl acrylate,
2-Hydroxybutyl methacrylate, 3-chloro-
2-(3-chloro-2-hydroxypropyloxy)propyl acrylate, 3-chloro-2-(3-chloro-
2-hydroxypropyloxy)propyl methacrylate, 1-methyl-2-hydroxyethylac+) v
-t, 1-methacrylate, 1-chloromethyl-2-hydroxyethyl methacrylate, 1-chloromethyl-2-hydroxyethyl methacrylate, and the like.
このヒドロキシ化合物を用いて上記共重合体の酸無水物
基をエステル化する際、該ヒドロキシ化合物は一種類だ
けでなく、二種類以上を組み合わせて用いることができ
る。また該ヒドロキシ化合メチル、クロルメチル、エチ
ル、ｃＨ２＝ ＣＨＣＯＯＣＨ２−１ＣＨ２＝Ｃ（ＣＨ
３）ＣＯＯＣＨ２−、ＣＨ２＝ＣＨＣＨ２０ＣＨ２−を
戎わす）で示されるエポキシ化合物とアクリル酸又はメ
タクリル酸との反応で得られるが、該エポキシ化合物と
アクリルば又はメタクリル酸との反応は従来公知の方法
で行なうことができる。When this hydroxy compound is used to esterify the acid anhydride group of the copolymer, not only one type of hydroxy compound but also a combination of two or more types can be used. In addition, the hydroxy compounds methyl, chloromethyl, ethyl, cH2=CHCOOCH2-1CH2=C(CH
3) COOCH2-, CH2=CHCH20CH2-) can be obtained by reacting an epoxy compound represented by acrylic acid or methacrylic acid, but the reaction between the epoxy compound and acrylic acid or methacrylic acid can be carried out by a conventionally known method. can be done.
例えばエポキシ化合物に触媒、１合禁止剤を添加した後
、一定温度でアクリル酸又はメタクリル酸を添加しなが
ら反応させることにニジヒドロキシ化合物が得られる。For example, a dihydroxy compound can be obtained by adding a catalyst and an inhibitor to an epoxy compound and then reacting the mixture at a constant temperature while adding acrylic acid or methacrylic acid.
反応触媒としては三級アミン、四級アンモニウム塩三フ
フ化ホウ素等や従来公知のエステル化触ａｔ−用いるこ
とができる。１合禁止剤としては従来公知のラジカル菖
合基止剤を用いることができる。反応温度は室温〜１５
０℃、好ましくは４０〜１２０℃の範囲内が過当である
。As the reaction catalyst, tertiary amines, quaternary ammonium salts such as boron trifluoride, and conventionally known esterification catalysts can be used. As the 1 group inhibitor, a conventionally known radical grouping grouping agent can be used. Reaction temperature is room temperature to 15
A temperature range of 0°C, preferably 40 to 120°C is appropriate.
本発明において用いるヒドロキシ化合物は、−クロルメ
チル、エチル、ＣＨ２＝ ＣＨＣＯＯＣＨ２−１ＣＨ２
＝Ｃ（ＣＨ３）ＣＯＯＣＨ，、ＣＨ２＝ＣＨＣＨ２０Ｃ
Ｈ２−’ｚ ｋ ワス） テ示されるエポキシ化合物と
アクリル酸又はメタクリル酸との反応で得られる化合物
と構造式が同一のものであれはいずれも使用でき、必す
しも上記ル酸又はメタクリル酸とから製造されたものに
限られるものではない。The hydroxy compound used in the present invention is -chloromethyl, ethyl, CH2= CHCOOCH2-1CH2
=C(CH3)COOCH,, CH2=CHCH20C
Any compound having the same structural formula as the compound obtained by the reaction of the epoxy compound shown with acrylic acid or methacrylic acid can be used, and it is not necessary to use the above-mentioned epoxy compound with acrylic acid or methacrylic acid. It is not limited to those manufactured from.
上記共１合体のば無水物基と賎ヒドロキシ化合物との反
応は、共Ｍ曾俸のＴ＆柩に該ヒドロキシ化合物、必要に
応じて触媒、重合禁止剤を加えて〃Ω熱、攪拌下に行な
われる。浴剤は共１合体を溶解するものであれは特に制
限はなく、ビニル化合物を溶剤として用いて実質無浴剤
で反応させることも可能である。The reaction between the anhydride group of the above polymer and the hydroxyl compound is carried out by adding the hydroxyl compound and, if necessary, a catalyst and a polymerization inhibitor to a T&coffin of the polymer under heat and stirring. It will be done. The bath agent is not particularly limited as long as it dissolves the comonomer, and it is also possible to carry out the reaction substantially without a bath agent by using a vinyl compound as a solvent.
共重合体の酸無水物基と反応させるヒドロキシ化合物の
証は樹脂の性能に合わせて適宜込択することができるが
、通常、共−合体のば無水物基１モルに対して０．１〜
１．０モルの範囲内でちる。必要に応じて用いられる触
媒としては、従来公知のエステル化触媒が用いられる。The amount of hydroxy compound to be reacted with the acid anhydride group of the copolymer can be selected as appropriate depending on the performance of the resin, but it is usually 0.1 to 1 mole of the anhydride group of the copolymer.
Chill within the range of 1.0 mol. As the catalyst used as necessary, a conventionally known esterification catalyst is used.
又、必要に応じて用いられる重合禁止剤としては従来公
知のラジカル重合禁止剤を用いることができる。加′熱
は室温〜１３０℃、好ましくは４０〜１００℃の範囲内
であり、また反応時間は反応温度、ヒドロキシ化合物の
反応性によって決定されるが、通常１〜２０時間が適当
である。Further, as the polymerization inhibitor used as necessary, a conventionally known radical polymerization inhibitor can be used. Heating is carried out at room temperature to 130 DEG C., preferably 40 DEG to 100 DEG C., and the reaction time is determined depending on the reaction temperature and the reactivity of the hydroxy compound, but is usually suitable for 1 to 20 hours.
このようにして得られたエステル化ポリマーは共重合体
の酸無水物基の一部、又は全部がエステル化され、共重
合体の側鎖に不飽和二重結合を有している。In the esterified polymer thus obtained, part or all of the acid anhydride groups of the copolymer are esterified, and the copolymer has an unsaturated double bond in the side chain.
上記共重合体とヒドロキシ化合物との反応において、未
反応のヒドロキシ化合物が残存することもあるが、該ヒ
ドロキシ化合物はラノカル重合性の不飽和二重結合を有
しているため、後述の樹脂の硬化反応の際に硬化体に組
み込まれるので、必ずしも未反応ヒドロキシ化合物を除
去する必要はなく、残存していても何ら差しつかえない
。In the reaction between the copolymer and the hydroxy compound, unreacted hydroxy compound may remain, but since the hydroxy compound has an unsaturated double bond that is lanocal polymerizable, it is difficult to cure the resin as described below. Since it is incorporated into the cured product during the reaction, it is not necessarily necessary to remove the unreacted hydroxy compound, and there is no problem even if it remains.
共重合体の酸無水物基をヒドロキシ化合物でエステル化
すると酸無水物基が開板して共重合体の側鎖にカルがキ
シル基が生成する。該カルボキシル基は場合によっては
樹脂の性能を低下させる原因となるので、工Ｉキシ基を
有する化合物と反応させてカルボキシル基の一部又はす
べてをエステル化する。When the acid anhydride group of the copolymer is esterified with a hydroxy compound, the acid anhydride group opens and a calxyl group is generated in the side chain of the copolymer. Since the carboxyl group may cause deterioration of the performance of the resin in some cases, part or all of the carboxyl group is esterified by reacting with a compound having an I-oxy group.
カルボキシル基と反応させるエポキシ化合物は、ル、ク
ロルメチル、エチル、ＣＨ２＝ＣＨＣ００ＣＨ２−１Ｃ
Ｈ２＝Ｃ（ＣＨ，）ＣＯＯＣＨ２−１ＣＨ２＝ ＣＨＣ
Ｈ２０ＣＨ２−を衣わす）テ示すし、例えはエチレンオ
キシド、ｆロピレンオキシド、ブチレンオキシド、エピ
クロルヒドリン、グリシジルアクリレート、グリシジル
メタクリレート、アリルグリシジルエーテル等がめけら
れる。The epoxy compound to be reacted with the carboxyl group is chloromethyl, ethyl, CH2=CHC00CH2-1C
H2=C(CH,)COOCH2-1CH2=CHC
Examples include ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, etc.
カルボキシル基と反応させるエポキシ化合物の黛は、樹
脂の性能に合わせて適宜選択することができるが１通常
共重合体中のカルボキシル基１モルに対して０．１〜１
．０モルが好ましい。The amount of the epoxy compound to be reacted with the carboxyl group can be appropriately selected depending on the performance of the resin, but it is usually 0.1 to 1 per mole of the carboxyl group in the copolymer.
．． 0 mol is preferred.
カルがキシル基とエポキシ化合物との反応ハ、上記ヒド
ロキシ化合物によってエステル化された共重合体溶液に
エポキシ化合物、必要に応じて触媒、重合禁止剤を添加
して行なう。反応温度は２０〜１２０℃、好ましくは４
０〜１００℃の範囲内である。また反応時間は１〜３０
時間、好ましくは３〜２０時間の範囲内である。この際
反応を促進するために触媒としてエステル化反応やエス
テル交換反応に用いられる従来公知の触媒を使用するこ
とができる。The reaction between the carxyl group and the epoxy compound is carried out by adding the epoxy compound and, if necessary, a catalyst and a polymerization inhibitor to the solution of the copolymer esterified with the hydroxyl compound. The reaction temperature is 20-120°C, preferably 4
It is within the range of 0 to 100°C. Also, the reaction time is 1 to 30
time, preferably within the range of 3 to 20 hours. At this time, in order to promote the reaction, conventionally known catalysts used in esterification reactions and transesterification reactions can be used as catalysts.
かくして得られた硬化性樹脂は、ビニル化合物の溶液と
して用いてビニル化合物と共重合することによシ硬化さ
せることもでき、またビニル化合物を併用しないでポリ
マーの不飽和結合同志の重合により架橋を行なうことも
できる。The curable resin thus obtained can be cured by copolymerizing it with a vinyl compound by using it as a solution of the vinyl compound, or it can be crosslinked by polymerizing the unsaturated bonds of the polymer without using a vinyl compound in combination. You can also do it.
本発明の硬化性樹脂は、従来公知の有機過酸化物を用い
て硬化させることができるが、これらに限定されるもの
ではなく、有機過酸化物とともに、又は単独で元、放射
線、を子線等に感応する硬化触媒等を利用することがで
きる。The curable resin of the present invention can be cured using conventionally known organic peroxides, but is not limited to these. A curing catalyst that is sensitive to etc. can be used.
本発明の硬化性樹脂は、必要に応じて充填材、補強材、
難燃剤、可塑剤、安定剤、潤滑剤、無機顔料、着色剤、
離型剤、促進剤、等を含有させることができる。The curable resin of the present invention may contain fillers, reinforcing materials,
Flame retardants, plasticizers, stabilizers, lubricants, inorganic pigments, colorants,
A mold release agent, an accelerator, etc. can be included.
実施例
〔無水マレイン酸−スチレン−ブタジェン共重合体の展
進〕
攪拌機、温度計、還流冷却器、ガス導入管、滴下ロート
を備えた５００−セパラブルフラスコにスチレン１５６
．２１ （１，５０ｍｏｔ ） 、メチルエチルケトン
１５６．２ｇ、アゾビスイソブチロニトリル４．６９ｐ
、ｎ−ドデシルメルカプタン０．６０．９を仕込んだ。Example [Development of maleic anhydride-styrene-butadiene copolymer] Styrene 156 was placed in a 500-separable flask equipped with a stirrer, thermometer, reflux condenser, gas inlet tube, and dropping funnel.
．． 21 (1,50mot), methyl ethyl ketone 156.2g, azobisisobutyronitrile 4.69p
, n-dodecyl mercaptan 0.60.9.
１，３−ブタジェンガスを少量ずつ吹き込みながら、無
水マレイン酸１９．６ｇ（０，２０ｍｏｔ） 、メチル
エチルケトン１９．Ｊ９との混合物を６０℃、４時間か
けて滴下し反応させた。反応後、１，３−ブタジェンは
１０．０．９が反応して共重合体成分となシ、スチレン
反応率２５％、無水マレイン酸反応率１００％であった
。While blowing 1,3-butadiene gas little by little, 19.6 g (0.20 mot) of maleic anhydride and 19.9 g of methyl ethyl ketone were added. A mixture with J9 was added dropwise at 60° C. over 4 hours to cause a reaction. After the reaction, 10.0.9 of 1,3-butadiene was reacted to form a copolymer component, and the styrene reaction rate was 25% and the maleic anhydride reaction rate was 100%.
〔３−クロル−２−ヒドロキシプロピルアクリレートの
製造〕
上記製造装置と同様の装置にエピクロルヒドリン９２．
５９ （１，Ｏｍｏｔ）、ｔ−ブチルカテコール０、５
ｇ、 塩化）リエチルペンジルアンモニウム１．ＯＩ
を仕込んだ。アクリル酸７２．１９ （１，０ｍｏｔ）
を８０℃、１時間かけて滴下後、８０℃５時間反応させ
た。その結果、エピクロルヒドリン、及びアクリル酸の
反応率は各々９５％であった。[Manufacture of 3-chloro-2-hydroxypropyl acrylate] Epichlorohydrin 92.
59 (1, Omot), t-butylcatechol 0,5
g, ethylpendylammonium chloride) 1. OI
I prepared it. Acrylic acid 72.19 (1.0mot)
was added dropwise at 80°C over 1 hour, and then reacted at 80°C for 5 hours. As a result, the reaction rates of epichlorohydrin and acrylic acid were each 95%.
攪拌機、温度計、還流冷却器、ガス導入管、滴下ロート
ｔ−備えた１０００−セパラブルフラスコに、上記共重
合体溶液３６６．８ｇ、上記３−クロル−２−ヒドロキ
シプロピルアンリレート反応液３３．２ｇを仕込んだ。Into a 1000-cm separable flask equipped with a stirrer, a thermometer, a reflux condenser, a gas introduction tube, and a dropping funnel were added 366.8 g of the above copolymer solution and 33.8 g of the above 3-chloro-2-hydroxypropyl anrylate reaction solution. 2g was charged.
６０℃６時間反応を行なった所、３−クロル−２−ヒド
ロキシプロピルアクリレートの反応率は７０％であった
。When the reaction was carried out at 60°C for 6 hours, the reaction rate of 3-chloro-2-hydroxypropyl acrylate was 70%.
上記反応物溶液４００．０ｇにエピクロルヒドリン９．
５１を仕込み、６０℃、８時間反応させた。Add 9.0 g of epichlorohydrin to 400.0 g of the above reactant solution.
51 was charged and reacted at 60°C for 8 hours.
その結果エピクロルヒドリンの反応率は９５％であった
。As a result, the reaction rate of epichlorohydrin was 95%.
この反応液４０９．５ｇから減圧蒸留によジメチルエチ
ルケトンを除去後、スチレンを添加し、スチレンモノマ
ー濃度３０ ｗｔ％の硬化性樹脂溶液を調製した。この
様にして得られた樹脂溶液は淡黄色透明で、２５℃粘度
が２０ポイズであった。After removing dimethyl ethyl ketone from 409.5 g of this reaction solution by vacuum distillation, styrene was added to prepare a curable resin solution with a styrene monomer concentration of 30 wt%. The resin solution thus obtained was pale yellow and transparent, and had a viscosity of 20 poise at 25°C.
上記樹脂溶液１００部に対してｔ−ブチルパーオキシベ
ンゾエート１．５部、ナフテン酸コバルト（１０％Ｃｏ
）０．５部を加え、常温硬化試験を行なった所、グル化
時間８分、最小硬化時間１２分、最高発熱温度１７０℃
であった。1.5 parts of t-butyl peroxybenzoate, cobalt naphthenate (10% Co
) 0.5 part was added and a room temperature curing test was performed, gluing time was 8 minutes, minimum curing time was 12 minutes, and maximum exothermic temperature was 170°C.
Met.
また硬化樹脂の物性は下記の如くであり、優れた耐衝撃
性を有していた。The physical properties of the cured resin were as shown below, and it had excellent impact resistance.
引張シ強さ ７．２に９／ｗ’曲げ強さ
１１．５に９７ｍ”曲げ弾性率 ３９０
ｋｇ７ｗ”熱変形温度 ８０ ℃
シャルピー衝撃 ５．７ ｋｇ −ｃｗｉｗｗ’
比較例
〔不飽和ポリエステル樹脂の製造〕
攪拌機、温度計、ガス導入管、冷却器を備えた１０００
−セパラブルフラスコにプロピレングリコール１００ｇ
、イソフタル酸８２ｇを仕込み、窒素吹き込み条件下、
縮合水を留出させながら１９０℃３時間反応させた。次
に７マル酸８７ｇを添加後１９０℃６時間反応させた。Tensile strength 7.2 to 9/w' bending strength
11.5 to 97m” Flexural modulus 390
kg7w" Heat deformation temperature 80 ℃ Charpy impact 5.7 kg -cwiww'
Comparative example [Production of unsaturated polyester resin] 1000 equipped with a stirrer, thermometer, gas introduction pipe, and cooler
-100g of propylene glycol in a separable flask
, 82 g of isophthalic acid was charged, and under nitrogen blowing conditions,
The reaction was carried out at 190° C. for 3 hours while distilling the condensed water. Next, 87 g of 7-maric acid was added and reacted at 190° C. for 6 hours.
最後に系内を５■−まで減圧にし、フラスコ内の温度を
２００部℃まで上げ反応を終了し、酸価３０の樹脂を得
た。Finally, the pressure in the system was reduced to 5 -, and the temperature in the flask was raised to 200 parts C. to complete the reaction, and a resin with an acid value of 30 was obtained.
この樹脂をスチレンに溶解し、スチレン濃度３０ｗｔ％
の不飽和ポリエステル樹脂を得た。This resin was dissolved in styrene, and the styrene concentration was 30 wt%.
An unsaturated polyester resin was obtained.
この樹脂液は淡黄色透明、２５℃粘度１５ポイズであっ
た。This resin liquid was transparent and pale yellow, and had a viscosity of 15 poise at 25°C.
上記樹脂液１００部に対してｔ−プチルノや−オキシベ
ンゾニー１１，５部、ナフテン酸コバルト（１０％Ｃｏ
）０．５部を加え、常温硬化試験を行なった所、グル化
時間９分、最小硬化時間１３分、最高発熱温度１６５℃
であった。For 100 parts of the above resin liquid, 11.5 parts of t-butylno-oxybenzony, cobalt naphthenate (10% Co
) 0.5 part was added and a room temperature curing test was performed, gluing time was 9 minutes, minimum curing time was 13 minutes, and maximum exothermic temperature was 165°C.
Met.
また、硬化樹脂の物性は下記の如くであり、脆いもので
あった。Further, the physical properties of the cured resin were as shown below, and it was brittle.
引張り強さ ５．Ｏｋｇ／■２
曲げ強さ ９．１ ｋｌｌ／ｗｓ２曲げ弾性
率 ３００ ゆ／■２
熱変形温度 ８４ ℃
シャルピー衝撃 ３．２ゆ・−一〔発明の効果〕
本発明方法で製造されるラジカル硬化性樹脂から得られ
る成形品は、非常に優れた耐衝撃性を有しているのみで
なく、耐熱性、耐薬品性、耐水性等に優れた性能を有し
ておシ、注型品、積層品、ＳＭＣ、ＢＭＣ、ＦＲＰ 、
等の形で電気材料、建材、自動車等の用途に広く利用で
きる。Tensile strength 5. 0kg/■2 Bending strength 9.1 kll/ws2 Flexural modulus 300 Yu/■2 Heat deformation temperature 84°C Charpy impact 3.2 Yu・-1 [Effects of the invention] Radical curable product produced by the method of the present invention Molded products obtained from resin not only have extremely high impact resistance, but also have excellent heat resistance, chemical resistance, water resistance, etc. Product, SMC, BMC, FRP,
It can be widely used in electrical materials, building materials, automobiles, etc.
Claims (1)
重合可能なビニル化合物、及び１，３−ジエン化合物と
からなる共重合体の酸無水物基を、一般式▲数式、化学
式、表等があります▼（ただしＸ、Ｙは水素、メチル、 クロルメチル、エチル、ＣＨ＿２＝ＣＨＣＯＯＣＨ＿２
−、ＣＨ＿２＝Ｃ（ＣＨ＿３）ＣＯＯＣＨ＿２−、ＣＨ
＿２＝ＣＨＣＨ＿２ＯＣＨ＿２−を表わす）で示される
エポキシ化合物とアクリル酸又はメタクリル酸とを反応
して得られるヒドロキシ化合物と同一の構造式をもつヒ
ドロキシ化合物によってエステル化して共重合体の側鎖
に不飽和二重結合を導入し、共重合体の酸無水物基が開
環して生成したカルボキシル基の一部またはすべてを一
般式▲数式、化学式、表等があります▼（ただしＸ、Ｙ
は水素、メチル、ク ロルメチル、エチル、ＣＨ＿２＝ＣＨＣＯＯＣＨ＿２、
ＣＨ＿２＝Ｃ（ＣＨ＿３）ＣＯＯＣＨ＿２−、ＣＨ＿２
＝ＣＨＣＨ＿２ＯＣＨ＿２−を表わす）で示されるエポ
キシ化合物と反応させることを特徴とするラジカル硬化
性樹脂の製造方法。[Claims] A copolymer acid anhydride consisting of an α,β-unsaturated acid anhydride, a vinyl compound copolymerizable with the α,β-unsaturated acid anhydride, and a 1,3-diene compound. The group can be expressed by a general formula▲mathematical formula, chemical formula, table, etc.▼ (where X and Y are hydrogen, methyl, chloromethyl, ethyl, CH_2=CHCOOCH_2
-, CH_2=C(CH_3) COOCH_2-, CH
_2=CHCH_2OCH_2-) is esterified with a hydroxy compound having the same structural formula as the hydroxy compound obtained by reacting the epoxy compound represented by _2=CHCH_2OCH_2- with acrylic acid or methacrylic acid. A part or all of the carboxyl group generated by introducing a double bond and opening the ring of the acid anhydride group of the copolymer is expressed by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, X, Y
is hydrogen, methyl, chloromethyl, ethyl, CH_2=CHCOOCH_2,
CH_2=C(CH_3)COOCH_2-, CH_2
=CHCH_2OCH_2-) A method for producing a radical curable resin, which comprises reacting with an epoxy compound represented by the formula: =CHCH_2OCH_2-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27298786A JPS63128004A (en) | 1986-11-18 | 1986-11-18 | Production of radically curable resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27298786A JPS63128004A (en) | 1986-11-18 | 1986-11-18 | Production of radically curable resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63128004A true JPS63128004A (en) | 1988-05-31 |
Family
ID=17521565
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27298786A Pending JPS63128004A (en) | 1986-11-18 | 1986-11-18 | Production of radically curable resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63128004A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017154439A1 (en) * | 2016-03-08 | 2017-09-14 | 住友ベークライト株式会社 | Method for manufacturing polymer, method for manufacturing negative-type photosensitive resin composition, method for manufacturing resin film, method for manufacturing electronic device, and polymer |
-
1986
- 1986-11-18 JP JP27298786A patent/JPS63128004A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017154439A1 (en) * | 2016-03-08 | 2017-09-14 | 住友ベークライト株式会社 | Method for manufacturing polymer, method for manufacturing negative-type photosensitive resin composition, method for manufacturing resin film, method for manufacturing electronic device, and polymer |
| JPWO2017154439A1 (en) * | 2016-03-08 | 2019-01-10 | 住友ベークライト株式会社 | Method for producing polymer, method for producing negative photosensitive resin composition, method for producing resin film, method for producing electronic device, and polymer |
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