JPH0415803B2 - - Google Patents
Info
- Publication number
- JPH0415803B2 JPH0415803B2 JP3623583A JP3623583A JPH0415803B2 JP H0415803 B2 JPH0415803 B2 JP H0415803B2 JP 3623583 A JP3623583 A JP 3623583A JP 3623583 A JP3623583 A JP 3623583A JP H0415803 B2 JPH0415803 B2 JP H0415803B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- compound
- meth
- ethylenically unsaturated
- polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000000839 emulsion Substances 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000000034 method Methods 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 238000007720 emulsion polymerization reaction Methods 0.000 description 6
- -1 2-hydroxypropyl Chemical group 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- IGDUBEZMULCNAF-UHFFFAOYSA-N 2-[(2-dodecylphenoxy)methyl]oxirane Chemical compound CCCCCCCCCCCCC1=CC=CC=C1OCC1OC1 IGDUBEZMULCNAF-UHFFFAOYSA-N 0.000 description 2
- WNISWKAEAPQCJQ-UHFFFAOYSA-N 2-[(2-nonylphenoxy)methyl]oxirane Chemical compound CCCCCCCCCC1=CC=CC=C1OCC1OC1 WNISWKAEAPQCJQ-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- WORJRXHJTUTINR-UHFFFAOYSA-N 1,4-dioxane;hydron;chloride Chemical compound Cl.C1COCCO1 WORJRXHJTUTINR-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 description 1
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 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
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Description
本発明は、安定な共重合体エマルジヨンの製造
法に関するものである。
従来の水媒体中でのエマルジヨン重合処方で
は、界面活性剤または保護コロイドとして水溶性
高分子物質の添加が必要であつた。
しかしながら、塗料、接着剤およびコンクリー
ト補強剤のような重合体エマルジヨンをそのまま
使用したり、SBRのようなゴムラテツクスを得
る場合には、これらの添加物に起因する望ましか
らぬ影響を受けることがある。
近年、そのもの自身は界面活性能は持たない
が、親水性を付与するような基を持つ単量体をエ
マルジヨン重合に使用することが知られている。
例えば、ｐ−スチレンスルホン酸ソーダ塩（特
開昭54−95636号公報、特公昭53−37271号公報、
特公昭53−6190号公報）がその代表的なものであ
る。
しかしながら、このものは製造上高価であり、
かつ不純物として臭化ナトリウムをかなりの量含
有することとなり、その毒性の面から懸念される
ものであり、またその混入量のコントロールが困
難であるという欠点を有する。
ところで、乳化力を持つだけでなく、自ら重合
または共重合する自己乳化性物質が知られてい
る。
例えば、塩基性または多塩基性の不飽和酸のオ
キシエチルエステルを使用する方法（特公昭36−
20385号公報）、またはマレイン酸、フマール酸も
しくはイタコン酸誘導体の共重合性乳化剤を使用
する方法（特開昭51−30284号公報、特開昭54−
83984号公報）等がある。
これらの方法においては、共重合するための手
段として、その構造中に含まれるマレイン基、フ
エニル基、イタコニル基の共重合性の低さ故に、
重合体エマルジヨンの主成分である（メタ）アク
リル酸エステル、スチレン、アクリロニトリル、
酢酸ビニル等との重合性の問題が生じる。
また、これらを使用して、得られた重合体エマ
ルジヨンからの樹脂皮膜は、前記した界面活性
剤、または水溶性高分子物質によるところの悪影
響を解消しうるものでない。
一方、使用方法に関しては、前述のスチレンス
ルホン酸ソーダ塩の如く、界面活性能は持たない
が、親水性を付与するような基を持つ単量体は、
その乳化重合への使用において、従来法とは異な
つた操作が必要であり、時には他の界面活性剤と
の併用が好ましいなど、使用時の困難さが伴うも
のである。
これに対して、後者の自己乳化性物質は、それ
自身が乳化力を有するために、通常行われる乳化
重合操作にて応用でき、取り扱いが容易という利
点を有する。
本発明者らは、特殊な乳化重合操作を必要とす
ることなく、自ら重合または共重合する自己乳化
性物質に着眼し、前記問題点を解消すべく、鋭意
研究を重ねた結果、本発明に到達したものであ
る。
すなわち、本発明は、
エチレン性不飽和単量体の少なくとも１種以上
を前記エチレン性不飽和単量体と共重合可能な、
一般式、
［ただし、式中R1は炭素数８〜20のアルキル
基、Ｍはアルカリ金属またはNH4である。］
で示される化合物の存在下で、水性媒体中で重合
させることを特徴とする安定な共重合体エマルジ
ヨンの製造法を提供するものである。
本発明で使用するエチレン性不飽和単量体とし
ては、例えば（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ｎ−ブチ
ル、（メタ）アクリル酸ラウリル、（メタ）アクリ
ル酸２−ヒドロキシエチル、（メタ）アクリル酸
２−ヒドロキシプロピル、（メタ）アクリル酸２
−ヒドロキシ−３−クロロプロピル、（メタ）ア
クリル酸ポリヒドロキシエチル、（メタ）アクリ
ル酸ポリヒドロキシプロピル、（メタ）アクリル
酸グリシジルエーテル等のアクリル酸エステル類
およびメタクリル酸エステル、アクリル酸、メタ
クリル酸、クロトン酸等のα−もしくはβ−不飽
和カルボン酸類もしくはその塩類、アクリルアマ
イド、メタクリルアマイド、Ｎ−メチルアクリル
アマイド、Ｎ−メチロールアクリルアマイド等の
α−もしくはβ−不飽和アマイド類、アクリロニ
トリル、メタクリロニトリル等の不飽和ニトリル
類、塩化ビニル、塩化ビニリデン等のハロゲン化
ビニル類、スチレン、α−メチルスチレン、ビニ
ルトルエン等のスチレン誘導体類、酢酸ビニル、
プロピオン酸ビニル、ラウリル酸ビニル等のビニ
ルエステル類、α−オレフイン類、ブタジエン等
の共役ジエン類、無水マレイン酸類、マレイン酸
エステル類、イタコン酸エステル類等が挙げられ
る。
一般式（）で示される化合物は、一般にアル
キルフエノールのグリシジルエーテルと（メタ）
アクリル酸とを、３級アミン、４級アンモニウム
塩、三フツ化ホウ素エーテル錯塩、ホウフツ化亜
鉛、四塩化錫、塩化アルミニウムなどの触媒およ
びハイドロキノン、ハイドロキノンモノメチルエ
ーテルなどの重合禁止剤の存在下に30〜150℃で
反応させて得られるエポキシ（メタ）アクリレー
トを無水硫酸、クロロスルホン酸などのスルホン
化剤で、必要ならば四塩化炭素、ジクロルメタン
などの溶媒を用い、−10〜50℃にてスルホン化後
アルカリ金属で中和して得られ、あるいはこの化
合物を塩化アンモニウムで複分解して得られる。
具体的に述べると、アルキルフエノールのグリ
シジルエーテルとしては、例えば、オクチルフエ
ニルグリシジルエーテル、ノニルフエニルグリシ
ジルエーテル、ドデシルフエニルグリシジルエー
テルなどが挙げられる。
硫酸化剤としては、例えば硫酸、発煙硫酸、ク
ロルスルホン酸、無水硫酸等が挙げられる。
アルカリ金属の水酸化物としては、例えば水酸
化ナトリウム、水酸化カリウムなどが挙げられ
る。
本発明において、一般式（）で示される化合
物の使用量は任意であるが、好ましくはエチレン
性不飽和単量体100重量部に対して0.01〜10重量
部、より好ましくは１〜５重量部である。
本発明の安定な共重合体エマルジヨンを得る場
合、任意に公知の界面活性剤を併用することも可
能であるが、本発明の一般式（）で示される化
合物みによつても充分に安定な共重合体エマルジ
ヨンが得られ、併用する場合も従来のエマルジヨ
ン重合処方において使用される量よりもかなり少
ない量で使用できる。
本発明に従つて得られる安定な共重合体エマル
ジヨンは、重合安定性および機械安定性に優れ、
従来から重合体エマルジヨンが使用されている
種々の分野、例えば塗料、接着剤およびコンクリ
ート補強剤等へ使用した場合、優れた効果を与え
る。また、本発明に従つて得られる安定な共重合
体エマルジヨンは、毒性の懸念もなく、かつ安価
である。
以下に本発明を実施例により具体的に説明す
る。
実施例 １
温度計、コンデンサー、撹拌装置、滴下ロート
を備えた300ml容四つ口フラスコにメタクリル酸
90.3ｇ、重合禁止剤としてハイドロキノンモノメ
チルエーテル0.20ｇ、触媒としてトリメチルベン
ジルアンモニウムクロリドを仕込み、撹拌する。
内温を80℃に上げ、滴下ロートよりノニルフエニ
ルグリシジルエーテル（エポキシ当量280）280ｇ
を徐々に滴下する。滴下とともに内温がわずかに
上昇するが、必要に応じ冷却し、液温を80〜85℃
に保つようにする。滴下は１時間30分かけて終了
するようにする。全量滴下後、その温度で１時間
熟成する。反応液を塩酸−ジオキサン法にてエポ
キシ量を測定したが、エポキシ酸素量として0.05
％であり、IRチヤートより920cm-1の吸収はほぼ
全滅していた。
実施例 ２
実施例１で得られたメタクリル酸エステル
374.2ｇを塩化メチレン300ｇに溶かし、１溶四
つ口フラスコに仕込む。窒素気流下に滴下ロート
よりクロルスルホン酸を滴下する。副生する塩酸
ガスは、遅滞なく反応系外に出し、中和処理す
る。
クロルスルホン酸128ｇを約２時間かけて滴下
する。その際の液温は５〜10℃に保持する。得ら
れたスルホン化物を、水酸化ナトリウム44ｇを含
む水1128ｇ中に撹拌しながら投入中和する。中和
温度は25℃を越えないようにする。最終中和液の
PHが６〜７になるように水酸化ナトリウムで調整
する。
下層の塩化メチレンを抜き取り、スルホン化物
を得る。
得られた化合物水溶液は、ドデシルメルカプタ
ン法による臭素価9.5揮発分70.5％、エプトン法
によるアニオン分（−SO3）5.10％、有機塩素
0.17％であり、次式（）の化合物92.6％と、次
式（）の化合物7.4％の混合物水溶液であるこ
とを確認した。
実施例 ３
実施例１で得られたメタクリル酸エステルを塩
化メチレン300ｇに溶かし、１四つ口フラスコ
に仕込む。同時にピリジン86ｇを混入しておく。
フラスコを氷冷しながら、クロルスルホン酸128
ｇを徐々に添加する。液温を０〜10℃に保ちなが
ら、２時間かけてクロルスルホン酸の添加を完了
する。
全量添加後、白色結晶を濾別し、濾液を水酸化
ナトリウム44ｇを含む水1128ｇ中に撹拌しながら
投入して中和する。
中和温度は、25℃を越えないようにする。
最終液のPHをチエツクし、中和のPHが６〜７に
なる様に水酸化ナトリウム水溶液にて調整する。
中和後、下層の塩化メチレンを抜き取り、スル
ホン化合物水溶液を得る。得られた化合物は揮発
分70.5％、ドデシルメルカプタン法による臭素価
10.0、エプトン法によるアニオン分51.3％、有機
塩素0.05％であり、前記式（）の化合物97.5％
と前記式（）の化合物2.5％の混合物水溶液で
あることを確認した。
実施例 ４
温度計、コンデンサー、撹拌装置、滴下ロート
を備えた300ml容四つ口フラスコにメタクリル酸
86ｇ、重合禁止剤としてハイドロキノンモノメチ
ルエーテル0.20ｇ、触媒としてトリメチルベンジ
ルアンモニウムクロライド1.2ｇを仕込み撹拌溶
解させる。
内温を80℃に上げ滴下ロートよりドデシルフエ
ニルグリシジルエーテル318ｇを徐々に添加する。
滴下を１時間30分で終了させ、その温度で、４時
間熟成する。
反応液のエポキシ酸素量は0.02％であり、反応
は終了していた。
実施例 ５
実施例４で得られたメタクリル酸エステル404
ｇを塩化メチレン300ｇに溶かし、２四つ口フ
ラスコに仕込む。同時にピリジン160ｇを混入し
ておく。
フラスコを氷冷しながら、クロルスルホン酸
118ｇを徐々に添加する。液温を０〜10℃に保ち
ながら２時間かけてクロルスルホン酸の添加を完
了する。
全量添加後、白色結晶を濾別し、濾液を水酸化
ナトリウム44ｇを含む水1183ｇ中に撹拌冷却しな
がら、温度が25℃を越えないようにして投入して
中和する。
下層の塩化メチレン層を抜取りスルホン化合物
水溶液を得る。
得られた化合物は揮発分69.5％、ドデシルメル
カプタン法による臭素価9.2、エプトン法による
アニオン分（−SO3）4.7％、有機塩素0.05％であ
り、次式（）の化合物97.3％と、次式（）の
化合物2.7％の混合物水溶液であることを確認し
た。
実施例 ６
エチレン性不飽和単量体の所定量の1/10量、一
般式（）で示される化合物および水を500ml容
四つ口フラスコに仕込み、70℃で加熱撹拌する。
次に重合開始剤を添加する。
数分乃至30分で発熱し、重合が開始する。
重合開始後、残りのエチレン性不飽和単量体を
添加する。重合温度は80±１℃で、添加時間は３
時間である。エチレン性不飽和単量体を全量添加
した後、80℃で１時間熟成し、各種共重合体エマ
ルジヨンを得た。それらを第１表に記載する。
実施例 ７
実施例６で得られた各種共重合体エマルジヨン
について各種安定性試験を行つた。それらを第２
表に記載する。
実施例 ８
実施例６にて得られたエマルジヨン100ｇをテ
トラヒドロフランに溶かし、セロハン膜に包み、
ソツクスレー抽出器にて煮沸し、エマルジヨン中
の乳化剤を抽出したところ、第３表の如くなり、
本発明において得られた化合物のの抽出量は少な
く、重合に関与していることが確認できた。
The present invention relates to a method for producing stable copolymer emulsions. Conventional emulsion polymerization formulations in aqueous media required the addition of water-soluble polymeric substances as surfactants or protective colloids. However, the raw use of polymer emulsions such as paints, adhesives and concrete reinforcements, or the production of rubber latexes such as SBR, may suffer from undesirable effects due to these additives. . In recent years, it has become known to use monomers in emulsion polymerization that do not themselves have surface-active properties but have groups that impart hydrophilicity. For example, p-styrene sulfonic acid sodium salt (Japanese Patent Application Laid-Open No. 54-95636, Japanese Patent Publication No. 53-37271,
Special Publication No. 53-6190) is a representative example. However, this product is expensive to manufacture;
Moreover, it contains a considerable amount of sodium bromide as an impurity, which is a concern from the viewpoint of toxicity, and has the drawback that it is difficult to control the amount of sodium bromide mixed in. By the way, self-emulsifying substances that not only have emulsifying power but also polymerize or copolymerize themselves are known. For example, a method using oxyethyl ester of a basic or polybasic unsaturated acid (Japanese Patent Publication No.
20385), or a method using a copolymerizable emulsifier of maleic acid, fumaric acid or itaconic acid derivatives (JP-A-51-30284, JP-A-54-
83984) etc. In these methods, as a means for copolymerization, due to the low copolymerizability of maleic, phenyl, and itaconyl groups contained in the structure,
The main components of polymer emulsion are (meth)acrylic acid ester, styrene, acrylonitrile,
Problems arise in polymerizability with vinyl acetate and the like. Furthermore, the resin film from the polymer emulsion obtained using these cannot eliminate the adverse effects caused by the above-mentioned surfactants or water-soluble polymer substances. On the other hand, regarding the method of use, monomers that do not have surfactant ability but have a group that imparts hydrophilicity, such as the above-mentioned sodium styrene sulfonate,
When used in emulsion polymerization, operations are required that differ from conventional methods, and sometimes it is preferable to use them in combination with other surfactants, leading to difficulties in use. On the other hand, since the latter self-emulsifying substance itself has emulsifying power, it has the advantage that it can be applied in commonly performed emulsion polymerization operations and is easy to handle. The present inventors focused on self-emulsifying substances that self-polymerize or copolymerize without the need for special emulsion polymerization operations, and as a result of intensive research to solve the above problems, the present invention was developed. It has been reached. That is, the present invention provides at least one type of ethylenically unsaturated monomer that is copolymerizable with the ethylenically unsaturated monomer.
general formula, [However, in the formula, R1 is an alkyl group having 8 to 20 carbon atoms, and M is an alkali metal or NH4 . ] Provides a method for producing a stable copolymer emulsion, which is characterized by polymerizing in an aqueous medium in the presence of a compound represented by the following. Examples of the ethylenically unsaturated monomer used in the present invention include methyl (meth)acrylate, (meth)
Ethyl acrylate, n-butyl (meth)acrylate, lauryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid 2
-Hydroxy-3-chloropropyl, polyhydroxyethyl (meth)acrylate, polyhydroxypropyl (meth)acrylate, glycidyl ether (meth)acrylate and other acrylic acid esters and methacrylic esters, acrylic acid, methacrylic acid, α- or β-unsaturated carboxylic acids such as crotonic acid or their salts, α- or β-unsaturated amides such as acrylamide, methacrylamide, N-methylacrylamide, N-methylolacrylamide, acrylonitrile, methacrylamide, etc. Unsaturated nitriles such as nitrile, vinyl chloride, vinyl halides such as vinylidene chloride, styrene derivatives such as styrene, α-methylstyrene, vinyltoluene, vinyl acetate,
Examples include vinyl esters such as vinyl propionate and vinyl laurate, α-olefins, conjugated dienes such as butadiene, maleic anhydride, maleic esters, and itaconic esters. The compound represented by the general formula () is generally a glycidyl ether of alkylphenol and (meth)
acrylic acid in the presence of a catalyst such as a tertiary amine, quaternary ammonium salt, boron trifluoride ether complex, zinc borofluoride, tin tetrachloride, or aluminum chloride, and a polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether. Epoxy (meth)acrylate obtained by reacting at ~150°C is sulfonated at -10 to 50°C using a sulfonating agent such as sulfuric anhydride or chlorosulfonic acid, and if necessary a solvent such as carbon tetrachloride or dichloromethane. It can be obtained by neutralizing with an alkali metal after conversion, or by metathesis of this compound with ammonium chloride. Specifically, examples of the glycidyl ether of alkylphenol include octylphenyl glycidyl ether, nonylphenyl glycidyl ether, and dodecyl phenyl glycidyl ether. Examples of the sulfating agent include sulfuric acid, oleum, chlorosulfonic acid, and sulfuric anhydride. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. In the present invention, the amount of the compound represented by the general formula () used is arbitrary, but preferably 0.01 to 10 parts by weight, more preferably 1 to 5 parts by weight based on 100 parts by weight of the ethylenically unsaturated monomer. It is. When obtaining the stable copolymer emulsion of the present invention, it is possible to optionally use a known surfactant, but it is also possible to obtain a sufficiently stable copolymer emulsion by using the compound represented by the general formula () of the present invention. Copolymer emulsions are obtained which, when used in combination, can be used in significantly lower amounts than those used in conventional emulsion polymerization formulations. The stable copolymer emulsion obtained according to the present invention has excellent polymerization stability and mechanical stability,
When used in various fields in which polymer emulsions have traditionally been used, such as paints, adhesives, and concrete reinforcing agents, they provide excellent effects. Furthermore, the stable copolymer emulsion obtained according to the present invention is free from toxicity concerns and is inexpensive. The present invention will be specifically explained below using examples. Example 1 Methacrylic acid was added to a 300 ml four-necked flask equipped with a thermometer, condenser, stirrer, and dropping funnel.
90.3 g, hydroquinone monomethyl ether 0.20 g as a polymerization inhibitor, and trimethylbenzylammonium chloride as a catalyst were charged and stirred.
Raise the internal temperature to 80℃ and add 280 g of nonylphenyl glycidyl ether (epoxy equivalent: 280) from the dropping funnel.
Gradually drip. The internal temperature will rise slightly as the liquid is dripped, but cool it down as necessary to keep the liquid temperature at 80-85℃.
Try to keep it. The dripping should take 1 hour and 30 minutes to complete. After dropping the entire amount, it is aged at that temperature for 1 hour. The amount of epoxy in the reaction solution was measured using the hydrochloric acid-dioxane method, and the amount of epoxy oxygen was 0.05.
%, and the absorption at 920 cm -1 was almost completely wiped out compared to the IR chart. Example 2 Methacrylic acid ester obtained in Example 1
Dissolve 374.2g in 300g of methylene chloride and charge it into a 1-dissolved four-necked flask. Chlorosulfonic acid is added dropwise from the dropping funnel under a nitrogen stream. The by-produced hydrochloric acid gas is discharged from the reaction system without delay and is neutralized. 128 g of chlorosulfonic acid is added dropwise over about 2 hours. The liquid temperature at that time is maintained at 5 to 10°C. The obtained sulfonated product was neutralized by adding it to 1128 g of water containing 44 g of sodium hydroxide while stirring. The neutralization temperature should not exceed 25°C. of final neutralization solution
Adjust the pH to 6-7 with sodium hydroxide. Methylene chloride in the lower layer is extracted to obtain a sulfonated product. The obtained compound aqueous solution had a bromine value of 9.5 by the dodecyl mercaptan method, a volatile content of 70.5%, an anion content (-SO 3 ) of 5.10% by the Epton method, and an organic chlorine content of 5.10% by the Epton method.
It was confirmed that it was a mixture aqueous solution of 92.6% of the compound of the following formula () and 7.4% of the compound of the following formula (). Example 3 The methacrylic acid ester obtained in Example 1 was dissolved in 300 g of methylene chloride and charged into a four-necked flask. At the same time, mix in 86g of pyridine.
While cooling the flask on ice, add chlorosulfonic acid 128
Gradually add g. The addition of chlorosulfonic acid is completed over 2 hours while maintaining the liquid temperature at 0 to 10°C. After the entire amount has been added, the white crystals are separated by filtration, and the filtrate is neutralized by pouring it into 1128 g of water containing 44 g of sodium hydroxide while stirring. The neutralization temperature should not exceed 25°C. Check the pH of the final solution and adjust it with an aqueous sodium hydroxide solution so that the neutralization pH is 6-7. After neutralization, methylene chloride in the lower layer is extracted to obtain an aqueous sulfone compound solution. The obtained compound has a volatile content of 70.5% and a bromine value determined by the dodecyl mercaptan method.
10.0, anion content 51.3% by Epton method, organic chlorine 0.05%, and compound of formula () 97.5%
It was confirmed that the solution was an aqueous mixture of 2.5% of the compound of formula () above. Example 4 Methacrylic acid was added to a 300 ml four-necked flask equipped with a thermometer, condenser, stirrer, and dropping funnel.
86 g, 0.20 g of hydroquinone monomethyl ether as a polymerization inhibitor, and 1.2 g of trimethylbenzylammonium chloride as a catalyst were charged and dissolved with stirring. Raise the internal temperature to 80°C and gradually add 318 g of dodecyl phenyl glycidyl ether through the dropping funnel.
The dropping was completed in 1 hour and 30 minutes, and the mixture was aged at that temperature for 4 hours. The amount of epoxy oxygen in the reaction solution was 0.02%, and the reaction was complete. Example 5 Methacrylic acid ester 404 obtained in Example 4
Dissolve g in 300 g of methylene chloride and charge into two four-necked flasks. At the same time, mix 160 g of pyridine. While cooling the flask on ice, add chlorsulfonic acid.
Gradually add 118g. The addition of chlorosulfonic acid is completed over 2 hours while maintaining the liquid temperature at 0 to 10°C. After the entire amount has been added, the white crystals are separated by filtration, and the filtrate is neutralized by pouring it into 1183 g of water containing 44 g of sodium hydroxide while stirring and cooling while ensuring that the temperature does not exceed 25°C. The lower methylene chloride layer is extracted to obtain a sulfone compound aqueous solution. The obtained compound had a volatile content of 69.5%, a bromine number of 9.2 by the dodecyl mercaptan method, an anion content (-SO 3 ) of 4.7% by the Epton method, and an organic chlorine of 0.05%, and 97.3% of the compound of the following formula () and the following formula It was confirmed that the mixture was a 2.7% aqueous solution of the compound (). Example 6 1/10 of the predetermined amount of ethylenically unsaturated monomer, the compound represented by the general formula (), and water are charged into a 500 ml four-necked flask, and heated and stirred at 70°C.
Next, a polymerization initiator is added. Heat is generated and polymerization begins in a few minutes to 30 minutes. After initiation of polymerization, the remaining ethylenically unsaturated monomer is added. The polymerization temperature was 80±1℃, and the addition time was 3
It's time. After adding the entire amount of ethylenically unsaturated monomer, the mixture was aged at 80°C for 1 hour to obtain various copolymer emulsions. They are listed in Table 1. Example 7 Various stability tests were conducted on the various copolymer emulsions obtained in Example 6. second them
Record in the table. Example 8 100g of the emulsion obtained in Example 6 was dissolved in tetrahydrofuran, wrapped in a cellophane membrane,
When boiled in a Soxhlet extractor to extract the emulsifier in the emulsion, the result was as shown in Table 3.
The extracted amount of the compound obtained in the present invention was small, and it was confirmed that it was involved in polymerization.
【表】【table】
【表】【table】
【表】【table】
Claims (1)
上を前記エチレン性不飽和単量体と共重合可能
な、一般式、 ［ただし、式中R1は炭素数８〜20のアルキル
基、Ｍはアルカリ金属またはNH4である。］ で示される化合物の存在下で、水性媒体中で重合
させることを特徴とする安定な共重合体エマルジ
ヨンの製造法。[Scope of Claims] 1 A general formula capable of copolymerizing at least one ethylenically unsaturated monomer with the ethylenically unsaturated monomer, [However, in the formula, R1 is an alkyl group having 8 to 20 carbon atoms, and M is an alkali metal or NH4 . ] A method for producing a stable copolymer emulsion, which comprises polymerizing in an aqueous medium in the presence of a compound represented by the formula.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3623583A JPS59161405A (en) | 1983-03-04 | 1983-03-04 | Preparation of stable copolymer emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3623583A JPS59161405A (en) | 1983-03-04 | 1983-03-04 | Preparation of stable copolymer emulsion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59161405A JPS59161405A (en) | 1984-09-12 |
| JPH0415803B2 true JPH0415803B2 (en) | 1992-03-19 |
Family
ID=12464107
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3623583A Granted JPS59161405A (en) | 1983-03-04 | 1983-03-04 | Preparation of stable copolymer emulsion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59161405A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2701237B2 (en) * | 1987-05-14 | 1998-01-21 | 日本カーバイド工業株式会社 | Toner for developing electrostatic images |
-
1983
- 1983-03-04 JP JP3623583A patent/JPS59161405A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59161405A (en) | 1984-09-12 |
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