JPH03188043A - Reactive monomer derived from lactone and production thereof - Google Patents
Reactive monomer derived from lactone and production thereofInfo
- Publication number
- JPH03188043A JPH03188043A JP1328059A JP32805989A JPH03188043A JP H03188043 A JPH03188043 A JP H03188043A JP 1328059 A JP1328059 A JP 1328059A JP 32805989 A JP32805989 A JP 32805989A JP H03188043 A JPH03188043 A JP H03188043A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- caprolactone
- methyl
- reaction
- lactone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000178 monomer Substances 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 150000002596 lactones Chemical class 0.000 title abstract description 21
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 16
- YHTLGFCVBKENTE-UHFFFAOYSA-N 4-methyloxan-2-one Chemical compound CC1CCOC(=O)C1 YHTLGFCVBKENTE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- XXCRXPYEAMCJKH-UHFFFAOYSA-N 3,3,4-trimethyloxepan-2-one Chemical compound CC1CCCOC(=O)C1(C)C XXCRXPYEAMCJKH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 20
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 11
- 150000003606 tin compounds Chemical class 0.000 claims description 2
- 150000003609 titanium compounds Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 10
- 238000000576 coating method Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- 230000000704 physical effect Effects 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 1
- 238000011109 contamination Methods 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 abstract 1
- 239000000806 elastomer Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- -1 lactone-modified hydroxyalkyl acrylate Chemical compound 0.000 description 16
- 229910001868 water Inorganic materials 0.000 description 15
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 10
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 9
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical class CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 9
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 9
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 9
- 235000011150 stannous chloride Nutrition 0.000 description 9
- 239000001119 stannous chloride Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000012467 final product Substances 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005809 transesterification reaction Methods 0.000 description 6
- 239000012442 inert solvent Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000007142 ring opening reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 241001550224 Apha Species 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- JTDNNCYXCFHBGG-UHFFFAOYSA-L tin(ii) iodide Chemical compound I[Sn]I JTDNNCYXCFHBGG-UHFFFAOYSA-L 0.000 description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- YBDQLHBVNXARAU-UHFFFAOYSA-N 2-methyloxane Chemical compound CC1CCCCO1 YBDQLHBVNXARAU-UHFFFAOYSA-N 0.000 description 1
- KBXUTBMGSKKPFL-UHFFFAOYSA-N 3-hydroxy-2-methylprop-2-enoic acid Chemical compound OC=C(C)C(O)=O KBXUTBMGSKKPFL-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- OSKVFHONCZMKCM-UHFFFAOYSA-N 4,6,6-trimethyloxepan-2-one Chemical compound CC1CC(=O)OCC(C)(C)C1 OSKVFHONCZMKCM-UHFFFAOYSA-N 0.000 description 1
- HFGHRUCCKVYFKL-UHFFFAOYSA-N 4-ethoxy-2-piperazin-1-yl-7-pyridin-4-yl-5h-pyrimido[5,4-b]indole Chemical compound C1=C2NC=3C(OCC)=NC(N4CCNCC4)=NC=3C2=CC=C1C1=CC=NC=C1 HFGHRUCCKVYFKL-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- OCIFJWVZZUDMRL-UHFFFAOYSA-N 6-hydroxyhexyl prop-2-enoate Chemical compound OCCCCCCOC(=O)C=C OCIFJWVZZUDMRL-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012045 crude solution Substances 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- GHJOIQFPDMIKHT-UHFFFAOYSA-N propane-1,2,3-triol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCC(O)CO GHJOIQFPDMIKHT-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229940108184 stannous iodide Drugs 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium(IV) ethoxide Substances [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は産業上有用な液状タイプのラクトン変性ヒドロ
キシアルキルアクリレートまたはメタクリレート化合物
およびその製造法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to an industrially useful liquid type lactone-modified hydroxyalkyl acrylate or methacrylate compound and a method for producing the same.
近年、コーティング分野におけるアクリル系塗料の重要
性が高まっている。In recent years, the importance of acrylic paints in the coating field has increased.
その理由は他のアルキッド樹脂、ポリエステル樹脂、エ
ポキシ樹脂と比較し耐候性、物性、耐化学性、耐汚染性
等においてすぐれた特徴をもつからである。The reason for this is that it has superior characteristics in terms of weather resistance, physical properties, chemical resistance, stain resistance, etc. compared to other alkyd resins, polyester resins, and epoxy resins.
そのため自動車、家庭電器、金属、建材等あらゆる分野
にアクリル系コーティングが使用されるに到っている。For this reason, acrylic coatings have come to be used in all fields such as automobiles, home appliances, metals, and building materials.
しかしながら、最近、自動車のバンパーのような弾性体
へのコーティングに要求されるが如く極めて伸びがあり
、かつ、強靭な塗膜が必要となってきた。However, recently there has been a need for coatings that are extremely stretchable and strong, as is required for coating elastic bodies such as automobile bumpers.
そのような要求を満たすアクリルポリオール樹脂として
ε−カプロラクトンで変性された2−ヒドロキシエチル
メタクリレートを共重合モノマーとして用いることが提
唱されている(特公昭63−66307)。As an acrylic polyol resin meeting such requirements, it has been proposed to use 2-hydroxyethyl methacrylate modified with ε-caprolactone as a copolymerizable monomer (Japanese Patent Publication No. 66307/1983).
(従来技術)
および
(発明が解決しようとする課題)
これらのラクトン変性ヒドロキシアルキルアクリル酸エ
ステルまたはメタクリル酸エステルは、ラクトンの付加
数が増えるに従い、結晶化しやすくなる。たとえばヒド
ロキシメタクリル酸エステルのε−カプロラクトン3モ
ル付加物は20℃前後で長時間放置するとペースト状と
なるために使用時に加温して均一にすることが必要とな
る。(Prior Art) and (Problems to be Solved by the Invention) These lactone-modified hydroxyalkyl acrylic esters or methacrylic esters become more likely to crystallize as the number of lactones added increases. For example, a 3 mole adduct of ε-caprolactone of hydroxy methacrylic acid ester becomes paste-like if left at around 20 DEG C. for a long period of time, so it is necessary to heat it to make it uniform before use.
またε−カプロラクトン4モル以上の付加物は室温で固
形化するために、長時間の溶解作業が必要となり、工業
的規模での作業としては相当量の設備および時間を必要
とするという欠点がある。In addition, since adducts containing 4 moles or more of ε-caprolactone solidify at room temperature, they require a long dissolution operation, which has the disadvantage of requiring a considerable amount of equipment and time for operations on an industrial scale. .
また、これらのラクトン変性モノマーを共重合させる割
合を大きくするとアクリルポリオール樹脂そのものがポ
リラクトンの結晶性のため白濁してくるという問題があ
る。Furthermore, if the proportion of copolymerization of these lactone-modified monomers is increased, there is a problem that the acrylic polyol resin itself becomes cloudy due to the crystallinity of the polylactone.
一方、ε−カプロラクトンを開環付加させた場合エステ
ル結合が生成するがこれらのエステル結合は、微量の酸
あるいはアルカリが存在すると加水分解が生じやすい傾
向があり、耐加水分解性の向上も必要とされている。On the other hand, when ε-caprolactone undergoes ring-opening addition, ester bonds are formed, but these ester bonds tend to be easily hydrolyzed in the presence of trace amounts of acid or alkali, so it is necessary to improve the hydrolysis resistance. has been done.
(問題を解決するための手段)
本発明は、これらの問題を解決するために、鋭意検討を
行った結果、ヒドロキシアルキルモノアクリレートまた
はメタクリレートにε−カプロラクトンと、β−メチル
−δ−バレロラクトンの混合物あるいはε−カプロラク
トンとトリメチルカプロラクトンの混合物を触媒存在下
で開環付加重合させることによって製造される反応性単
量体が極めて有効であることを見出し本発明に到達した
。(Means for Solving the Problems) In order to solve these problems, the present invention, as a result of extensive research, has developed a system that combines ε-caprolactone and β-methyl-δ-valerolactone in hydroxyalkyl monoacrylate or methacrylate. The inventors have discovered that a reactive monomer produced by ring-opening addition polymerization of a mixture or a mixture of ε-caprolactone and trimethylcaprolactone in the presence of a catalyst is extremely effective, and has thus arrived at the present invention.
即ち、アルキル基を有したラクトン、たとえばβ−メチ
ルーδバレロラクトン、トリメチルカプロラクトンとε
−カプロラクトンを共重合させた重合体はエステル結合
近傍にメチル基が存在するために、ε−カプロラクトン
重合体のみのものと比べて、エステル近傍の疎水性が高
まり、加水分解しにくくなる。一方、ε−カプロラクト
ン重合体よりも、メチル基を有したラクトンが共重合す
ることにより結晶性が崩れるため、融点が低下するもの
と考えられる。That is, lactones having an alkyl group, such as β-methyl-δvalerolactone, trimethylcaprolactone and ε
- Since a polymer copolymerized with caprolactone has a methyl group near the ester bond, the hydrophobicity near the ester increases compared to a polymer containing only ε-caprolactone, making it difficult to be hydrolyzed. On the other hand, it is thought that the melting point is lower than that of the ε-caprolactone polymer because the crystallinity is disrupted by copolymerization of the lactone having a methyl group.
一方、従来β−メチル−δ−バレロラクトンの開環重合
は強アルカリ、強酸性触媒で進行することが知られてい
るが、重合率が低く、また、使用する触媒の量も多いた
め除去する必要があった。On the other hand, it is conventionally known that the ring-opening polymerization of β-methyl-δ-valerolactone proceeds with strong alkali or strong acid catalysts, but the polymerization rate is low and the amount of catalyst used is large, so it is necessary to remove the catalyst. There was a need.
これはバレロラクトンの有するメチル基が立体障害を有
しているために、開環重合しにくいためである。This is because the methyl group of valerolactone has steric hindrance, making ring-opening polymerization difficult.
しかし立体障害のないε−カプロラクトンと共重合させ
ることにより立体障害が解け、再び反応性が向上すると
いうメリットがあり、比較的マイルドな触媒を少量添加
させることにより反応が進行し、触媒の除去も必ずしも
必要でなく、極めて工業的に有利な製法となることを見
出した。However, by copolymerizing with ε-caprolactone, which has no steric hindrance, the steric hindrance is removed and the reactivity is improved again, which is an advantage.The reaction progresses by adding a small amount of a relatively mild catalyst, and the removal of the catalyst is also possible. It has been found that this method is not necessarily necessary, but is an extremely industrially advantageous manufacturing method.
(発明の構成)
即ち、本発明は
「下記(I)式で表される反応性単量体RROR2R3
■
1
cH−C−C−OCH−CH−0−R4・・ (1)
[R,R、RS R−H,CH3
23
R4′
1
−C−(CH) O−・ ・ ・ ・ (A)5
CH3
1
CCH2
■
CHCH2
H2O−
・ ・ ・ (B)
(以下余白)
CH3
CH3
1
CCH2
CHCHCCH20−
CH3
・ ・ ・ ・ (C)
0 CH3
1
−CCHC−CH2CH−CH20−
CHCH−φ ・ ・ (D)
3
R4はAおよびBの共重合体またはAおよびC1Aおよ
びDSAおよびCおよびDの共重合およびASBおよび
CおよびDで、末端にOH基を有する]」
および
[下記(II)式で表されるヒドロキシアルキルモノア
クリレートまたはメタクリレートRROR2R3
■
1
CH−C−C−OCH−CH−OH
(11)
[RSRSR2、R−HSCH3]
3
にε−カプロラクトンと、β−メチル−δ−バレロラク
トンの混合物あるいはε−カプロラクトンとトリメチル
カプロラクトンの混合物を反応させることを特徴とする
反応性単量体の製造方法」である。(Structure of the Invention) That is, the present invention relates to "a reactive monomer RROR2R3 represented by the following formula (I) 1 cH-C-C-OCH-CH-0-R4... (1) [R,R , RS R-H, CH3 23 R4' 1 -C-(CH) O-・ ・ ・ ・ (A) 5 CH3 1 CCH2 ■ CHCH2 H2O- ・ ・ ・ (B) (Margin below) CH3 CH3 1 CCH2 CHCHCCH20- CH3 ・ ・ ・ ・ (C) 0 CH3 1 -CCHC-CH2CH-CH20- CHCH-φ ・ ・ (D) 3 R4 is a copolymer of A and B or a copolymer of A and C1A and DSA and C and D and ASB, C and D, having an OH group at the end] and [Hydroxyalkyl monoacrylate or methacrylate RROR2R3 represented by the following formula (II) 1 CH-C-C-OCH-CH-OH (11) [ RSRSR2, R-HSCH3] 3 with a mixture of ε-caprolactone and β-methyl-δ-valerolactone or a mixture of ε-caprolactone and trimethylcaprolactone. be.
(原料)
本発明の反応性単量体の製造において、出発原料成分で
あるヒドロキシアルキルアクリレートまたはメタクリレ
ートはアクリル酸あるいはメタクリル酸とアルキレンオ
キサイドを触媒の存在下反応させ、蒸溜することにより
工業的に生産されている。(Raw material) In the production of the reactive monomer of the present invention, the starting material component, hydroxyalkyl acrylate or methacrylate, is industrially produced by reacting acrylic acid or methacrylic acid with alkylene oxide in the presence of a catalyst and distilling the reaction mixture. has been done.
例えば、ヒドロキシエチルアクリレートまたはメタクリ
レート、ヒドロキシプロピルアクリレートまたはメタク
リレート、ヒドロキシブチルアクリレートまたはメタク
リレート、ヒドロキシへキシルアクリレートまたはメタ
クリレート、グリセリンモノアクリレートまたはメタク
リレート、カージョラEのアクリル酸またはメタクリル
酸反応物等を用いることが出来る。For example, hydroxyethyl acrylate or methacrylate, hydroxypropyl acrylate or methacrylate, hydroxybutyl acrylate or methacrylate, hydroxyhexyl acrylate or methacrylate, glycerin monoacrylate or methacrylate, an acrylic acid or methacrylic acid reaction product of Carjola E, etc. can be used.
また、もう一方の出発原料成分であるラクトン類として
は、ε−カプロラクトン、3.3.5−トリメチルカプ
ロラクトン、3.5.5−)リメチルカブロラクトン、
β−メチル−6−バレロラクトン等がありこれらを少な
くとも2種類任意の比率で混合して用いることができる
。In addition, the lactones that are the other starting material component include ε-caprolactone, 3.3.5-trimethylcaprolactone, 3.5.5-)limethylcaprolactone,
There are β-methyl-6-valerolactone and the like, and at least two types of these can be mixed and used in any ratio.
工業的にはε−カプロラクトンを主体として用い、その
目的に応じ、3,3.5)リメチルカブロラクトン、3
,5.5トリメチルカプロラクトンまたはβ−メチル−
δ−バレロラクトンを任意の比率で添加することが有利
である。Industrially, ε-caprolactone is mainly used, and depending on the purpose, 3, 3.5) Limethylcabrolactone, 3
, 5.5 trimethylcaprolactone or β-methyl-
It is advantageous to add δ-valerolactone in any proportion.
本発明で用いるε−カプロラクトン、3,3゜5トリメ
チルカブラクトン、3.5.5)リメチルカブロラクト
ンはシクロヘキサノン、3.3゜5トリメチルシクロヘ
キサノンを過酸を用いバイヤービリガー反応により酸化
することによって製造することができる。ε-caprolactone, 3,3゜trimethylcabralactone, 3.5.5) Limethylcabrolactone used in the present invention can be obtained by oxidizing cyclohexanone, 3.3゜trimethylcyclohexanone by Baeyer-Billiger reaction using peracid. It can be manufactured by
特に3,5.5−)リメチルカプロラクトンおよび3.
3.5−)リメチルカプロラクトンは33.5−)リメ
チルシクロヘキサノンを過酸で反応させると混合物とし
て得ることができるが混合物は梯々の方法で分離し、単
独で重合することもできるし、混合物のまま用いること
もできる。In particular 3,5.5-)limethylcaprolactone and 3.
3.5-) Limethylcaprolactone can be obtained as a mixture by reacting 33.5-)limethylcyclohexanone with peracid, but the mixture can be separated by a series of methods and polymerized alone. It can also be used as a mixture.
β−メチル−δ−バレロラクトンは2−ヒドロキシ−4
−メチルテトラヒドロピランを原料として製造すること
ができる。β-Methyl-δ-valerolactone is 2-hydroxy-4
- Can be produced using methyltetrahydropyran as a raw material.
ラクトン類はヒドロキシアルキルアクリル酸エステルま
たは、ヒドロキシアルキルメタクリル酸エステル1モル
に対し1〜20モル好ましくは1〜10モル反応させる
。The lactones are reacted in an amount of 1 to 20 moles, preferably 1 to 10 moles, per mole of the hydroxyalkyl acrylate or hydroxyalkyl methacrylate.
ヒドロキシアルキルメタクリル酸エステル1モルに対し
、2種類のラクトン1モルずつ(計2モル)を反応させ
た場合、ヒドロキシアルキルメタクリル酸エステルの水
酸基へのラクトンの開環反応速度と生成物のラクトン末
端の水酸基へのラクトンの開環反応速度は大きく変らな
いため反応物は式(II)で表わされる化合物で
RROR2R3
1
CH−C−C−0−CH−CHO−
Ra
1
[−C−(C) −〇−] Hx
n
R1R、R2、R3−R5CH3
Ra5RbはHSCH3のいずれかでありR,、Rbは
は同時に各々の基にも換えることができる。When 1 mole of hydroxyalkyl methacrylate is reacted with 1 mole of each of the two types of lactones (2 moles in total), the ring-opening reaction rate of the lactone to the hydroxyl group of the hydroxyalkyl methacrylate and the lactone terminal of the product are Since the ring-opening reaction rate of lactone to a hydroxyl group does not change significantly, the reactant is a compound represented by formula (II), RROR2R3 1 CH-C-C-0-CH-CHO- Ra 1 [-C-(C) - 〇-] Hx
n R1R, R2, R3-R5CH3 Ra5Rb is any of HSCH3, and R, and Rb can be replaced with each group at the same time.
X−4,5
nは2を平均としてn−0の未反応物から、n−1,2
,3,4,5・・・の付加物が統計的に分布する。X-4,5 n is 2 on average, from n-0 unreacted material to n-1,2
, 3, 4, 5... adducts are statistically distributed.
しかしながら、これらを分離精製する必要はなく、種々
のラクトン付加物を有する単量体の混合物のままでアク
リル樹脂の合成に共重合モノマーとして用いることがで
きる。However, there is no need to separate and purify these, and a mixture of monomers having various lactone adducts can be used as a comonomer in the synthesis of acrylic resins.
反応速度は50〜150℃好ましくは30℃である。The reaction rate is 50-150°C, preferably 30°C.
50℃より低いと反応が遅く、150℃より高いと反応
中にアクリルの熱重合が起り、ゲル化する危険性がある
。If the temperature is lower than 50°C, the reaction will be slow, and if it is higher than 150°C, thermal polymerization of acrylic will occur during the reaction, and there is a risk of gelation.
反応系には重合禁止剤を添加することが好ましい。重合
禁止剤としてはハイドロキノン、ハイドロキノンモノメ
チルエーテル、フェノチアジン等を0.001〜5%好
ましくは、0.05〜1゜0%の範囲で用いる。It is preferable to add a polymerization inhibitor to the reaction system. As the polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, phenothiazine, etc. are used in an amount of 0.001 to 5%, preferably 0.05 to 1.0%.
反応系には窒素のような不活性ガスを通じるとラジカル
重合が起りやすくなるため、全くガスを通さないか、あ
るいは、空気等を通じることが反応物の熱重合を防止す
るのに役立つ。When an inert gas such as nitrogen is passed through the reaction system, radical polymerization tends to occur, so it is useful to prevent thermal polymerization of the reactants by not passing any gas at all, or by passing air or the like.
反応終了後、重合禁止剤を水洗等の手段により除去する
こともできるが、含有したままでも差支えない用途に対
してはそのまま用いることができる。After completion of the reaction, the polymerization inhibitor can be removed by washing with water or the like, but it can be used as is for applications where it is acceptable to keep it contained.
ラクトン類の開環重合に用いる触媒としてはテトラブチ
ルチタネート、テトラプロピルチタネート、テトラエチ
ルチタネート等のチタン化合物、オクチル酸スズ、ジブ
チルスズオキシド、ジブチルスズラウート等の有機スズ
化合物、さらには塩化第1スズ、臭化第1スズ、ヨウ化
第1スズ等のハロゲン化第1スズ、リンタングステン酸
のへテロポリ酸等を用いることができる。Catalysts used in the ring-opening polymerization of lactones include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and tetraethyl titanate, organic tin compounds such as tin octylate, dibutyltin oxide, and dibutyltin laut, and also stannous chloride and odors. Stannous halides such as stannous oxide and stannous iodide, heteropolyacids such as phosphotungstic acid, and the like can be used.
しかしこのような金属化合物を多量に添加することは、
この目的をアクリル樹脂の共重合モノマーとして使用す
る場合悪影響をおよぼすことが多い。However, adding large amounts of such metal compounds
When used as a copolymerization monomer for acrylic resins for this purpose, adverse effects often occur.
チタン系の触媒は比較的活性が強く目的物を得ることが
可能であるが、この触媒は、同時にエステル交換触媒と
して極めて活性が強いため、反応中にエステル交換反応
が進行し、ヒドロキシアルキルアクリレートまたはヒド
ロキシアルキルメタクリレート2モルから、多価アルコ
ールがはずれヒドロキシアルキルジアクリレートまたは
ヒドロキシアルキルジメタクリレートを副生する。Titanium-based catalysts have relatively high activity and can obtain the desired product, but at the same time, this catalyst is extremely active as a transesterification catalyst, so the transesterification reaction proceeds during the reaction, resulting in hydroxyalkyl acrylate or Polyhydric alcohol is removed from 2 moles of hydroxyalkyl methacrylate to produce hydroxyalkyl diacrylate or hydroxyalkyl dimethacrylate as a by-product.
このことは以下の反応式によって示される(2−ヒドロ
キシエチルメタクリレートの場合)。This is shown by the following reaction formula (in the case of 2-hydroxyethyl methacrylate).
CH3
2CH2−CCoocH2cH2oH
H3
CH2−CCOOCH2CH200C−CH3
−C−CH+ HOCH2CH20Hこのようなジア
クリレートまたはジメタクリレートは沸点が高いため、
目的物との分離が困難である。かつこれらの副生物を含
んだ目的物を他のアクリル酸エステルと溶媒中でラジカ
ル共重合させると、樹脂は三次元架橋が生じ粘度が著る
しく増大するか、さらにはゲル化に到ってしまう。CH3 2CH2-CCoocH2cH2oH H3 CH2-CCOOCH2CH200C-CH3 -C-CH+ HOCH2CH20H Since such diacrylates or dimethacrylates have a high boiling point,
Difficult to separate from target object. If the desired product containing these by-products is radically copolymerized with other acrylic esters in a solvent, the resin will undergo three-dimensional crosslinking, resulting in a significant increase in viscosity or even gelation. Put it away.
スズ系化合物や、リンタングステン酸等の触媒はエステ
ル交換反応に対し比較的活性が少ない。Catalysts such as tin-based compounds and phosphotungstic acid have relatively low activity for transesterification reactions.
しかもフッ素を除くハロゲン化第1スズを触媒として、
ラクトンをヒドロキシアルキルアクリル酸エステルまた
はメタクリル酸エステルに開環重合させると触媒活性が
強いため、80〜130℃の低い温度、かつ少ない触媒
量で十分反応が進行し、しかもエステル交換反応におよ
ぼす影響は小さい。Moreover, using a stannous halide excluding fluorine as a catalyst,
Ring-opening polymerization of lactone to hydroxyalkyl acrylic ester or methacrylic ester has strong catalytic activity, so the reaction proceeds sufficiently at a low temperature of 80 to 130°C and with a small amount of catalyst, and has no effect on the transesterification reaction. small.
これらより用いる触媒としてはスズ系触媒を用いるのが
望ましい。Among these, it is desirable to use a tin-based catalyst.
これらの触媒は本発明の方法で製造されるラクトン変性
反応性単量体中に含まれたままアクリルポリオール樹脂
等の製造に用いることができる。These catalysts can be used in the production of acrylic polyol resins and the like while remaining contained in the lactone-modified reactive monomer produced by the method of the present invention.
したがって、必ずしも除去する必要はない。Therefore, it is not necessarily necessary to remove it.
どうしても除去する必要がある場合にはキレート剤等に
よる吸着除去あるいは水洗等の方法によって除去するこ
とができる。If it is absolutely necessary to remove it, it can be removed by adsorption using a chelating agent or the like, or by washing with water.
反応は無溶剤で行ってもよいし、トルエン、キシレン、
メチルエチルケトン、メチルイソブチルケトン等の活性
水素を持たない不活性な溶剤中で行なっても良い。The reaction may be carried out without a solvent, or with toluene, xylene,
The reaction may be carried out in an inert solvent having no active hydrogen such as methyl ethyl ketone or methyl isobutyl ketone.
不活性な溶剤を使用するのは反応終了後の系内の反応粗
液の粘度を低下させる効果があり、がっ、反応中の温度
コントロールなどを容易にするためである。The reason for using an inert solvent is that it has the effect of lowering the viscosity of the reaction crude liquid in the system after the reaction is completed, and it also makes it easier to control the temperature during the reaction.
不活性な溶剤の使用の有無は本発明の反応性単量体組成
物の使用目的に応じて任意に選定できる。Whether or not an inert solvent is used can be arbitrarily selected depending on the intended use of the reactive monomer composition of the present invention.
すなわち、塗料等溶剤が含まれていても良いような製品
向けの場合には使用可能である。That is, it can be used for products such as paints that may contain solvents.
また、不活性な溶剤は反応終了後の反応粗液に後添加し
ても良い。Further, the inert solvent may be added to the reaction crude solution after the reaction is completed.
不活性な溶剤の使用量は5〜80重量%、好ましくは、
10〜50重量%である。The amount of inert solvent used is 5 to 80% by weight, preferably
It is 10 to 50% by weight.
但し、エステル結合を有する溶剤は好ましくない。なぜ
なら反応中にポリラクトンのエステル基とエステル交換
反応を起し、ヒドロキシアルキルアクリレートまたはメ
タクリレートに結合していないラクトン重合体が生成す
る恐れがあるからである。However, solvents having ester bonds are not preferred. This is because, during the reaction, a transesterification reaction may occur with the ester group of polylactone, resulting in the production of a lactone polymer that is not bonded to hydroxyalkyl acrylate or methacrylate.
塩化第1スズを触媒に用いる場合には、エステル交換反
応をほとんど促進しないので、エステル系の溶剤を用い
ることも可能である。When using stannous chloride as a catalyst, it is also possible to use an ester solvent since it hardly promotes the transesterification reaction.
用いる原料の水分は極力少ない方が好ましい。It is preferable that the moisture content of the raw materials used be as low as possible.
用いるヒドロキシアルキルアクリレートまたはメタクリ
レート中の水分は、0.001〜1,0%、ラクトン中
の水分は望ましくは0.001〜0.02%の範囲であ
る。The water content in the hydroxyalkyl acrylate or methacrylate used is preferably in the range of 0.001 to 1.0%, and the water content in the lactone is preferably in the range of 0.001 to 0.02%.
原料中の水分は反応中ラクトンを開環して、製品の酸価
を上昇させ、製品に悪影響をおよぼすからである。This is because water in the raw materials opens the lactone during the reaction, increases the acid value of the product, and has an adverse effect on the product.
酸価の高いラクトン変性ヒドロキシアルキルアクリル酸
エステルまたはメタクリル酸エステル、すなわち、本発
明の組成物中の主成分である反応性単量体はそれ自体耐
水性が悪くなり加水分解を生じやすくなる。A lactone-modified hydroxyalkyl acrylic ester or methacrylic ester having a high acid value, that is, a reactive monomer which is a main component in the composition of the present invention, itself has poor water resistance and is susceptible to hydrolysis.
また、水分はラクトンの開環反応に用いる金属触媒と反
応して触媒を不活性にしてしまう。Furthermore, water reacts with the metal catalyst used in the ring-opening reaction of lactone, rendering the catalyst inactive.
したがって原料中に水分が多い時は触媒を投入して反応
を開始する前に減圧下で加熱して水のみを留去する方が
好ましい。Therefore, when there is a lot of water in the raw material, it is preferable to heat it under reduced pressure to distill off only the water before introducing the catalyst and starting the reaction.
また、ラクトンは例えばモレキュラーシーブのような脱
水剤を用いて脱水してもよい。The lactone may also be dehydrated using a dehydrating agent such as a molecular sieve.
この反応において、未反応のε−カプロラクトンの含有
量は1%未満が好ましい。In this reaction, the content of unreacted ε-caprolactone is preferably less than 1%.
しかしながら、そのとき共重合に用いた他のラクトン類
はε−カプロラクトンより反応性が小さいため数%〜数
十%残存している場合もある。However, other lactones used in the copolymerization have lower reactivity than ε-caprolactone, and therefore may remain in an amount of several percent to several tens of percent.
これら未反応のラクトン類は溶剤と見なすことができる
ので特に除去する必要はない。Since these unreacted lactones can be considered as a solvent, there is no need to remove them.
以下、実施例を揚げて本発明の特定な具体例を説明する
が、本発明はこれらの実施例により限定されるものでは
ない。Hereinafter, specific examples of the present invention will be explained with reference to Examples, but the present invention is not limited to these Examples.
実施例−1
窒素導入管、温度計、冷却管、攪拌装置を備えた214
つロフラスコに2−ヒドロキシエチルメタクリレート2
71.2gr、ε−カプロラクトン1189.5gr、
β−メチル−6−パレロラクトン715.3gr、ヒド
ロキノンモノメチルエーテル1.0924gr、塩化第
一スズ(1%ε〜カプロラクトン溶液)0.108gr
仕込み、空気を拭き込みながら7.5時間、115℃で
反応させた。Example-1 214 equipped with nitrogen introduction tube, thermometer, cooling tube, and stirring device
2-Hydroxyethyl methacrylate 2 in a two-flask
71.2 gr, ε-caprolactone 1189.5 gr,
β-Methyl-6-parerolactone 715.3 gr, hydroquinone monomethyl ether 1.0924 gr, stannous chloride (1% ε ~ caprolactone solution) 0.108 gr
The mixture was prepared and reacted at 115° C. for 7.5 hours while wiping out air.
これを冷却し、取出して性状を調べた結果以下の通りで
あった。This was cooled, taken out, and examined for properties, and the results were as follows.
外観(APIA) 380〃(20℃)
液状
酸価(mgKOHIg) 3.62oH
価 54.0
粘度(cp/45℃> 140 H2O(%)
0.074
下の通りであった。Appearance (APIA) 380〃(20℃)
Liquid acid value (mgKOHIg) 3.62oH
Value 54.0 Viscosity (cp/45℃> 140 H2O (%)
0.074 It was as shown below.
外観(APIA) 110
〃(20℃) 固体
酸価(mgKOHIg) 2. 120H価(〃
) 53.40
粘度(CP740℃) 264
水分(%) 0.008
最終生成物は、ε−カプロラクトン1.80%、β−メ
チル−6−バレロラクトン9.80%を含有することが
確認された。Appearance (APIA) 110〃(20℃) Solid acid value (mgKOHIg) 2. 120H value (〃
) 53.40 Viscosity (CP740°C) 264 Moisture (%) 0.008 The final product was confirmed to contain 1.80% ε-caprolactone and 9.80% β-methyl-6-valerolactone .
比較例−1
実施例−1と同様な装置でヒドロキシエチルアクリレー
ト 132.0gr、ε−カプロラクトン11170.
Ogr、塩化スズ(1%ε−カプロラクトン溶液)0.
30gr 、ヒドロキノンモノメチルエーテル3.28
gr 、を仕込み空気を拭き込みなから18hr120
℃で反応させた。Comparative Example-1 Hydroxyethyl acrylate 132.0gr and ε-caprolactone 11170gr were used in the same apparatus as in Example-1.
Ogr, tin chloride (1% ε-caprolactone solution) 0.
30gr, hydroquinone monomethyl ether 3.28
Prepare gr and wipe out the air for 18 hours and 120 hours.
The reaction was carried out at ℃.
これを冷却し、取り出して性状を調べた結果以最終生成
物は白色固体でε−カプロラクトン0.8%、ヒドロキ
シエチルアクリレートo、ot%を含有することが確認
された。The product was cooled, taken out, and examined for properties. As a result, it was confirmed that the final product was a white solid containing 0.8% of ε-caprolactone and 0.0% of hydroxyethyl acrylate.
実施例−2
窒素導入管、温度計、冷却管、攪拌装置を備えた0、5
14つロフラスコに2−ヒドロキシエチルメタクリレー
ト40.54gr、ε−カプロラクトン284.45g
r、β−メチル−δ−バレロラクトン78.22grs
ヒドロキノンモノメチルエーテル0.20gr、塩化
第一スズ(1%ε−カプロラクトン溶液)2.1363
gr仕込み、空気を拭き込みながら12時間、115℃
で反応させた。Example-2 0, 5 equipped with nitrogen introduction tube, thermometer, cooling tube, and stirring device
40.54g of 2-hydroxyethyl methacrylate and 284.45g of ε-caprolactone in 14 flasks.
r, β-methyl-δ-valerolactone 78.22 grs
Hydroquinone monomethyl ether 0.20g, stannous chloride (1% ε-caprolactone solution) 2.1363
gr preparation, 115℃ for 12 hours while wiping out air
I reacted with
これを冷却し、取出して性状を調べた結果以下の通りで
あった。This was cooled, taken out, and examined for properties, and the results were as follows.
外観(八PHA) 300〃(20℃)
液状
酸価(mgKOH/g) 2 、 99
OH価 40.60
粘度(c p / 45℃) 241H20(%)
0.036最終生成物は、ε−カ
プロラクトン0.73%、β−メチル−δ−バレロラク
トン6.15%を含有することが確認された。Appearance (8 PHA) 300 (20℃)
Liquid acid value (mgKOH/g) 2, 99
OH value 40.60 Viscosity (c p / 45℃) 241H20 (%)
The final product was found to contain 0.73% ε-caprolactone and 6.15% β-methyl-δ-valerolactone.
実施例−3
窒素導入管、温度計、冷却管、攪拌装置を備えた0、5
N4つロフラスコに2−ヒドロキシエチルメタクリレー
ト40.03gr、ε−カプロラクトン208.56g
r、β−メチル−δ−バレロラクトン140.3gr、
ヒドロキノンモノメチルエーテル0.1983gr、塩
化第一スズ(1%εカプロラクトン溶液)2.0013
gr仕込み、空気を拭き込みながら17時間、115℃
で反応させた。Example-3 0, 5 equipped with nitrogen introduction tube, thermometer, cooling tube, and stirring device
40.03g of 2-hydroxyethyl methacrylate and 208.56g of ε-caprolactone in a 4-N flask.
r, β-methyl-δ-valerolactone 140.3 gr,
Hydroquinone monomethyl ether 0.1983 gr, stannous chloride (1% ε-caprolactone solution) 2.0013
gr preparation, 115℃ for 17 hours while wiping out the air.
I reacted with
これを冷却し、取出して性状を調べた結果以下の通りで
あった。This was cooled, taken out, and examined for properties, and the results were as follows.
外観(APHA) 300〃(20℃)
液状
酸価(mgKOH/g) 3. 31O
H価 43.71
粘度(c p/45℃) 164
H20(%) 0.034最終生
成物は、ε−カプロラクトン0.07%、β−メチル−
δ−バレロラクトン15.65%を含有することが確認
された。Appearance (APHA) 300〃(20℃)
Liquid acid value (mgKOH/g) 3. 31O
H number 43.71 Viscosity (c p/45°C) 164 H20 (%) 0.034 The final product contains ε-caprolactone 0.07%, β-methyl-
It was confirmed that it contained 15.65% of δ-valerolactone.
実施例−4
窒素導入管、温度計、冷却管、攪拌装置を備えた0、1
4つロフラスコに2−ヒドロキシエチルメタクリレート
40.08gr、ε−カプロラクトン281.26gr
、β−メチル−δ−バレロラクトン140.61gr、
ヒドロキノンモノメチルエーテル0.25gr、塩化第
一スズ(1%ε−カプロラクトン溶液)2.359gr
仕込み、空気を拭き込みながら17時間、115℃で反
応させた。Example-4 0 and 1 equipped with nitrogen introduction tube, thermometer, cooling tube, and stirring device
40.08 gr of 2-hydroxyethyl methacrylate, 281.26 gr of ε-caprolactone in a 4-bottle flask.
, β-methyl-δ-valerolactone 140.61 gr,
Hydroquinone monomethyl ether 0.25 gr, stannous chloride (1% ε-caprolactone solution) 2.359 gr
The mixture was prepared and reacted at 115° C. for 17 hours while wiping out air.
これを冷却し、取出して性状を調べた結果以下の通りで
あった。This was cooled, taken out, and examined for properties, and the results were as follows.
外観(APHA) 300〃(20℃)
液状
酸価(mgKOH/g) 3. 13o
H価 14.52
粘度(cp/45℃) 230
H2O(%) 0.031最終生成
物は、ε−カプロラクトン0.06%、β−メチル−δ
−バレロラクトン11.88%を含有することが確認さ
れた。Appearance (APHA) 300〃(20℃)
Liquid acid value (mgKOH/g) 3. 13o
H number 14.52 Viscosity (cp/45°C) 230 H2O (%) 0.031 The final product contains ε-caprolactone 0.06%, β-methyl-δ
- Confirmed to contain 11.88% valerolactone.
実施例−5
窒素導入管、温度計、冷却管、攪拌装置を備えたO、’
14つ目フラスコに2−ヒドロキシエチルメタクリレー
ト40.03gr、と−カプロラクトン263.31g
r、β−メチル−6−バレロラクトン105.33gr
、ヒドロキノンモノメチルエーテル0.2072gr、
塩化第一スズ(1%E−カプロラクトン溶液)2.06
37gr仕込み、空気を拭き込みながら11時間、11
5℃で反応させた。Example-5 O equipped with a nitrogen introduction pipe, thermometer, cooling pipe, and stirring device.'
In the 14th flask, 40.03g of 2-hydroxyethyl methacrylate and 263.31g of caprolactone.
r, β-methyl-6-valerolactone 105.33 gr
, hydroquinone monomethyl ether 0.2072gr,
Stannous chloride (1% E-caprolactone solution) 2.06
37gr preparation, 11 hours while wiping out the air, 11
The reaction was carried out at 5°C.
これを冷却し、取出して性状を調べた結果以下の通りで
あった。This was cooled, taken out, and examined for properties, and the results were as follows.
外観(APIA) 300〃(20℃)
液状
酸価(ggKOH/g) 3 、 03
OH価 25. 15粘度(c p/
45℃) 214
H20(%) 0.026最終生
成物は、ε−カプロラクトン0.07%、β−メチル−
δ−バレロラクトン10.13%を含有することが確認
された。Appearance (APIA) 300〃(20℃)
Liquid acid value (ggKOH/g) 3, 03
OH value 25. 15 viscosity (c p/
45°C) 214 H20 (%) 0.026 The final product contains ε-caprolactone 0.07%, β-methyl-
It was confirmed that it contained 10.13% of δ-valerolactone.
実施例−6
窒素導入管、温度計、冷却管、攪拌装置を備えた0、5
14つロフラスコに2−ヒドロキシエチルメタクリレー
ト40.01gr、ε−カブロラクトン245.58g
r、β−メチル−δ−バレロラクトン140.33gr
、ヒドロキノンモノメチルエーテル0.2145gr、
塩化第一スズ(1%ε−カプロラクトン溶液)4.26
gr仕込み、空気を拭き込みながら13時間、115℃
で反応させた。これを冷却し、取出して性状を調べた結
果以下の通りであった。Example-6 0, 5 equipped with nitrogen introduction tube, thermometer, cooling tube, and stirring device
40.01g of 2-hydroxyethyl methacrylate and 245.58g of ε-cabrolactone in 14 flasks.
r, β-methyl-δ-valerolactone 140.33 gr
, hydroquinone monomethyl ether 0.2145gr,
Stannous chloride (1% ε-caprolactone solution) 4.26
gr preparation, 115℃ for 13 hours while wiping out the air.
I reacted with This was cooled, taken out, and examined for properties, and the results were as follows.
外観(APHA) 300〃(20℃)
液状
酸価(lI1gKOH/g) 3 、
94oH価 36.26
粘度(c p/45℃) 207
H20(%) 0.029最終生
成物は、ε−カプロラクトン0.25%、β−メチル−
δ−バレロラクトン9.17%を含有することが確認さ
れた。Appearance (APHA) 300〃(20℃)
Liquid acid value (lI1gKOH/g) 3,
94oH value 36.26 Viscosity (c p/45°C) 207 H20 (%) 0.029 The final product contains ε-caprolactone 0.25%, β-methyl-
It was confirmed that it contained 9.17% of δ-valerolactone.
実施例−7
窒素導入管、温度計、冷却管、攪拌装置を備えたO、’
14つロフラスコに2−ヒドロキシエチルメタクリレー
ト40.00gr、ε−カプロラクトン245.58g
r、β−メチル−δ−バレロラクトン140.3:3g
r、ヒドロキノンモノメチルエーテル0.2180gr
、塩化第一スズ(1%ε−カプロラクトン溶液)2.3
243gr仕込み、空気を拭き込みながら13時間、1
15℃で反応させた。これを冷却し、取出して性状を調
べた結果以下の通りであった。Example-7 O equipped with a nitrogen introduction tube, thermometer, cooling tube, and stirring device.'
40.00g of 2-hydroxyethyl methacrylate and 245.58g of ε-caprolactone in 14 flasks.
r, β-methyl-δ-valerolactone 140.3: 3g
r, hydroquinone monomethyl ether 0.2180gr
, stannous chloride (1% ε-caprolactone solution) 2.3
Prepare 243gr, 13 hours while wiping out the air, 1
The reaction was carried out at 15°C. This was cooled, taken out, and examined for properties, and the results were as follows.
外観(APIA) 300〃(20℃)
液状
酸価(mgKOH/g) 3 、03O
H価 33.19
粘度(c p/45℃) 187
H20(%) 0.026最終生成
物は、ε−カプロラクトン0.22%、β−メチル−δ
−バレロラクトン10.02%を含有することが確認さ
れた。Appearance (APIA) 300〃(20℃)
Liquid acid value (mgKOH/g) 3,03O
H number 33.19 Viscosity (c p/45°C) 187 H20 (%) 0.026 The final product contains ε-caprolactone 0.22%, β-methyl-δ
- Confirmed to contain 10.02% valerolactone.
Claims (3)
化学式、表等があります▼・・・・( I ) [R、R_1、R_2、R_3=H、CH_3R_4; ▲数式、化学式、表等があります▼・・・・(A) ▲数式、化学式、表等があります▼・・・・(B) ▲数式、化学式、表等があります▼・・・・(C) ▲数式、化学式、表等があります▼・・・・(D) [R_4はAおよびBの共重合体又はAおよびC、Aお
よびD、AおよびCおよびDの共重合およびA、Bおよ
びCおよびDで、末端にOH基を有する]。(1) Reactive monomer represented by the following formula (I) ▲ Formula,
There are chemical formulas, tables, etc.▼・・・(I) [R, R_1, R_2, R_3=H, CH_3R_4; ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・(A) ▲Mathematical formulas, chemical formulas, tables etc.▼・・・(B) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(C) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(D) [R_4 is A and A copolymer of B or a copolymer of A and C, A and D, A, C and D, and A, B, C and D having an OH group at the end].
アクリレートまたはメタクリレート ▲数式、化学式、表等があります▼・・・・(II) [R、R_1、R_2、R_3=H、CH_3]にε−
カプロラクトンと、β−メチル−δ−バレロラクトンの
混合物あるいはε−カプロラクトンとトリメチルカプロ
ラクトンの混合物を反応させることを特徴とする反応性
単量体の製造方法。(2) Hydroxyalkyl monoacrylate or methacrylate represented by the following formula (II)▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) ε in [R, R_1, R_2, R_3=H, CH_3] −
1. A method for producing a reactive monomer, which comprises reacting a mixture of caprolactone and β-methyl-δ-valerolactone or a mixture of ε-caprolactone and trimethylcaprolactone.
て使用する特許請求の範囲第(2)項記載の反応性単量
体の製造方法。(3) The method for producing a reactive monomer according to claim (2), which uses a tin compound and/or a titanium compound as a catalyst.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1328059A JP3023917B2 (en) | 1989-12-18 | 1989-12-18 | Method for producing reactive monomer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP1328059A JP3023917B2 (en) | 1989-12-18 | 1989-12-18 | Method for producing reactive monomer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH03188043A true JPH03188043A (en) | 1991-08-16 |
JP3023917B2 JP3023917B2 (en) | 2000-03-21 |
Family
ID=18206057
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP1328059A Expired - Fee Related JP3023917B2 (en) | 1989-12-18 | 1989-12-18 | Method for producing reactive monomer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3023917B2 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0683215A1 (en) * | 1994-05-17 | 1995-11-22 | Flachglas Aktiengesellschaft | Cast resin mixture for bonding substantially sheet-shaped elements |
CN103772666A (en) * | 2012-10-17 | 2014-05-07 | 成都市新津托展油墨有限公司 | Polyester modified polyacrylate resin and preparation method thereof |
CN115850673A (en) * | 2022-12-15 | 2023-03-28 | 青岛科技大学 | Preparation method of low molecular weight poly (gamma-butyrolactone) polyalcohol |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01151537A (en) * | 1987-12-09 | 1989-06-14 | Nippon Kayaku Co Ltd | (meth)acrylic acid ester |
-
1989
- 1989-12-18 JP JP1328059A patent/JP3023917B2/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01151537A (en) * | 1987-12-09 | 1989-06-14 | Nippon Kayaku Co Ltd | (meth)acrylic acid ester |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0683215A1 (en) * | 1994-05-17 | 1995-11-22 | Flachglas Aktiengesellschaft | Cast resin mixture for bonding substantially sheet-shaped elements |
CN103772666A (en) * | 2012-10-17 | 2014-05-07 | 成都市新津托展油墨有限公司 | Polyester modified polyacrylate resin and preparation method thereof |
CN115850673A (en) * | 2022-12-15 | 2023-03-28 | 青岛科技大学 | Preparation method of low molecular weight poly (gamma-butyrolactone) polyalcohol |
Also Published As
Publication number | Publication date |
---|---|
JP3023917B2 (en) | 2000-03-21 |
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