JPS60223806A - Production of composite resin - Google Patents
Production of composite resinInfo
- Publication number
- JPS60223806A JPS60223806A JP8255784A JP8255784A JPS60223806A JP S60223806 A JPS60223806 A JP S60223806A JP 8255784 A JP8255784 A JP 8255784A JP 8255784 A JP8255784 A JP 8255784A JP S60223806 A JPS60223806 A JP S60223806A
- Authority
- JP
- Japan
- Prior art keywords
- polyvinyl alcohol
- added
- water
- compound
- reaction system
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000805 composite resin Substances 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 21
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 21
- -1 phosphate ester compound Chemical class 0.000 claims abstract description 17
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 8
- 239000010452 phosphate Substances 0.000 claims abstract description 8
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 4
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 230000008719 thickening Effects 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003377 acid catalyst Substances 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000011541 reaction mixture Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 150000001412 amines Chemical class 0.000 abstract description 2
- 229910021529 ammonia Inorganic materials 0.000 abstract description 2
- 239000003518 caustics Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 238000010926 purge Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- UDXXYUDJOHIIDZ-UHFFFAOYSA-N 2-phosphonooxyethyl prop-2-enoate Chemical compound OP(O)(=O)OCCOC(=O)C=C UDXXYUDJOHIIDZ-UHFFFAOYSA-N 0.000 description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- AWDJENYXWMHLGG-UHFFFAOYSA-N 1-dodecoxydodecane prop-2-enoic acid Chemical compound C(C=C)(=O)O.C(CCCCCCCCCCC)OCCCCCCCCCCCC AWDJENYXWMHLGG-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- GMCNAQYARMUGJX-UHFFFAOYSA-N 4-phosphonooxybutyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOP(O)(O)=O GMCNAQYARMUGJX-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 238000006359 acetalization reaction Methods 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- LJXTYJXBORAIHX-UHFFFAOYSA-N diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1 LJXTYJXBORAIHX-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、複合樹脂の製造法に関するもので、より詳述
すれば、柔軟で強い皮膜形成性、増粘性を有する改良さ
れた水溶性複合樹脂の製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a composite resin, and more specifically, to a method for producing an improved water-soluble composite resin having flexibility, strong film-forming properties, and thickening properties. be.
従来より、皮ｎり形成性、増粘性を有する水溶性高分子
化合物は各種の用途に使用されている。しかしながら、
用途によってはそれらの数種の併用が必要な場合もあり
、必ずしも全てが要求される性能を十分溝たし、かつ増
粘性を有するものとは限らない。BACKGROUND ART Water-soluble polymer compounds having skin-forming and thickening properties have been used for various purposes. however,
Depending on the application, it may be necessary to use several types of them in combination, and not all of them will necessarily meet the required performance and have thickening properties.
本発明者等は、前記の如き実情に鑑み鋭意研究を重ねた
結果、本発明を提供するに至ったものである。すなわち
、
ポリビニルアルコールの水溶液中で、かつ重合触媒の存
在下でポリビニルアルコールに対し１〜５０重量％のα
、β不飽和基を有するリン酸エステル化合物（以下リン
酸エステル化合物という）を重合させた後、アルデヒド
化合物によりアセタール化することを特徴とする複合樹
脂の製造法である。The present inventors have conducted extensive research in view of the above-mentioned actual circumstances, and as a result have come to provide the present invention. That is, in an aqueous solution of polyvinyl alcohol and in the presence of a polymerization catalyst, 1 to 50% by weight of α based on polyvinyl alcohol.
, is a method for producing a composite resin characterized by polymerizing a phosphate ester compound having a β-unsaturated group (hereinafter referred to as a phosphate ester compound) and then acetalizing it with an aldehyde compound.
本発明に使用するポリビニルアルコールは、一般に水溶
性のもので若干変性されているもので、ポリビニルアル
コールとされるものであれば何れでもよい。The polyvinyl alcohol used in the present invention is generally water-soluble and slightly modified, and any polyvinyl alcohol may be used.
次にリン酸エステル化合物は、一般式 （１）で示す化合物である。Next, the phosphate ester compound has the general formula This is the compound shown in (1).
一般式（１）で示す具体的な化合物は、たとえばメタク
リロイルオキシエチル燐酸モノエステル、アクリロイル
オキシエチル燐酸モノエスル、アクリロイルオキシプロ
ポキシエチル燐酸モノエステル、メタ クリロイルオキ
シブチル燐酸モノエステル、アクリロイルオキシトリエ
トキシエチル燐酸モノエステル、メタ クリロイルオキ
シフェニルエトキシエチル燐酸モノエステル等で少量の
燐酸ジエスン、過硫酸カリ、アゾビスイソブチロニトリ
ル、ジターシャリブチルパーオキサイド、過酸化ベンゾ
イル等のα、β不飽和結合を有する化合物の重合に使用
出来るものであれば何れでもよい。Specific compounds represented by the general formula (1) include, for example, methacryloyloxyethyl phosphate monoester, acryloyloxyethyl phosphate monoester, acryloyloxypropoxyethyl phosphate monoester, methacryloyloxybutyl phosphate monoester, and acryloyloxytriethoxyethyl phosphate. Monoester, methacryloyloxyphenylethoxyethyl phosphate monoester, etc., with small amounts of α and β unsaturated bonds such as diethone phosphate, potassium persulfate, azobisisobutyronitrile, ditert-butyl peroxide, benzoyl peroxide, etc. Any material that can be used for polymerization of compounds may be used.
アセタく−ル化に使用されるアルデヒド化合物は、たと
えばホルムアルデヒド、アセトアルデヒド、ブチルアル
デヒド、イソブチルアルデヒド、アクロ レイン、ベン
ツアルデヒド等である。The aldehyde compounds used for acetaldehyde include, for example, formaldehyde, acetaldehyde, butyraldehyde, isobutyraldehyde, acrolein, benzaldehyde and the like.
またアセタール化に使用する酸触媒はたとえば、塩酸、
硫酸、燐酸、アルキル硫酸エステル、ベンゼンスルホン
酸、トルエンスルホン酸、アルキルベンゼンスルホン酸
等が挙げられる。In addition, acid catalysts used for acetalization include, for example, hydrochloric acid,
Examples include sulfuric acid, phosphoric acid, alkyl sulfate, benzenesulfonic acid, toluenesulfonic acid, alkylbenzenesulfonic acid, and the like.
本発明の製造法を具体的に説明すると次の通りである。The manufacturing method of the present invention will be specifically explained as follows.
ポリビニルアルコールを水に溶解せしめた後、反応系内
を窒素置換し、重合触媒を加えた後、ポリビニルアルコ
ールに対し１〜５０重量％のリン酸エステル化合物を加
え４０〜１００℃に加温し、重合させる。After dissolving polyvinyl alcohol in water, purging the reaction system with nitrogen, adding a polymerization catalyst, adding 1 to 50% by weight of a phosphoric acid ester compound to the polyvinyl alcohol, and heating to 40 to 100°C. Polymerize.
リン酸エステル化合物の量が、前記範囲より外れた場合
、本発明の目的が達成されない。If the amount of the phosphoric acid ester compound is outside the above range, the object of the present invention will not be achieved.
次いで重合完了後、酸触媒の存在下１０〜８０℃でアル
デヒド化合物をポリビニルアルコールに対し、好ましく
は１〜３０重量％加え、アセタール化する。反応終了後
苛性アルカリ、アンモニア、有機アミン等で中和し、ｐ
Ｈ６〜９にした状１！７使用する０本発明において、必
要に応じてリン酸エステルの一部を共重合可能な七ツマ
−に置換えてもよい。共重合可能な七ツマ−は、たとえ
ばヒドロキシエチルアクリレート、ヒドロキシプロピル
メタクリレート、ポリエチレングリコールモノメチルエ
ーテルアクリレート、ポリエチレングリコールモノメタ
クリレート、ポリエチレングリコールモノラウリルエー
テルアクリレート、メトキシエチルメタクリレート、メ
チルアクリレート、ブチルアクリレート等で、それらは
混合状態でも使用可能である。Then, after the polymerization is completed, an aldehyde compound is preferably added in an amount of 1 to 30% by weight to the polyvinyl alcohol at 10 to 80° C. in the presence of an acid catalyst to acetalize the polyvinyl alcohol. After the reaction is complete, neutralize with caustic alkali, ammonia, organic amine, etc.
In the present invention, a part of the phosphoric acid ester may be replaced with a copolymerizable hexamer, if necessary. Examples of copolymerizable seven polymers include hydroxyethyl acrylate, hydroxypropyl methacrylate, polyethylene glycol monomethyl ether acrylate, polyethylene glycol monomethacrylate, polyethylene glycol monolauryl ether acrylate, methoxyethyl methacrylate, methyl acrylate, butyl acrylate, etc. It can also be used in a mixed state.
一般にポリビニルアルコール水溶液あるいは、水溶性ポ
リビニルアセタール溶液とポリアクリル酸塩の水溶液は
透明に混溶しないが、本発明の複合樹脂はポリビニルア
ルコール水溶液、ポリビニルブチラール水溶液、ポリア
クリル酸塩水溶液と相互に混溶する。Generally, polyvinyl alcohol aqueous solution or water-soluble polyvinyl acetal solution and polyacrylate aqueous solution do not mix transparently, but the composite resin of the present invention is mutually miscible with polyvinyl alcohol aqueous solution, polyvinyl butyral aqueous solution, and polyacrylate aqueous solution. do.
本発明の製造法に従って得られる複合樹脂は、強い皮膜
形成性を有し、繊維処理剤、乳化重合安定剤、農薬添加
剤、塗料、顔料添加剤、ラテックス添加剤、セラミック
添加剤、紙処理剤、塗工紙バインダー、感熱・感圧記録
紙７へインター、土木・鉱業用水溶性高分子として、さ
らに水溶性樹脂改質剤としても有効である。The composite resin obtained according to the production method of the present invention has strong film-forming properties, and has fiber processing agents, emulsion polymerization stabilizers, agricultural chemical additives, paints, pigment additives, latex additives, ceramic additives, and paper processing agents. It is effective as a coated paper binder, as an interlayer for heat-sensitive/pressure-sensitive recording paper 7, as a water-soluble polymer for civil engineering and mining, and as a water-soluble resin modifier.
次に実施例を挙げて本発明を、より詳細に説明するが、
本発明は、それらの実施例に限定されるものではない。Next, the present invention will be explained in more detail with reference to Examples.
The invention is not limited to these examples.
なお、実施例中「％Ａは重量基準である。In addition, in the examples, "%A" is based on weight.
実施例１
市販ポリビニルアルコール（日本合成化学工業■、ゴー
セノールＧＬ−０５）１００重量部を水４００重量部に
加え撹拌し、８０℃に加熱し、完全に溶解する。Example 1 100 parts by weight of commercially available polyvinyl alcohol (Nippon Gosei Kagaku Kogyo ■, Gohsenol GL-05) was added to 400 parts by weight of water, stirred, and heated to 80°C to completely dissolve.
次いで２５°Ｃに冷却し、過硫酸アンモ７１重量部を加
え、窒素気流下にアクリロイルオキシエチル燐酸モノエ
ステル２０重量部を加え、６０°Ｃで５時間反応する。Then, the mixture was cooled to 25°C, 71 parts by weight of ammonium persulfate was added, 20 parts by weight of acryloyloxyethyl phosphate monoester was added under a nitrogen stream, and the mixture was reacted at 60°C for 5 hours.
重合性二重結合の消滅後、反応混合物を１５°Ｃに冷却
し、濃塩酸５ｍｌを加えた後、ｎ−ブチルアルデヒド９
．４重量部を力１ｒえ４０〜５０°Ｃで２時間反応する
。反応生成物を２０°Ｃに冷却し２８％ＮＨＮＨ４ＯＨ
２Ｏを加え中和する。After the polymerizable double bonds disappeared, the reaction mixture was cooled to 15°C, 5 ml of concentrated hydrochloric acid was added, and n-butyraldehyde 9
．． 4 parts by weight are reacted at 40-50°C for 2 hours under 1r of force. The reaction product was cooled to 20 °C and diluted with 28% NHNH4OH.
Add 2O to neutralize.
温度約２ｆ％、粘度 １０，０ＯＯＧＰＳの透明な液状
の複合樹脂を得た。A transparent liquid composite resin having a temperature of about 2f% and a viscosity of 10.0 OOGPS was obtained.
燐含量￥’Ｂ２ ％
分解温度 ２２０°Ｃ
ブチラール化度 １１．０％（ポリビニルアルコールに
対し）
実施例２
市販ポリビニルアルコール（日本合成化学工業■、ゴー
セノールＧＬ−０３、ＧＬ−１４Ｌのｌ：ｌ混合物）１
００重量部を水４００重量部に加え撹拌し、８０°Ｃに
加熱し溶解する。次いで２５°Ｃに冷却し、過硫酸アン
モ７１重量部を加え、窒素気流下にアクリロイルオキシ
エチル燐酸モノエステル２０重量部とメトキシエチルメ
タクリレート２重量部を加え、６０°Ｃで５時間反応す
る。Phosphorus content ￥'B2% Decomposition temperature 220°C Degree of butyralization 11.0% (based on polyvinyl alcohol) Example 2 L:l mixture of commercially available polyvinyl alcohol (Nippon Gohsei ■, Gohsenol GL-03, GL-14L) )1
00 parts by weight were added to 400 parts by weight of water, stirred, and heated to 80°C to dissolve. Then, the mixture was cooled to 25°C, 71 parts by weight of ammonium persulfate was added, 20 parts by weight of acryloyloxyethyl phosphate monoester and 2 parts by weight of methoxyethyl methacrylate were added under a nitrogen stream, and the mixture was reacted at 60°C for 5 hours.
重合性二重結合の消滅後、反応混合物を１５°Ｃに冷却
し、濃塩酸３１を加えた後、ｎ−ブチルアルデヒド８．
４重量部を加え、４０〜５ｏ ’ｃで２時間反応する。After the disappearance of the polymerizable double bonds, the reaction mixture was cooled to 15°C, and after adding 31% of concentrated hydrochloric acid, 8.0% of n-butyraldehyde was added.
Add 4 parts by weight and react at 40-5 o'C for 2 hours.
反応生成物を２０°Ｃに冷却し、２８％ＮＨ４ＯＨ１８
ｍ１を加え中和する。The reaction product was cooled to 20 °C and diluted with 28% NH4OH18
Add m1 to neutralize.
温度約２１／−％、粘度 １８，０ＯＯＣＰＳ 、の透
明な液状の複合樹脂を得た。A transparent liquid composite resin having a temperature of about 21% and a viscosity of 18.0OOCPS was obtained.
燐含量粕２ ％
分解温度 ２３０℃
ブチラール化度 １１．２％（ポリビニルアルコールに
対し）
実施例３
実施例１．２の複合樹脂について厚み縦０．１腸ｍの皮
膜を８０℃４８時間の乾燥条件で作成した。この皮膜に
ついて引張強さ、伸びの測定をＪＩＳＫ−６３０１に準
じ行った。なお試験片は上記条件で作成した皮膜を、ダ
ンベル状４号の大きさにしたものを用いた。Phosphorus content: 2% Decomposition temperature: 230°C Degree of butyralization: 11.2% (based on polyvinyl alcohol) Example 3 A film with a thickness of 0.1 m in length was dried at 80°C for 48 hours using the composite resin of Example 1.2. Created with conditions. The tensile strength and elongation of this film were measured according to JISK-6301. The test piece used was a film prepared under the above conditions and shaped into a size 4 dumbbell.
同時に比較例として市販ポリビニルアルコール（日本合
成化学工業■、ゴーセノールＧＬ−０３）について測定
した。At the same time, as a comparative example, commercially available polyvinyl alcohol (Nippon Gosei Kagaku Kogyo ■, Gohsenol GL-03) was measured.
結果を第１表に示す。The results are shown in Table 1.
第ｌ衷 特許出願人 第−工業製薬株式会社First side patent applicant Dai-Kogyo Seiyaku Co., Ltd.
Claims (1)
在下でポリビニルアルコールに対し１〜５０重量％のα
、β不飽和基を有するリン酸エステル化合物を重合させ
た後、アルデヒド化合物によりアセタール化することを
特徴とする複合樹脂の製造法。In an aqueous solution of polyvinyl alcohol and in the presence of a polymerization catalyst, 1 to 50% by weight of α based on polyvinyl alcohol
, a method for producing a composite resin, which comprises polymerizing a phosphate ester compound having a β-unsaturated group and then acetalizing it with an aldehyde compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8255784A JPS60223806A (en) | 1984-04-23 | 1984-04-23 | Production of composite resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8255784A JPS60223806A (en) | 1984-04-23 | 1984-04-23 | Production of composite resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60223806A true JPS60223806A (en) | 1985-11-08 |
Family
ID=13777790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8255784A Pending JPS60223806A (en) | 1984-04-23 | 1984-04-23 | Production of composite resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60223806A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0597917A (en) * | 1991-10-03 | 1993-04-20 | Sekisui Chem Co Ltd | Water-soluble polyvinyl acetal resin and ink composition for marking pen |
| CN1303115C (en) * | 2004-04-01 | 2007-03-07 | 营口市向阳催化剂有限责任公司 | Catalysis system of nitrogen-accessory ingredient of oxygen and nickel in use for polymerizaton of norborene and ramification, preparation method and application |
| WO2016047752A1 (en) * | 2014-09-26 | 2016-03-31 | 株式会社クラレ | Nonwoven fabric formed from polyvinyl butyral continuous fibers, and manufacturing method therefor |
-
1984
- 1984-04-23 JP JP8255784A patent/JPS60223806A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0597917A (en) * | 1991-10-03 | 1993-04-20 | Sekisui Chem Co Ltd | Water-soluble polyvinyl acetal resin and ink composition for marking pen |
| CN1303115C (en) * | 2004-04-01 | 2007-03-07 | 营口市向阳催化剂有限责任公司 | Catalysis system of nitrogen-accessory ingredient of oxygen and nickel in use for polymerizaton of norborene and ramification, preparation method and application |
| WO2016047752A1 (en) * | 2014-09-26 | 2016-03-31 | 株式会社クラレ | Nonwoven fabric formed from polyvinyl butyral continuous fibers, and manufacturing method therefor |
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