JPS6228164B2 - - Google Patents
Info
- Publication number
- JPS6228164B2 JPS6228164B2 JP53017095A JP1709578A JPS6228164B2 JP S6228164 B2 JPS6228164 B2 JP S6228164B2 JP 53017095 A JP53017095 A JP 53017095A JP 1709578 A JP1709578 A JP 1709578A JP S6228164 B2 JPS6228164 B2 JP S6228164B2
- Authority
- JP
- Japan
- Prior art keywords
- crosslinking monomer
- indene
- maleic anhydride
- manufacturing
- polymer
- 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
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 17
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 15
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 6
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical group C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 238000004132 cross linking Methods 0.000 claims 5
- 238000004519 manufacturing process Methods 0.000 claims 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- -1 allyl ethers Chemical class 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229940052303 ethers for general anesthesia Drugs 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000003381 solubilizing effect Effects 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 229960000834 vinyl ether Drugs 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- WVAFEFUPWRPQSY-UHFFFAOYSA-N 1,2,3-tris(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1C=C WVAFEFUPWRPQSY-UHFFFAOYSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- JQGGYGKXKWTXTF-UHFFFAOYSA-N 1-ethenoxy-3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propane Chemical compound C=CCOCC(COCC=C)(COCC=C)COC=C JQGGYGKXKWTXTF-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2,2'-azo-bis-isobutyronitrile Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- TURITJIWSQEMDB-UHFFFAOYSA-N 2-methyl-n-[(2-methylprop-2-enoylamino)methyl]prop-2-enamide Chemical compound CC(=C)C(=O)NCNC(=O)C(C)=C TURITJIWSQEMDB-UHFFFAOYSA-N 0.000 description 1
- KCMITHMNVLRGJU-CMDGGOBGSA-N Allyl cinnamate Chemical compound C=CCOC(=O)\C=C\C1=CC=CC=C1 KCMITHMNVLRGJU-CMDGGOBGSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-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
- XNNQFQFUQLJSQT-UHFFFAOYSA-N bromo(trichloro)methane Chemical compound ClC(Cl)(Cl)Br XNNQFQFUQLJSQT-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 150000005218 dimethyl ethers Chemical class 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- PBZROIMXDZTJDF-UHFFFAOYSA-N hepta-1,6-dien-4-one Chemical compound C=CCC(=O)CC=C PBZROIMXDZTJDF-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007788 liquid Substances 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
- 125000005394 methallyl group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- BBPYPXKLPMGHGP-UHFFFAOYSA-N tetrakis(ethenyl)germane Chemical compound C=C[Ge](C=C)(C=C)C=C BBPYPXKLPMGHGP-UHFFFAOYSA-N 0.000 description 1
- UFHILTCGAOPTOV-UHFFFAOYSA-N tetrakis(ethenyl)silane Chemical compound C=C[Si](C=C)(C=C)C=C UFHILTCGAOPTOV-UHFFFAOYSA-N 0.000 description 1
- LGLLRRNQRDPDEE-UHFFFAOYSA-N tetrakis(prop-2-enyl)germane Chemical compound C=CC[Ge](CC=C)(CC=C)CC=C LGLLRRNQRDPDEE-UHFFFAOYSA-N 0.000 description 1
- AKRQMTFHUVDMIL-UHFFFAOYSA-N tetrakis(prop-2-enyl)silane Chemical compound C=CC[Si](CC=C)(CC=C)CC=C AKRQMTFHUVDMIL-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 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
- 239000008096 xylene Substances 0.000 description 1
Description
本発明はインデン−無水マレイン酸−橋かけ単
量体の水膨潤性重合体の製造法に関する。
本発明者等は、無水マレイン酸、インデン、お
よび複数のすなわち１個より多い重合性CH2＝Ｃ
〓基を含んでいる橋かけ剤の単量体混合物を重合
することによつて、すぐれた効率を有するシツク
ナーを製造できることを見出した。この重合体組
成物は化粧品、製薬剤、クリーニングおよびつや
出し化合物、ラテツクスコーテイング用、織物印
なつ、さく井せん孔、水精製に有用性を有する水
シツクナーおよび沈殿防止剤として有用である。
無水マレイン酸およびインデンのほかに、本発
明の組成物の製造に有用な第３の必須単量体は、
複数のCH2＝Ｃ〓基を含み共重合において無水マ
レイン酸およびインデンと反応性の重合性物質で
あればいずれのものでもよい。多不飽和の炭化水
素、エステル、アミド、ニトリル、酸、スルホ
ン、多不飽和の酸無水物、多不飽和のエーテルた
とえば１分子当り２〜７個またはそれ以上のアル
ケニルエーテル基を含んでいるジビニルエーテ
ル、ジアリルエーテル、ジアリルエチレングリコ
ールエーテル、１・４・５・８−ナフタレンテト
ロエーテル、ビニル、アリル、メタリルおよびク
ロチルポリエーテル、多不飽和ケトンたとえばジ
ビニルケトン、ジアリルケトン、β−アリルオキ
シプロピオン酸アリル、アリルメタクリリルスク
ロース、マレイン酸モノアリル、および多価アル
コールの部分アリルエーテルたとえばジアリルグ
リセリンエーテル等が挙げられる。
本発明のポリオレフイン単量体の好ましい群
は、ジビニルベンゼン、トリビニルベンゼン、ジ
ビニルナフタレン、シアヌル酸トリアリル、メチ
レンビスアクリルアミド、メチレンビスメタクリ
ルアミド、トリアクリリルトリアジン、トリメタ
クリリルトリアジン、ヘキサアリルトリメチレン
トリスルホン、テトラアリルメタン、テトラブテ
ニルメタン、テトラアリルシラン、テトラビニル
シラン、テトラアリルゲルマン、テトラビニルゲ
ルマン、エチレングリコールジアクリラート、ペ
ンタエリトリトールテトラアクリラート、アクリ
ル酸アリル、ケイ皮酸アリル、マレイン酸ジアリ
ル、フタル酸ジアリル、ジビニルエーテル、ジア
リルエーテル、３・９−ジビニル−２・４・８・
10−テトラオキソスピロ〔５・５〕ウンデカン、
ジビニルケトン、ポリアリルスクロースのような
多価アルコールのポリアルケニルポリエーテル、
テトラアリルペンタエリスリトールなどを含む。
本発明に於て、当該橋かけ剤の量は他の単量体
の0.01〜約10重量％と変化できる。
無水マレイン酸とインデンとは交互共重合体を
形成する強い傾向が明らかであるから、これらの
１対１モル比からはるかに変化した単量体割合を
使うことは実際的でない。
本発明の重合法においては、無水マレイン酸と
インデンを実質上等モル割合で存在させまた当該
ターポリマーに所望の性質を得るために橋かけ剤
を変えることのできる単量体混合物を使うのが大
変好ましい。等モル以外の無水マレイン酸および
インデンの割合を使うと、重合体の収量は著しく
減少し、得られる重合体はもとの単量体仕込物中
に存在していた割合よりも比較的多い割合の橋か
け剤をふつう含む。
当該単量体成分の一つまたはそれ以上に若干の
可溶化作用を有するが生成重合体には実質上可溶
化作用をもたない不活性有機希釈剤中で無水マレ
イン酸とインデンと橋かけ剤を重合させることに
より、本発明の重合体を製造する。塊状重合を使
用できるが、不完全な転化および得られる固体塊
の処理で遭遇する困難性の理由から好ましくはな
い。溶剤可溶触媒の存在で、単量体の溶媒である
が重合体の非溶媒である有機液体または上記溶剤
の混合物中での重合が最も好ましい。ごく細かい
砕け易いまたしばしば綿毛状の沈殿として生成物
がふつう得られ、溶剤除去後使用前に粉砕または
他の処理を必要とすることはまれだからである。
本発明の目的に適した溶剤はベンゼン、キシレ
ン、テトラリン、ヘキサン、ヘプタン、四塩化炭
素、塩化メチレン、塩化エチレン、ブロモトリク
ロロメタンなど、およびその混合物を含む。
遊離基開始剤の存在で密閉溶器中で不活性雰囲
気で自然発生圧下にまたは開放容器中で常圧で還
流下に、有機希釈媒体中での重合を実施できる。
重合体に望む分子量に大きく依存して、重合温度
は０℃またはそれ以下から100℃またはそれ以上
まで変化できる。
次の実施例は本発明の生成物と方法とをさらに
例示するものであつて、本発明の範囲を限定する
意図はない。ことわらない限り成分量は重量部で
示す。
実施例 １
(A) 次の成分からインデン、無水マレイン酸、お
よびジビニルベンゼンのターポリマーをつくつ
た。成 分
部
ベンゼン 300
インデン 54
無水マレイン酸 46
ジビニルベンゼン（活性） 0.50
α′・α′−アゾビスイソブチロニトリル触媒 0.3
成分を反応器に入れ、ついで窒素でパージし、
密閉した。反応混合物をかきまぜ60℃で４時間
重合反応を実施した。生成固体白色重合体を
過で単離した。重合体を乾燥した。希釈水性ア
ンモニア中の重合体の１重量％溶液はブルツク
フイールド粘度（モデルLVTスピンドル４、
6rpm）30500センチポイズを示した。
(B) ジビニルベンゼンを使わずに上記(A)をくり返
し、ブルツクフイールド粘度10センチポイズを
有する重合体を得た。
(C) 上記(A)に従つてジビニルベンゼンの量を変え
て一連の重合体をつくり、0.6rpmで次の水性
ブルツクフイールド粘度が得られた。
The present invention relates to a process for producing water-swellable polymers of indene-maleic anhydride-crosslinked monomers. We have discovered that maleic anhydride, indene, and multiple or more than one polymerizable CH 2 ═C
It has been found that by polymerizing monomer mixtures of crosslinking agents containing the 〓 group, thickeners with excellent efficiency can be produced. The polymer compositions are useful as water thickeners and suspending agents with utility in cosmetics, pharmaceuticals, cleaning and polishing compounds, latex coatings, textile markings, well drilling, water purification. In addition to maleic anhydride and indene, the third essential monomer useful in making the compositions of the present invention is
Any polymerizable substance containing a plurality of CH 2 =C groups and reactive with maleic anhydride and indene in copolymerization may be used. Polyunsaturated hydrocarbons, esters, amides, nitriles, acids, sulfones, polyunsaturated acid anhydrides, polyunsaturated ethers, such as dimethyl ethers containing from 2 to 7 or more alkenyl ether groups per molecule. Vinyl ether, diallyl ether, diallyl ethylene glycol ether, 1,4,5,8-naphthalenetetroether, vinyl, allyl, methallyl and crotyl polyether, polyunsaturated ketones such as divinyl ketone, diallyl ketone, β-allyloxypropionic acid Partial allyl ethers of allyl, allyl methacrylyl sucrose, monoallyl maleate, and polyhydric alcohols, such as diallyl glycerin ether, may be mentioned. Preferred groups of polyolefin monomers of the invention are divinylbenzene, trivinylbenzene, divinylnaphthalene, triallyl cyanurate, methylenebisacrylamide, methylenebismethacrylamide, triacrylyltriazine, trimethacrylyltriazine, hexaallyltrimethylene triazine. Sulfone, tetraallylmethane, tetrabutenylmethane, tetraallylsilane, tetravinylsilane, tetraallylgermane, tetravinylgermane, ethylene glycol diacrylate, pentaerythritol tetraacrylate, allyl acrylate, allyl cinnamate, diallyl maleate, Diallyl phthalate, divinyl ether, diallyl ether, 3,9-divinyl-2,4,8.
10-tetraoxospiro[5.5]undecane,
polyalkenyl polyethers of polyhydric alcohols, such as divinyl ketone, polyallylsucrose,
Contains tetraallylpentaerythritol, etc. In the present invention, the amount of crosslinking agent can vary from 0.01% to about 10% by weight of other monomers. Because of the apparent strong tendency of maleic anhydride and indene to form alternating copolymers, it is impractical to use monomer proportions that vary significantly from their 1:1 molar ratio. In the polymerization method of the present invention, maleic anhydride and indene are present in substantially equimolar proportions, and a monomer mixture is used in which the crosslinking agent can be varied in order to obtain the desired properties of the terpolymer. Very desirable. When using proportions of maleic anhydride and indene other than equimolar, the polymer yield is significantly reduced and the resulting polymer has a relatively higher proportion than was present in the original monomer charge. Usually contains cross-linking agents. Maleic anhydride, indene, and a crosslinking agent in an inert organic diluent that has a slight solubilizing effect on one or more of the monomer components but no substantial solubilizing effect on the resulting polymer. The polymer of the present invention is produced by polymerizing. Bulk polymerization can be used, but is not preferred because of incomplete conversion and the difficulties encountered in processing the resulting solid mass. Most preferred is polymerization in an organic liquid or mixture of the above solvents which is a solvent for the monomers but a non-solvent for the polymers in the presence of a solvent-soluble catalyst. This is because the product is usually obtained as a very fine, friable and often fluffy precipitate and rarely requires grinding or other treatment after solvent removal before use.
Solvents suitable for the purposes of this invention include benzene, xylene, tetralin, hexane, heptane, carbon tetrachloride, methylene chloride, ethylene chloride, bromotrichloromethane, etc., and mixtures thereof. The polymerization can be carried out in an organic diluent medium in a closed vessel under an inert atmosphere under autogenous pressure in the presence of a free radical initiator or in an open vessel at normal pressure and under reflux.
Depending largely on the desired molecular weight of the polymer, polymerization temperatures can vary from 0°C or less to 100°C or more. The following examples further illustrate the products and methods of the invention and are not intended to limit the scope of the invention. Component amounts are expressed in parts by weight unless otherwise specified. Example 1 (A) A terpolymer of indene, maleic anhydride, and divinylbenzene was made from the following ingredients: Ingredients Benzene 300 Indene 54 Maleic anhydride 46 Divinylbenzene (active) 0.50 α′・α′-Azobisisobutyronitrile catalyst 0.3 The components were placed in a reactor and then purged with nitrogen.
It was sealed. The reaction mixture was stirred and the polymerization reaction was carried out at 60°C for 4 hours. The resulting solid white polymer was isolated by filtration. The polymer was dried. A 1% by weight solution of the polymer in dilute aqueous ammonia has a Bruckfield viscosity (model LVT spindle 4,
6rpm) showed 30500 centipoise. (B) The above (A) was repeated without using divinylbenzene to obtain a polymer having a Bruckfield viscosity of 10 centipoise. (C) A series of polymers were made according to (A) above with varying amounts of divinylbenzene, resulting in the following aqueous Bruckfield viscosities at 0.6 rpm:
【表】
実施例 ２
ジビニルベンゼンの代りにＮ・N′−メチレン
ビスアクリルアミドを使つて実施例１(C)の操作を
くり返した。水性アンモニア中１％溶液の生成重
合体は0.6rpmで次のブルツクフイールド粘度を
もつことがわかつた。[Table] Example 2 The procedure of Example 1(C) was repeated using N·N'-methylenebisacrylamide in place of divinylbenzene. The resulting polymer in a 1% solution in aqueous ammonia was found to have a Bruckfield viscosity at 0.6 rpm:
【表】
実施例 ３
ジビニルベンゼンの代りにシアヌル酸トリアリ
ル８部を使う以外は、実施例１(A)の操作をくり返
した。希釈水性アンモニア中の生成重合体の１％
溶液のブルツクフイールド粘度は0.6rpmで5000
センチポイズであることがわかつた。
実施例 ４
シアヌル酸トリアリルの代りに３・９−ジビニ
ル−２・４・８・10−テトラオキソスピロ〔５・
５〕ウンデカンを使つて実施例３の操作をくり返
した。希水性アンモニア中１％溶液の生成重合体
のブルツクフイールド粘度は0.6rpmで170センチ
ポイズであることがわかつた。[Table] Example 3 The procedure of Example 1(A) was repeated except that 8 parts of triallyl cyanurate was used in place of divinylbenzene. 1% of produced polymer in dilute aqueous ammonia
The Brutzfield viscosity of the solution is 5000 at 0.6 rpm
It turned out to be centipoise. Example 4 3,9-divinyl-2,4,8,10-tetraoxospiro[5.
5] The operation of Example 3 was repeated using undecane. The Bruckfield viscosity of the resulting polymer in a 1% solution in dilute aqueous ammonia was found to be 170 centipoise at 0.6 rpm.
Claims (1)
と無水マレイン酸とインデンの合計重量基準で
0.01〜10重量％の複数の重合性CH2＝Ｃ〓基を有
する橋かけ単量体との混合物を、不活性有機希釈
剤中で遊離基開始剤の存在で、０〜100℃の範囲
の温度で重合させることを特徴とする橋かけした
水膨潤性の固体重合体組成物の製造方法。 ２ 橋かけ単量体がジビニルベンゼンである特許
請求の範囲１記載の製造方法。 ３ 橋かけ単量体がメチレンビスアクリルアミド
である特許請求の範囲１記載の製造方法。 ４ 橋かけ単量体がシアヌル酸トリアリルである
特許請求の範囲１記載の製造方法。 ５ 橋かけ単量体が、３・９−ジビニル−２・
４・８・10−テトラオキソスピロ〔５・５〕ウン
デカンである特許請求の範囲１記載の製造方法。[Claims] 1 Based on substantially equimolar amounts of maleic anhydride and indene and the total weight of maleic anhydride and indene.
A mixture with 0.01-10% by weight of a crosslinking monomer having multiple polymerizable CH 2 =C groups is reacted in the presence of a free radical initiator in an inert organic diluent at temperatures ranging from 0 to 100°C. A method for producing a crosslinked water-swellable solid polymer composition, characterized in that it is polymerized at temperature. 2. The manufacturing method according to claim 1, wherein the crosslinking monomer is divinylbenzene. 3. The manufacturing method according to claim 1, wherein the crosslinking monomer is methylenebisacrylamide. 4. The production method according to claim 1, wherein the crosslinking monomer is triallyl cyanurate. 5 The crosslinking monomer is 3,9-divinyl-2.
4.8.10-Tetraoxospiro[5.5]undecane is the manufacturing method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1709578A JPS54111594A (en) | 1978-02-16 | 1978-02-16 | Crosslinked and water swellable indeneemaleic anhydride interpolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1709578A JPS54111594A (en) | 1978-02-16 | 1978-02-16 | Crosslinked and water swellable indeneemaleic anhydride interpolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS54111594A JPS54111594A (en) | 1979-08-31 |
| JPS6228164B2 true JPS6228164B2 (en) | 1987-06-18 |
Family
ID=11934429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1709578A Granted JPS54111594A (en) | 1978-02-16 | 1978-02-16 | Crosslinked and water swellable indeneemaleic anhydride interpolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS54111594A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0217658U (en) * | 1988-07-22 | 1990-02-05 | ||
| JPH02156151A (en) * | 1988-12-07 | 1990-06-15 | Toshiba Corp | Flange-surface inspecting apparatus |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0348975B1 (en) * | 1988-06-30 | 1994-08-17 | Kawasaki Steel Corporation | Copolymer of polymerizable components in naphtha oil and maleic anhydride, process for producing said copolymer, and derivatives thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51125679A (en) * | 1974-08-05 | 1976-11-02 | Monsanto Co | Concentrating agent and manufacture of same |
| JPS5243880A (en) * | 1975-10-03 | 1977-04-06 | Asahi Dow Ltd | Lapping films and its method of manufacturing |
-
1978
- 1978-02-16 JP JP1709578A patent/JPS54111594A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51125679A (en) * | 1974-08-05 | 1976-11-02 | Monsanto Co | Concentrating agent and manufacture of same |
| JPS5243880A (en) * | 1975-10-03 | 1977-04-06 | Asahi Dow Ltd | Lapping films and its method of manufacturing |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0217658U (en) * | 1988-07-22 | 1990-02-05 | ||
| JPH02156151A (en) * | 1988-12-07 | 1990-06-15 | Toshiba Corp | Flange-surface inspecting apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS54111594A (en) | 1979-08-31 |
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