JPS6243448B2 - - Google Patents
Info
- Publication number
- JPS6243448B2 JPS6243448B2 JP14362179A JP14362179A JPS6243448B2 JP S6243448 B2 JPS6243448 B2 JP S6243448B2 JP 14362179 A JP14362179 A JP 14362179A JP 14362179 A JP14362179 A JP 14362179A JP S6243448 B2 JPS6243448 B2 JP S6243448B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- eva
- monomer
- saponified
- vinyl
- 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
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 34
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 34
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 30
- 239000000178 monomer Substances 0.000 claims description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 229920000578 graft copolymer Polymers 0.000 claims description 9
- 238000007127 saponification reaction Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000003505 polymerization initiator Substances 0.000 claims description 4
- 239000012736 aqueous medium Substances 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 1
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- YQIZHRDZHOSRLH-UHFFFAOYSA-N 2,2-dimethoxypentanenitrile Chemical compound COC(C#N)(CCC)OC YQIZHRDZHOSRLH-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- NSGQRLUGQNBHLD-UHFFFAOYSA-N butan-2-yl butan-2-yloxycarbonyloxy carbonate Chemical compound CCC(C)OC(=O)OOC(=O)OC(C)CC NSGQRLUGQNBHLD-UHFFFAOYSA-N 0.000 description 1
- IWTBWSGPDGPTIB-UHFFFAOYSA-N butanoyl butaneperoxoate Chemical compound CCCC(=O)OOC(=O)CCC IWTBWSGPDGPTIB-UHFFFAOYSA-N 0.000 description 1
- DDMBAIHCDCYZAG-UHFFFAOYSA-N butyl 7,7-dimethyloctaneperoxoate Chemical compound CCCCOOC(=O)CCCCCC(C)(C)C DDMBAIHCDCYZAG-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- BSVQJWUUZCXSOL-UHFFFAOYSA-N cyclohexylsulfonyl ethaneperoxoate Chemical compound CC(=O)OOS(=O)(=O)C1CCCCC1 BSVQJWUUZCXSOL-UHFFFAOYSA-N 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- -1 ethylene, propylene, ethyl Chemical group 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 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
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
Landscapes
- Graft Or Block Polymers (AREA)
Description
本発明は、耐油性、加熱変形性、引張強度を改
良した軟質系グラフト共重合体の製造法に係るも
のである。更に詳しくは、ケン化エチレン−酢酸
ビニル共重合体（以下、ケン化EVAと略す）、水
媒体、分散剤、油溶性重合開始剤の存在下、塩化
ビニル或は塩化ビニル及び塩化ビニルと共重合可
能な単量体混合物（以下、塩化ビニル系単量体と
略す）と水酸基或はカルボキシル基を有する重合
性単量体（以下、OH基含有単量体と略す）との
混合物をグラフト重合し、耐油性、加熱変形性、
引張強度を改良した軟質系グラフト共重合体の製
造法に関するものである。
従来、エチレン−酢酸ビニル共重合体（以下、
EVAと略す）に塩化ビニルをグラフトする方法
は既知であるが、該法では耐油性、加熱変形性、
引張強度が不充分であつたため、耐油性分野、高
温材料分野に使用出来なかつた。本発明は、かか
る欠点を改良した軟質系樹脂の製造法に関するも
のである。
本発明で用いるケン化EVAは、酢酸ビニル含
量５〜80重量％、好ましくは20〜60重量％の
EVAを部分的にケン化したもので、ケン化度は
５〜90モル％、好ましくは30〜70モル％のケン化
EVAがよい。５モル％未満のケン化度では目的
とする改良効果が少なく、90モル％をこえると水
溶性となり、重合安定性が悪くなり好ましくな
い。
本発明で用いるOH基含有単量体は、アクリル
酸、メタクリル酸、アリルアルコール、マレイン
酸、フマル酸、イタコン酸、マレイン酸モノエス
テル等がある。その使用量は、塩化ビニル系単量
体に対し３重量％以上がよいが、好ましくは10〜
50重量％がよい。３重量％未満では、目的とする
改良効果は少ない。
本発明で用いる油溶性重合開始剤は、２・2′−
アゾビス−２・４−ジメチルバレロニトリル、
２・2′−アゾビス−２・４−ジメチル−２・４−
ジメトキシバレロニトリル等のアゾ化合物、ラウ
リルパーオキサイド、ブチロイルパーオキサイ
ド、ジ−イソプロピルバーオキシジカーボネー
ト、ジ−２−エチルヘキシルパーオキシジカーボ
ネート、sec−ブチルパーオキシジカーボネー
ト、tert−ブチルパーオキシピバレート、tert−
ブチルパーオキシネオデカネート、アセチルシク
ロヘキシルスルホニルパーオキサイド等の過酸化
物等の公知の重合開始剤があり、これらは単独或
は併用して用いられる。その使用量は、塩化ビニ
ル系単量体に対し0.01〜１重量％がよい。
本発明で用いる分散剤は、部分ケン化ポリ酢酸
ビニル、メチルセルロース、エチルセルロース、
ヒドロキシメチルセルロース、ヒドロキシエチル
セルロース、ポリアクリル酸、ポリメタクリル
酸、リン酸カルシウム等の有機・無機分散剤があ
り、これらは単独または併用してもよい。使用量
は、塩化ビニル系単量体に対し、0.01〜２重量％
がよい。
本発明の重合温度は、30〜70℃がよい。
本発明での水媒体／（ケン化EVA＋塩化ビニ
ル系単量体）の仕込比は１／１〜１／３がよい。
本発明でのケン化EVA−塩化ビニルグラフト
共重合体中のケン化EVA含量は20〜80重量％が
よい。
本発明で塩化ビニル系単量体とは、塩化ビニル
単独、或は塩化ビニル及び塩化ビニルと共重合可
能な単量体混合物である。ここで塩化ビニルと共
重合可能な単量体としては、酢酸ビニル、エチレ
ン、プロピレン、アクリル酸エチル、アクリル酸
ブチル、アクリロニトリル等の公知の単量体であ
ればよい。またその量は、塩化ビニルに対し、20
重量％以下であればよい。
本発明では、トリクレン、メルカプタン類、四
塩化炭素等の公知の連鎖移動剤を使用しても支障
がない。
本発明では、仕込時のケン化EVA量、塩化ビ
ニル量、OH基含有単量体仕込比並びに重合時間
を変える事によりケン化EVA−塩化ビニルグラ
フト共重合体中のケン化EVA含有量、塩化ビニ
ル含量OH基含有単量体含有量を任意にコントロ
ール出来る。
以下に、本発明の実施例を示すが、これらは何
ら本発明を限定するものではない。
以下の実施例における物性評価は下記に従つ
た。
The present invention relates to a method for producing a soft graft copolymer with improved oil resistance, heat deformability, and tensile strength. More specifically, in the presence of a saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as saponified EVA), an aqueous medium, a dispersant, and an oil-soluble polymerization initiator, it is copolymerized with vinyl chloride or vinyl chloride and vinyl chloride. A mixture of possible monomer mixtures (hereinafter referred to as vinyl chloride monomers) and polymerizable monomers having hydroxyl or carboxyl groups (hereinafter referred to as OH group-containing monomers) is graft-polymerized. , oil resistance, heat deformability,
This invention relates to a method for producing a soft graft copolymer with improved tensile strength. Conventionally, ethylene-vinyl acetate copolymer (hereinafter referred to as
A method of grafting vinyl chloride onto EVA (abbreviated as EVA) is known, but this method has oil resistance, heat deformability,
Because the tensile strength was insufficient, it could not be used in the oil-resistant and high-temperature material fields. The present invention relates to a method for producing a soft resin that overcomes these drawbacks. The saponified EVA used in the present invention has a vinyl acetate content of 5 to 80% by weight, preferably 20 to 60% by weight.
Partially saponified EVA, with a degree of saponification of 5 to 90 mol%, preferably 30 to 70 mol%
EVA is good. If the degree of saponification is less than 5 mol%, the desired improvement effect will be small, and if it exceeds 90 mol%, it will become water-soluble and the polymerization stability will deteriorate, which is not preferable. Examples of the OH group-containing monomer used in the present invention include acrylic acid, methacrylic acid, allyl alcohol, maleic acid, fumaric acid, itaconic acid, and maleic acid monoester. The amount used is preferably 3% by weight or more based on the vinyl chloride monomer, but preferably 10 to 10% by weight.
50% by weight is good. If it is less than 3% by weight, the desired improvement effect will be small. The oil-soluble polymerization initiator used in the present invention is 2,2'-
azobis-2,4-dimethylvaleronitrile,
2,2'-azobis-2,4-dimethyl-2,4-
Azo compounds such as dimethoxyvaleronitrile, lauryl peroxide, butyroyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, sec-butyl peroxydicarbonate, tert-butyl peroxypivalate , tert−
There are known polymerization initiators such as peroxides such as butyl peroxyneodecanate and acetylcyclohexylsulfonyl peroxide, and these may be used alone or in combination. The amount used is preferably 0.01 to 1% by weight based on the vinyl chloride monomer. Dispersants used in the present invention include partially saponified polyvinyl acetate, methyl cellulose, ethyl cellulose,
There are organic and inorganic dispersants such as hydroxymethyl cellulose, hydroxyethyl cellulose, polyacrylic acid, polymethacrylic acid, and calcium phosphate, and these may be used alone or in combination. The amount used is 0.01 to 2% by weight based on the vinyl chloride monomer.
Good. The polymerization temperature in the present invention is preferably 30 to 70°C. In the present invention, the charging ratio of aqueous medium/(saponified EVA+vinyl chloride monomer) is preferably 1/1 to 1/3. In the present invention, the content of saponified EVA in the saponified EVA-vinyl chloride graft copolymer is preferably 20 to 80% by weight. In the present invention, the vinyl chloride monomer refers to vinyl chloride alone, or vinyl chloride and a monomer mixture copolymerizable with vinyl chloride. The monomer copolymerizable with vinyl chloride may be any known monomer such as vinyl acetate, ethylene, propylene, ethyl acrylate, butyl acrylate, and acrylonitrile. Also, the amount is 20% for vinyl chloride.
It may be less than % by weight. In the present invention, there is no problem in using known chain transfer agents such as tricrene, mercaptans, and carbon tetrachloride. In the present invention, the content of saponified EVA in the saponified EVA-vinyl chloride graft copolymer can be adjusted by changing the amount of saponified EVA, the amount of vinyl chloride, the OH group-containing monomer charging ratio, and the polymerization time during the preparation. Vinyl content and OH group-containing monomer content can be controlled arbitrarily. Examples of the present invention are shown below, but these are not intended to limit the present invention in any way. Physical property evaluations in the following examples were conducted in accordance with the following.
【表】
表−１の配合物を140℃のロールで５分間混練
し、シートを作る。
(A) 引張強度
シートからJIS−K6723に従つて、No.３のダ
ンベル片を打ち抜く。次いで、恒温室中でオー
トグラフにより引張強度を測定した。
(B) 耐油性
シートからNo.３のダンベル片を打抜き、JIS
−K6723に従つて、抗張力残率、伸び残率を測
定した。
(C) 加熱変形性
加熱変形性はJIS−C3005に従つて評価し
た。加熱変形率が小さい程良い。
(D) 重合安定性
重合安定性は下記に従つて判定した。[Table] The composition shown in Table 1 is kneaded with a roll at 140°C for 5 minutes to form a sheet. (A) Tensile strength Punch out No. 3 dumbbell pieces from the sheet according to JIS-K6723. Next, the tensile strength was measured using an autograph in a constant temperature room. (B) Oil resistance Punch out No. 3 dumbbell pieces from the sheet and JIS
- Tensile strength retention and elongation retention were measured in accordance with K6723. (C) Heat deformability Heat deformability was evaluated according to JIS-C3005. The smaller the heating deformation rate, the better. (D) Polymerization stability Polymerization stability was determined according to the following.
【表】
実施例 １〜５
比較例 １
撹拌翼を備えた内容積50の重合器に部分ケン
化ポリ酢酸ビニル25ｇを溶解したイオン交換水25
Kg、酢酸ビニル含量35重量％のEVAを部分的に
ケン化したケン化EVA5Kg、ジ−２−エチルヘキ
シルパーオキシジカーボネート３ｇ、アクリル酸
１Kg、を仕込み脱気后、塩化ビニル10Kgを仕込み
58℃で所定時間重合した。重合結果内容を表−３
に示す。[Table] Examples 1 to 5 Comparative Example 1 25g of ion-exchanged water in which 25g of partially saponified polyvinyl acetate was dissolved in a polymerization vessel with an internal volume of 50mm equipped with a stirring blade.
Kg, 5 Kg of saponified EVA which is partially saponified EVA with a vinyl acetate content of 35%, 3 g of di-2-ethylhexyl peroxydicarbonate, and 1 Kg of acrylic acid, and after deaeration, 10 Kg of vinyl chloride is charged.
Polymerization was carried out at 58°C for a predetermined period of time. Table 3 shows the polymerization results.
Shown below.
【表】
表−３から、EVA中酢酸ビニルのケン化度が
90モル％をこえると重合安定性が悪くなる事が判
る。
実施例 ６〜12
撹拌翼を備えた内容積50の重合器に部分ケン
化ポリ酢酸ビニル10ｇ、メチルセルロース10ｇを
溶解したイオン交換水25Kg、酢酸ビニル含量25重
量％のEVAを部分的にケン化したケン化EVA
（EVA中、酢酸ビニルのケン化度30モル％）、
２・2′−アゾビス−２・４−ジメチルバレロニト
リル2.5ｇ、アクリル酸を仕込み、脱気后塩化ビ
ニルを仕込み、62℃で所定時間重合した。その結
果を表−４に示した。[Table] From Table 3, the degree of saponification of vinyl acetate in EVA is
It can be seen that when it exceeds 90 mol%, polymerization stability deteriorates. Examples 6 to 12 10 g of partially saponified polyvinyl acetate, 25 kg of ion-exchanged water in which 10 g of methyl cellulose was dissolved, and EVA with a vinyl acetate content of 25% by weight were partially saponified in a polymerization vessel equipped with a stirring blade and having an internal volume of 50. saponified EVA
(Saponification degree of vinyl acetate in EVA: 30 mol%),
2.5 g of 2,2'-azobis-2,4-dimethylvaleronitrile and acrylic acid were charged, and after degassing, vinyl chloride was charged and polymerized at 62°C for a predetermined time. The results are shown in Table-4.
【表】
表−４から、ケン化EVA仕込量、塩化ビニル
仕込量、アクリル酸仕込量、並びに重合時間を変
える事により、ケン化EVA−塩化ビニルグラフ
ト共重合体中のケン化EVA含有量、塩化ビニル
含有量、アクリル酸含有量が変化する事が判る。
実施例 13〜15
比較例 ２〜４
EVA中酢酸ビニルのケン化度（モル％）及び
塩化ビニル含量、アクリル酸含量の異なるケン化
EVA−塩化ビニルグラフト共重合体を58℃の重
合温度で作り、これを表−１に従つた配合で物性
評価を行なつた。結果を表−５に示す。表−５に
は、比較例として非ケン化EVAを使つた場合、
及びケン化EVAに塩化ビニルを単独グラフト重
合し、それにポリアクリル酸をブレンドした場合
の例も示す。尚、本例では、EVA中酢酸ビニル
含量が25重量％のEVA（非ケン化EVA）をケン
化して用いた。[Table] From Table 4, by changing the amount of saponified EVA, vinyl chloride, acrylic acid, and polymerization time, the saponified EVA content in the saponified EVA-vinyl chloride graft copolymer, It can be seen that the vinyl chloride content and acrylic acid content change. Examples 13-15 Comparative Examples 2-4 Saponification of vinyl acetate in EVA with different degrees of saponification (mol%), vinyl chloride content, and acrylic acid content
An EVA-vinyl chloride graft copolymer was prepared at a polymerization temperature of 58°C, and its physical properties were evaluated using a formulation according to Table 1. The results are shown in Table-5. Table 5 shows that when non-saponified EVA is used as a comparative example,
Also shown is an example in which vinyl chloride is homograft-polymerized to saponified EVA and polyacrylic acid is blended therewith. In this example, EVA with a vinyl acetate content of 25% by weight (non-saponified EVA) was saponified and used.
【表】
表−５より、ケン化EVA並びにOH基含有単量
体が共存し、且つOH基含有単量体がグラフト共
重合している場合、耐油性、引張強度、加熱変形
性が改良される事が判る。
実施例 16〜20
比較例 ５〜６
EVA中酢酸ビニル含量が30重量％のEVAをケ
ン化し、ケン化度10％のケン化EVAを作つた。
次いで、該ケン化EVAに塩化ビニルとOH基含有
単量体混合物をグラフト重合し、ケン化EVA含
量、塩化ビニル含有量、OH基含有単量体含有量
の異なるケン化EVA−塩化ビニルグラフト共重
合体を作つた。
次いで、表−１に従つた配合で物性評価を行な
つた。結果を表−６に示す。表−６にはOH基含
有単量体が存在しない場合のデータも示した。[Table] From Table 5, oil resistance, tensile strength, and heat deformability are improved when saponified EVA and an OH group-containing monomer coexist, and when the OH group-containing monomer is graft copolymerized. It turns out that Examples 16-20 Comparative Examples 5-6 EVA containing 30% by weight of vinyl acetate in EVA was saponified to produce saponified EVA with a degree of saponification of 10%.
Next, a mixture of vinyl chloride and an OH group-containing monomer is graft-polymerized onto the saponified EVA to obtain a saponified EVA-vinyl chloride graft mixture having different saponified EVA content, vinyl chloride content, and OH group-containing monomer content. I made a polymer. Next, physical properties were evaluated using the formulations shown in Table 1. The results are shown in Table-6. Table 6 also shows data when no OH group-containing monomer was present.
【表】【table】
【表】
表−６から、OH基含有単量体と塩化ビニルの
混合物をグラフトした場合、耐油性、引張強度、
加熱変形性は改良されるが、塩化ビニル単独のグ
ラフトでは、これら諸物性が改良されない事が判
る。[Table] From Table 6, when a mixture of OH group-containing monomer and vinyl chloride is grafted, oil resistance, tensile strength,
It can be seen that although the heat deformability is improved, the grafting of vinyl chloride alone does not improve these physical properties.
Claims (1)
（以下、ケン化EVAと略す）、水媒体、油溶性重
合開始剤、分散剤の存在下、塩化ビニル或は塩化
ビニル及び塩化ビニルと共重合可能な単量体混合
物（以下、塩化ビニル系単量体と略す）と水酸基
或はカルボキシル基を有する重合性単量体（以
下、OH基含有単量体と略す）との混合物をグラ
フト重合することを特徴とするケン化EVA−塩
化ビニルグラフト共重合体の製造法。 ２ ケン化EVA中の酢酸ビニル含量が５〜80重
量％であり、且つケン化度が５〜90モル％である
特許請求の範囲第１項記載のグラフト共重合体の
製造法。 ３ OH基含有単量体の使用量が塩化ビニル系単
量体に対し３重量％以上である特許請求の範囲第
１項記載のグラフト共重合体の製造法。[Claims] 1. Vinyl chloride or vinyl chloride and chloride in the presence of a partially saponified ethylene-vinyl acetate copolymer (hereinafter abbreviated as saponified EVA), an aqueous medium, an oil-soluble polymerization initiator, and a dispersant. A mixture of a monomer mixture copolymerizable with vinyl (hereinafter abbreviated as a vinyl chloride monomer) and a polymerizable monomer having a hydroxyl group or a carboxyl group (hereinafter abbreviated as an OH group-containing monomer) 1. A method for producing a saponified EVA-vinyl chloride graft copolymer, which comprises graft polymerizing. 2. The method for producing a graft copolymer according to claim 1, wherein the vinyl acetate content in the saponified EVA is 5 to 80% by weight, and the degree of saponification is 5 to 90 mol%. 3. The method for producing a graft copolymer according to claim 1, wherein the amount of the OH group-containing monomer used is 3% by weight or more based on the vinyl chloride monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14362179A JPS5667320A (en) | 1979-11-05 | 1979-11-05 | Production of graftcopolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14362179A JPS5667320A (en) | 1979-11-05 | 1979-11-05 | Production of graftcopolymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5667320A JPS5667320A (en) | 1981-06-06 |
| JPS6243448B2 true JPS6243448B2 (en) | 1987-09-14 |
Family
ID=15343001
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14362179A Granted JPS5667320A (en) | 1979-11-05 | 1979-11-05 | Production of graftcopolymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5667320A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6375015A (en) * | 1986-09-19 | 1988-04-05 | Mitsui Toatsu Chem Inc | Vinyl chloride resin for molded article having improved coating performance |
-
1979
- 1979-11-05 JP JP14362179A patent/JPS5667320A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5667320A (en) | 1981-06-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1226385A (en) | Structured latex particles which are film forming and a process for their preparation | |
| KR20160042041A (en) | Dispersion stabilizer for suspension polymerization, and manufacturing method for vinyl resin | |
| JPH06206950A (en) | Production of graft copolymer latex of core/shell disperse particle with improved phase bond between core and shell | |
| KR102310659B1 (en) | Secondary suspending agent for suspension polymerisation reaction | |
| JPS6243448B2 (en) | ||
| JP2004269877A (en) | Method for producing acrylic copolymer latex and method for producing vinyl chloride-based resin by using the same | |
| EP0177956B1 (en) | Low molecular weight vinyl halide/vinyl ester copolymers by aqueous polymerization | |
| JP3210408B2 (en) | Method for producing vinyl chloride polymer | |
| JPH04117402A (en) | Dispersion aid and dispersion stabilizer for suspension polymerization of vinyl compound | |
| JP2910774B2 (en) | Method for producing vinyl chloride resin | |
| JP2823681B2 (en) | Method for producing vinyl chloride polymer | |
| JPH0225923B2 (en) | ||
| JP2009102609A (en) | Vinyl chloride-based resin molded body and method for manufacturing the same | |
| JP2996418B2 (en) | Dispersion stabilizer for suspension polymerization | |
| JPS6173713A (en) | Production of vinyl chloride resin | |
| JPS61266421A (en) | Production of vinyl chloride resin excellent in flow and heat stability | |
| JP3584591B2 (en) | Method for producing vinyl chloride polymer | |
| JP4504490B2 (en) | Vinyl chloride resin, molded article thereof and method for producing molded article | |
| JP3400075B2 (en) | Dispersion stabilizer for emulsion polymerization | |
| JP3414026B2 (en) | Method for producing vinyl chloride polymer | |
| JPH0534366B2 (en) | ||
| JP3663500B2 (en) | Method for producing vinyl chloride polymer | |
| JP2003119341A (en) | Polyvinyl chloride-based resin composition | |
| JPH0576966B2 (en) | ||
| JPH0742370B2 (en) | Process for producing vinyl chloride resin composition having improved thermal stability |