JPH0580494B2 - - Google Patents
Info
- Publication number
- JPH0580494B2 JPH0580494B2 JP4815785A JP4815785A JPH0580494B2 JP H0580494 B2 JPH0580494 B2 JP H0580494B2 JP 4815785 A JP4815785 A JP 4815785A JP 4815785 A JP4815785 A JP 4815785A JP H0580494 B2 JPH0580494 B2 JP H0580494B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- vinyl chloride
- emulsion
- added
- ester
- 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 - Lifetime
Links
- 239000000839 emulsion Substances 0.000 claims description 28
- 238000006116 polymerization reaction Methods 0.000 claims description 27
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 15
- -1 acrylic ester Chemical class 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000000178 monomer Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 5
- 239000003995 emulsifying agent Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-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
- 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
- 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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- SBVKVAIECGDBTC-UHFFFAOYSA-N 4-hydroxy-2-methylidenebutanamide Chemical compound NC(=O)C(=C)CCO SBVKVAIECGDBTC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920001214 Polysorbate 60 Chemical class 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 229920013820 alkyl cellulose Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- JQRRFDWXQOQICD-UHFFFAOYSA-N biphenylen-1-ylboronic acid Chemical compound C12=CC=CC=C2C2=C1C=CC=C2B(O)O JQRRFDWXQOQICD-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-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
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-M ethenesulfonate Chemical compound [O-]S(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-M 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229920013821 hydroxy alkyl cellulose Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 230000007774 longterm Effects 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
- 239000000463 material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 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
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate 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
- 238000009849 vacuum degassing Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Description
〔産業上の利用分野〕
本発明は得られたエマルジヨンの可塑化物の粘
度安定性や貯蔵安定性が良い塩化ビニル共重合体
エマルジヨンの製造法に関する。
〔従来の技術〕
従来塩化ビニル共重合体エマルジヨンを製造す
る方法としては一括仕込法、モノマー添加法、エ
マルジヨン添加法、播種重合法等が知られてい
る。エマルジヨン粒子内のポリマー組成を均一化
する為には、重合開始剤、乳化剤、保護コロイ
ド、水などを含有し、かつモノマー類を含有しな
い系に、塩化ビニルとそれと共重合可能なモノマ
ーそれぞれの使用する全量を、連続して又は分割
して添加重合することが有効である。
この様にして重合した塩化ビニル共重合体エマ
ルジヨンは接着剤、塗料、各種バインダー、セメ
ント混和剤等に使用されているが、最低造膜温度
を下げる場合、可塑剤を添加して室温ないしは
150℃程度で可塑化される。しかし、ここで得ら
れる可塑化物は長期間保存しておくと粘度が増粘
したり、可塑剤の分離がおこり易い。貯蔵温度が
50℃以上になるとそれらの現象は促進され、はな
はだしい時には可塑化物はゲル化する。
参考文献 エマルジヨンラテツクスハンドブツ
ク 大成社 Ｐ−277〜288 塩ビとポリマー
13（４）10〜25
〔発明が解決しようとする問題点〕
本発明は、従来技術の問題点を解決するために
なされたものであり、可塑化物の粘度安定性、貯
蔵安定性などの改良された塩化ビニル共重合体エ
マルジヨンの製造法を提供することを目的とす
る。
〔問題点を解決する為の手段〕
本発明は、塩化ビニルとアクリル酸エステル又
はメタクリル酸エステルを乳化共重合するに際
し、塩化ビニル全使用量の３〜30重量％を仕込ん
で重合を開始し、その後塩化ビニルの残量及びア
クリル酸エステル又はメタクリル酸エステルの全
使用量を連続して又は分割して重合系に添加する
ことを特徴とする塩化ビニル共重合体エマルジヨ
ンの製造法である。
以下、本発明を詳細に説明する。
本発明では重合開始前に仕込む初期添加モノマ
ーは塩化ビニルのみであつて、その量は塩化ビニ
ル全使用量の３〜30重量％であり、特に５〜15重
量％が好ましい。３重量％未満では得られるエマ
ルジヨンの可塑化物の粘度安定性と貯蔵安定性は
改良されず、30重量％を越えるとエマルジヨン粒
子中のポリマー組成を均一化できない。
また、本発明においては重合開始前の系に種エ
マルジヨンを存在させることができる。
本発明の製造法においては、重合開始後に、塩
化ビニルの残量並びに（メタ）アクリル酸エステ
ル及び所望により用いる第３モノマーそれぞれの
全使用量を、連続して又は分割して重合系に後添
加する。これらのモノマーは、任意の方法、例え
ば各モノマーそれぞれを単独で、モノマー同士を
混合して、モノマーを乳化液と混合して又はこれ
らを組合せた方法により、重合系に連続して又は
分割して後添加される。
本発明においては、重合開始以降後添加モノマ
ーの添加終了までの間に、乳化剤、水などを含有
する乳化液を、連続して又は分割して添加するこ
とが好ましい。
本発明で第２モノマーとして用いる（メタ）ア
クリル酸エステルとしては、例えば、アクリル酸
メチル、アクリル酸エチル、アクリル酸ブチル、
アクリル酸２−エチルヘキシル等のアクリル酸エ
ステル類、メタクリル酸メチル、メタクリル酸エ
チル、メタクリル酸ブチル等のメタクリル酸エス
テルが挙げられる。
本発明では、塩化ビニル及び（メタ）アクリル
酸エステルの他に、所望により第３モノマーとし
てこれらと共重合可能なモノマー、例えばスチレ
ン、アクリロニトリル、塩化ビニリデン、アクリ
ル酸、メタクリル酸等の不飽和一塩基酸及びそれ
らの塩類、イタコン酸、マレイン酸等の不飽和二
塩基酸及びそれらの塩類や半エステル類、２−ヒ
ドロキシエチルアクリルアミド、Ｎ−メチロール
アクリロアミド等の水酸基含有ビニル化合物類、
トリアリルシアヌレート、トリメチロールプロパ
ンジアリルエーテル、ジアリルフタレート等のア
リル化合物類、グリシジルメタアクリレート、ア
リルグリシジルエーテル等のエポキシ基含有不飽
和化合物、メタクリル酸−２−（１−アジリジル）
エチル等のアジリジン化合物等を、使用する塩化
ビニル及び（メタ）アクリル酸エステルの合計重
量に対し10重量％以内の範囲で使用できる。
この重合に用いられる乳化剤及び保護コロイド
は、従来公知のもので良く例えば、各種アルキル
金属塩、アルキルアリルスルフオン酸塩、アルキ
ルスルフオン酸塩、ポリオキシエチレンアルキル
アリールエーテル、ポリオキシエチレンソルビタ
ン誘導体などのアニオン及びノニオン系界面活性
剤、ビニルスルフオン酸塩等の反応型界面活性
剤、ポリビニルアルコール、アルキルセルロー
ス、ヒドロキシアルキルセルロース、ポリアクリ
ル酸塩等の水溶性保護コロイド等がある。
また、重合開始剤は従来公知なもので良く、例
えば、過硫酸カリウム、過硫酸アンモニウム等の
水溶性重合開始剤、ベンゾイルパーオキサイド等
の油溶性開始剤、又は、これらの過酸化物と還元
剤よりなるレドツクス系重合開始剤等を使用する
ことができる。
更に、連鎖移動剤、無機金属塩類、アンモニウ
ム塩類等従来公知のものを使用することができ
る。
実施例
以下、実施例及び比較例により本発明を説明す
る。
尚、以下、特にことわりのない限り「％」は重
量％を表す。
実施例 １
〈重合〉
攪拌機付50重合缶（ステンレス製）に表１の
初期添加の欄に記載の乳化剤、種エマルジヨン、
ピロリン酸ソーダ、過硫酸カリ、アンモニア水及
び純水を仕込み、攪拌下に真空脱気後窒素封入、
再度真空脱気の操作を３回繰り返して行ない、充
分に脱酸素した後50℃に昇温した。次いで、初期
添加の塩化ビニル1330ｇを仕込んだ。重合缶内液
温が再度50℃に達した時点を重合開始とし、後添
の塩化ビニル12600ｇを、重合開始から約30時間
かけて重合系に分割添加（30分に１回の割合で、
１回当り210ｇずつ添加）し、かつ後添の第２モ
ノマー、第３モノマー及び乳化液を重合開始後約
30時間にわたり重合系に連続添加した。
重合を完結させるため、上記分割及び連続添加
終了後更に５時間重合を継続して、塩化ビニル共
重合体エマルジヨンを得た。
尚、重合温度は50℃一定に維持した。
〈可塑化〉
上記で得られたエマルジヨンを、攪拌機付1.5
オートクレーブ（ステンレス製）に仕込み、下
記条件で可塑化した。
可塑化条件
エマルジヨン 700ｇ
純 水 130ｇ
ジオクチルフタレート 140ｇ
ネオペレツクスNo.６ 13ｇ
28％アンモニア水 6.5ｇ
可塑化温度 120℃
可塑化時間 ２時間
ここで得られたエマルジヨンの物性を表３に示
す。
実施例 ２〜９
重合条件を表１に示すように変えた以外は実施
例１と同様に重合を行なつた。得られたエマルジ
ヨンを実施例１と同様にして可塑化したエマルジ
ヨンの物性を表３に示す。
比較例 １〜８
重合条件を表２に示すように変えた以外は実施
例１と同様にして重合を行なつた。得られたエマ
ルジヨンを実施例１と同様にして可塑化したエマ
ルジヨンの物性を表４に示す。
[Industrial Field of Application] The present invention relates to a method for producing a vinyl chloride copolymer emulsion that has good viscosity stability and storage stability of the resulting plasticized emulsion. [Prior Art] Conventionally known methods for producing vinyl chloride copolymer emulsions include a bulk charging method, a monomer addition method, an emulsion addition method, and a seed polymerization method. In order to homogenize the polymer composition within the emulsion particles, vinyl chloride and a monomer copolymerizable with it are used in a system that contains a polymerization initiator, emulsifier, protective colloid, water, etc., but does not contain monomers. It is effective to carry out addition polymerization of the entire amount, either continuously or in portions. Vinyl chloride copolymer emulsions polymerized in this way are used in adhesives, paints, various binders, cement admixtures, etc., but when lowering the minimum film forming temperature, plasticizers are added to
Plasticized at around 150℃. However, if the plasticized product obtained here is stored for a long period of time, the viscosity increases and the plasticizer tends to separate. storage temperature
At temperatures above 50°C, these phenomena are accelerated, and in extreme cases, the plasticized material gels. References Emulsion Latex Handbook Taiseisha P-277-288 PVC and Polymer
13 (4) 10-25 [Problems to be solved by the invention] The present invention was made to solve the problems of the prior art, and aims to improve the viscosity stability, storage stability, etc. of plasticized products. An object of the present invention is to provide a method for producing a vinyl chloride copolymer emulsion. [Means for Solving the Problems] In the present invention, when emulsion copolymerizing vinyl chloride and acrylic ester or methacrylic ester, polymerization is started by charging 3 to 30% by weight of the total amount of vinyl chloride used, Thereafter, the remaining amount of vinyl chloride and the total amount of acrylic ester or methacrylic ester used are added to the polymerization system continuously or in portions. The present invention will be explained in detail below. In the present invention, vinyl chloride is the only monomer initially added before the start of polymerization, and the amount thereof is 3 to 30% by weight, preferably 5 to 15% by weight, based on the total amount of vinyl chloride used. If it is less than 3% by weight, the viscosity stability and storage stability of the resulting plasticized emulsion will not be improved, and if it exceeds 30% by weight, the polymer composition in the emulsion particles cannot be made uniform. Further, in the present invention, a seed emulsion can be present in the system before the initiation of polymerization. In the production method of the present invention, after the start of polymerization, the remaining amount of vinyl chloride and the total amount of each of the (meth)acrylic acid ester and the optional third monomer are post-added to the polymerization system, either continuously or in portions. do. These monomers can be added to the polymerization system continuously or in portions by any method, such as using each monomer alone, mixing the monomers with each other, mixing the monomers with an emulsion, or a combination of these. Added later. In the present invention, it is preferable to add an emulsion containing an emulsifier, water, etc. continuously or in portions between the start of polymerization and the end of addition of post-added monomers. Examples of the (meth)acrylic ester used as the second monomer in the present invention include methyl acrylate, ethyl acrylate, butyl acrylate,
Examples include acrylic esters such as 2-ethylhexyl acrylate, and methacrylic esters such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate. In the present invention, in addition to vinyl chloride and (meth)acrylic acid ester, a monomer copolymerizable with these as a third monomer, for example, an unsaturated monobase such as styrene, acrylonitrile, vinylidene chloride, acrylic acid, methacrylic acid, etc. Acids and their salts, unsaturated dibasic acids such as itaconic acid and maleic acid, and their salts and half esters, hydroxyl group-containing vinyl compounds such as 2-hydroxyethylacrylamide and N-methylolacrylamide,
Allyl compounds such as triallyl cyanurate, trimethylolpropane diallyl ether, diallyl phthalate, epoxy group-containing unsaturated compounds such as glycidyl methacrylate, allyl glycidyl ether, 2-(1-aziridyl methacrylate)
An aziridine compound such as ethyl can be used within a range of 10% by weight based on the total weight of vinyl chloride and (meth)acrylic acid ester used. The emulsifier and protective colloid used in this polymerization may be conventionally known ones, such as various alkyl metal salts, alkylaryl sulfonates, alkyl sulfonate salts, polyoxyethylene alkylaryl ethers, polyoxyethylene sorbitan derivatives, etc. Examples include anionic and nonionic surfactants, reactive surfactants such as vinyl sulfonate, and water-soluble protective colloids such as polyvinyl alcohol, alkyl cellulose, hydroxyalkyl cellulose, and polyacrylate. Further, the polymerization initiator may be a conventionally known one, such as a water-soluble polymerization initiator such as potassium persulfate or ammonium persulfate, an oil-soluble polymerization initiator such as benzoyl peroxide, or a combination of these peroxides and a reducing agent. Redox-based polymerization initiators, etc., can be used. Furthermore, conventionally known chain transfer agents, inorganic metal salts, ammonium salts, and the like can be used. Examples The present invention will be explained below with reference to Examples and Comparative Examples. In addition, hereinafter, unless otherwise specified, "%" represents % by weight. Example 1 <Polymerization> In a 50-meter polymerization can (stainless steel) equipped with a stirrer, the emulsifier, seed emulsion, and
Sodium pyrophosphate, potassium persulfate, aqueous ammonia and pure water are prepared, vacuum degassed while stirring, and then filled with nitrogen.
The vacuum degassing operation was repeated three times to sufficiently remove oxygen, and then the temperature was raised to 50°C. Next, 1330 g of vinyl chloride, which was initially added, was charged. Polymerization was started when the temperature of the liquid in the polymerization reactor reached 50°C again, and 12,600 g of vinyl chloride was added to the polymerization system in portions over about 30 hours from the start of polymerization (once every 30 minutes).
210 g each time), and the second monomer, third monomer, and emulsion liquid added later were added at a rate of about 210 g after the start of polymerization.
It was added continuously to the polymerization system over a period of 30 hours. In order to complete the polymerization, the polymerization was continued for an additional 5 hours after the completion of the above division and continuous addition to obtain a vinyl chloride copolymer emulsion. Note that the polymerization temperature was kept constant at 50°C. <Plasticization> The emulsion obtained above was heated to 1.5 mm with a stirrer.
It was placed in an autoclave (made of stainless steel) and plasticized under the following conditions. Plasticizing conditions Emulsion 700 g Pure water 130 g Dioctyl phthalate 140 g Neopellex No. 6 13 g 28% ammonia water 6.5 g Plasticizing temperature 120°C Plasticizing time 2 hours The physical properties of the emulsion obtained here are shown in Table 3. Examples 2 to 9 Polymerization was carried out in the same manner as in Example 1, except that the polymerization conditions were changed as shown in Table 1. The obtained emulsion was plasticized in the same manner as in Example 1, and the physical properties of the emulsion are shown in Table 3. Comparative Examples 1 to 8 Polymerization was carried out in the same manner as in Example 1, except that the polymerization conditions were changed as shown in Table 2. The obtained emulsion was plasticized in the same manner as in Example 1, and the physical properties of the emulsion are shown in Table 4.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】【table】
塩化ビニル共重合体エマルジヨン可塑化物の粘
度安定性と貯蔵安定性が改良され、高温での長期
間の保存にも耐えられるようになり、品質の安定
した塩化ビニル系樹脂エマルジヨンが得られた。
The viscosity stability and storage stability of the plasticized vinyl chloride copolymer emulsion were improved, and it became possible to withstand long-term storage at high temperatures, resulting in a vinyl chloride resin emulsion with stable quality.
Claims (1)
リル酸エステルを乳化共重合するに際し、塩化ビ
ニル全使用量の３〜30重量％を仕込んで重合を開
始し、その後塩化ビニルの残量及びアクリル酸エ
ステル又はメタクリル酸エステルの全使用量を連
続して又は分割して重合系に添加することを特徴
とする塩化ビニル系共重合体エマルジヨンの製造
法。1 When emulsion copolymerizing vinyl chloride and acrylic ester or methacrylic ester, polymerization is started by charging 3 to 30% by weight of the total amount of vinyl chloride used, and then the remaining amount of vinyl chloride and acrylic ester or methacrylic acid are added. A method for producing a vinyl chloride copolymer emulsion, characterized in that the entire amount of ester used is added to the polymerization system either continuously or in portions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4815785A JPS61207417A (en) | 1985-03-13 | 1985-03-13 | Production of vinyl chloride copolymer emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4815785A JPS61207417A (en) | 1985-03-13 | 1985-03-13 | Production of vinyl chloride copolymer emulsion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61207417A JPS61207417A (en) | 1986-09-13 |
| JPH0580494B2 true JPH0580494B2 (en) | 1993-11-09 |
Family
ID=12795537
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4815785A Granted JPS61207417A (en) | 1985-03-13 | 1985-03-13 | Production of vinyl chloride copolymer emulsion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61207417A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1798244A1 (en) | 2005-12-15 | 2007-06-20 | VESTOLIT GmbH & Co. KG | Process for the preparation of aqueous dispersions of vinyl chloride/(meth)acrylate copolymers |
| JP5169344B2 (en) * | 2008-03-14 | 2013-03-27 | 東ソー株式会社 | Method for producing vinyl chloride resin for paste processing |
-
1985
- 1985-03-13 JP JP4815785A patent/JPS61207417A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61207417A (en) | 1986-09-13 |
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