JPH04213302A - Polymerization of vinyl acetate monomer - Google Patents
Polymerization of vinyl acetate monomerInfo
- Publication number
- JPH04213302A JPH04213302A JP3136891A JP3136891A JPH04213302A JP H04213302 A JPH04213302 A JP H04213302A JP 3136891 A JP3136891 A JP 3136891A JP 3136891 A JP3136891 A JP 3136891A JP H04213302 A JPH04213302 A JP H04213302A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl acetate
- polymerization
- polymerizing
- acetate monomer
- 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.)
- Pending
Links
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000006116 polymerization reaction Methods 0.000 title description 11
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 5
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims abstract description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 abstract description 16
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 2
- -1 acrylic ester Chemical class 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000004372 Polyvinyl alcohol Substances 0.000 description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 239000002904 solvent Substances 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
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QUPCNWFFTANZPX-UHFFFAOYSA-M paramenthane hydroperoxide Chemical compound [O-]O.CC(C)C1CCC(C)CC1 QUPCNWFFTANZPX-UHFFFAOYSA-M 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZORJPNCZZRLEDF-UHFFFAOYSA-N (3-methoxy-3-methylbutoxy)carbonyloxy (3-methoxy-3-methylbutyl) carbonate Chemical compound COC(C)(C)CCOC(=O)OOC(=O)OCCC(C)(C)OC ZORJPNCZZRLEDF-UHFFFAOYSA-N 0.000 description 1
- CRJIYMRJTJWVLU-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yl 3-(5,5-dimethylhexyl)dioxirane-3-carboxylate Chemical compound CC(C)(C)CCCCC1(C(=O)OC(C)(C)CC(C)(C)C)OO1 CRJIYMRJTJWVLU-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- VGZZAZYCLRYTNQ-UHFFFAOYSA-N 2-ethoxyethoxycarbonyloxy 2-ethoxyethyl carbonate Chemical compound CCOCCOC(=O)OOC(=O)OCCOCC VGZZAZYCLRYTNQ-UHFFFAOYSA-N 0.000 description 1
- ZIDNXYVJSYJXPE-UHFFFAOYSA-N 2-methylbutan-2-yl 7,7-dimethyloctaneperoxoate Chemical compound CCC(C)(C)OOC(=O)CCCCCC(C)(C)C ZIDNXYVJSYJXPE-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
- UUPWEGAONCOIFJ-UHFFFAOYSA-N CCCCC(CC)COC(=O)OOC(O)=O Chemical compound CCCCC(CC)COC(=O)OOC(O)=O UUPWEGAONCOIFJ-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- HRYGOPGASPGRAD-UHFFFAOYSA-N carboxyoxy 1,2-dimethoxypropan-2-yl carbonate Chemical compound COCC(C)(OC)OC(=O)OOC(O)=O HRYGOPGASPGRAD-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 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
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-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
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 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
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerization Catalysts (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、酢酸ビニル単量体単独
またはそれと共重合可能なビニル単量体との混合物を重
合させる際に、特定の重合開始剤を用いることにより、
熱安定性の良い重合物を得る方法に関するものである。[Industrial Application Field] The present invention provides a method for polymerizing vinyl acetate monomer alone or a mixture of vinyl monomers copolymerizable with vinyl acetate by using a specific polymerization initiator.
This invention relates to a method for obtaining a polymer with good thermal stability.
【０００２】0002
【従来の技術】酢酸ビニル系単量体の重合方法は従来溶
液重合法、懸濁重合法あるいは乳化重合法等が用いられ
ている。その際用いられる重合開始剤としては、過硫酸
カリウムなどの過硫酸塩、パラメンタンヒドロペルオキ
シドなどのヒドロペルオキシド、アゾビスイソブチロニ
トリルなどのアゾ系開始剤、ベンゾイルペルオキシドな
どのジアシルペルオキシドなどが知られている。また米
国特許第３０３６０５４号公報明細書の記載にはジ（イ
ソプロピルペルオキシ）ジカーボネートを用いる方法が
開示されている。BACKGROUND OF THE INVENTION Conventional methods for polymerizing vinyl acetate monomers include solution polymerization, suspension polymerization, and emulsion polymerization. Known polymerization initiators used in this case include persulfates such as potassium persulfate, hydroperoxides such as para-menthane hydroperoxide, azo initiators such as azobisisobutyronitrile, and diacyl peroxides such as benzoyl peroxide. It is being Further, US Pat. No. 3,036,054 discloses a method using di(isopropylperoxy)dicarbonate.
【０００３】0003
【発明が解決しようとする課題】従来知られている重合
開始剤を用いて酢酸ビニル系単量体を重合した重合体は
耐熱安定性が悪く、加熱により着色するという問題があ
った。本発明の目的は、酢酸ビニル系単量体を重合する
際、特定の重合開始剤を使用することにより、熱安定性
のよい着色しない重合体を提供する。[Problems to be Solved by the Invention] Polymers obtained by polymerizing vinyl acetate monomers using conventionally known polymerization initiators have a problem of poor heat resistance stability and coloring when heated. An object of the present invention is to provide a non-colored polymer with good thermal stability by using a specific polymerization initiator when polymerizing a vinyl acetate monomer.
【０００４】0004
【課題を解決するための手段】本発明者らは、上記の従
来法の問題点について長期にわたって研究した結果、特
定の重合開始剤を用いることにより、従来の開始剤を使
用したときと比較して耐熱安定性の良好な酢酸ビニル系
重合体が得られるる方法を見出して本発明を完成した。[Means for Solving the Problems] As a result of long-term research into the problems of the above-mentioned conventional methods, the present inventors have found that by using a specific polymerization initiator, compared to when using a conventional initiator, The present invention was completed by discovering a method for obtaining a vinyl acetate polymer with good heat resistance stability.
【０００５】本発明は、酢酸ビニル単量体単独またはそ
れと共重合可能なビニル単量体との混合物を重合させる
際に重合開始剤として、一般式
（式中Ｒは炭素数３〜１０のアルキル基あるいはア
ルコキシアルキル基あるいはアルキルシクロヘキシル基
、ただし炭素数３のときはｎープロピル基である。）で
示される有機過酸化物、及び一般式
（式中Ｒ１は炭素数３〜１０のα分岐のアルキル基
を表し、Ｒ２は炭素数４〜１０の３級アルキル基を表す
。）で示される有機過酸化物からなる群から選ばれる１
種以上を使用することを特徴とする酢酸ビニル系単量体
の重合方法である。[0005] The present invention provides a polymerization initiator for polymerizing vinyl acetate monomer alone or a mixture of vinyl monomers copolymerizable with vinyl acetate monomer, in which R is an alkyl group having 3 to 10 carbon atoms. or an alkoxyalkyl group or an alkylcyclohexyl group, however, when the number of carbon atoms is 3, it is an n-propyl group. R2 represents a tertiary alkyl group having 4 to 10 carbon atoms.
This is a method for polymerizing vinyl acetate monomers, characterized in that more than one type of vinyl acetate monomer is used.
【０００６】本発明に使用される有機過酸化物は、
としては、例えば、ジーｎープロピルペルオキシジカー
ボネート、ジー２ーエトキシエチルペルオキシジカーボ
ネート、ジメトキシイソプロピルペルオキシジカーボネ
ート、ジ（３ーメチルー３ーメトキシブチル） ペルオ
キシジカーボネート、２ーエチルヘキシルペルオキシジ
カーボネート、４ーｔーブチルペルオキシシクロヘキシ
ルパーオキシジカールボネートが挙げられ、また[0006] The organic peroxide used in the present invention is
Examples include di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate, di(3-methyl-3-methoxybutyl) peroxydicarbonate, 2-ethylhexyl peroxydicarbonate, 4-t- butylperoxycyclohexylperoxydicarbonate, and
【００
０７】
としては、例えば、クミルペルオキシネオデカノエ
ート、ｔーブチルペルオキシネオデカノエート、１，１
ージメチルプロピルペルオキシネオデカノエート、１，
１ージメチルブチルペルオキシネオデカノエートおよび
１，１，３，３ーテトラメチルブチルペルオキシネオデ
カノエートが挙げられる。00
Examples include cumyl peroxyneodecanoate, t-butylperoxyneodecanoate, 1,1
-dimethylpropyl peroxyneodecanoate, 1,
Mention may be made of 1-dimethylbutyl peroxyneodecanoate and 1,1,3,3-tetramethylbutylperoxyneodecanoate.
【０００８】本発明に使用される酢酸ビニル単量体と共
重合可能なビニル単量体としては、例えばメタクリル酸
、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、メタクリル酸オクチルなどのメタクリル酸
エステル類、アクリル酸、アクリル酸メチル、アクリル
酸エチル、アクリル酸ブチル、アクリル酸オクチルなど
のアクリル酸エステル類、アクリロニトリル、メタクリ
ロニトリル、クロトン酸等が用いられる。またこれらの
単量体の他に分子量を調節する目的で各種連鎖移動剤を
添加したものでもよい。連鎖移動剤としてはｎーオクチ
ルメルカプタン、ｎードデシルメルカプタンなどのメル
カプタン類などが挙げられる。Examples of vinyl monomers copolymerizable with the vinyl acetate monomer used in the present invention include methacrylic acid esters such as methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and octyl methacrylate. Acrylic acid esters such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and octyl acrylate, acrylonitrile, methacrylonitrile, crotonic acid, and the like are used. In addition to these monomers, various chain transfer agents may be added for the purpose of controlling the molecular weight. Examples of the chain transfer agent include mercaptans such as n-octyl mercaptan and n-dodecyl mercaptan.
【０００９】本発明において用いられる重合開始剤の添
加量は重合温度、重合に用いる単量体の種類あるいはそ
の組み合わせにより異なるが一般に、単量体の仕込量１
００重量部に対して純品換算で０．００１〜１重量部で
あり、好ましくは０．０１〜０．１重量部である。その
量が０．００１重量部未満では重合速度が遅くなる傾向
にある。また１重量部を越えると重合速度の調節が困難
になる。[0009] The amount of the polymerization initiator used in the present invention varies depending on the polymerization temperature, the type of monomers used in the polymerization, or a combination thereof, but in general, the amount of monomers charged is 1
The amount is 0.001 to 1 part by weight in terms of pure product, preferably 0.01 to 0.1 part by weight. If the amount is less than 0.001 part by weight, the polymerization rate tends to be slow. Moreover, if it exceeds 1 part by weight, it becomes difficult to control the polymerization rate.
【００１０】本発明において用いられる重合方法は、通
常の溶液重合、乳化重合あるいは懸濁重合法で重合温度
は一般に４０〜 ７０℃の温度範囲である。溶液重合に
おいては溶剤としてメタノール、エタノール、イソプロ
パノール等のアルコール系溶剤が用いられる。The polymerization method used in the present invention is a conventional solution polymerization, emulsion polymerization or suspension polymerization method, and the polymerization temperature is generally in the range of 40 to 70°C. In solution polymerization, alcoholic solvents such as methanol, ethanol, and isopropanol are used as solvents.
【００１１】本発明によって得られた重合物は、これを
無溶剤あるいはメタノール中で、水酸化ナトリウム等の
アルカリあるいは、酸等を触媒として用いる通常のケン
化方法でケン化することによりポリビニルアルコールを
製造することができる。それにより得られるポリビニル
アルコールは着色が少なくかつ熱安定性が高い。[0011] The polymer obtained by the present invention is saponified to polyvinyl alcohol by a conventional saponification method using an alkali such as sodium hydroxide or an acid as a catalyst without a solvent or in methanol. can be manufactured. The polyvinyl alcohol obtained thereby has little coloration and high thermal stability.
【００１２】0012
【実施例】以下、本発明を実施例、参考例、比較例によ
り具体的に説明する。
（実施例１〜９および比較例１〜２）
攪拌器、温度計、還流冷却器および窒素導入管を備えた
容量５００ｍｌ４つ口フラスコに酢酸ビニル１５０ｇお
よびメタノール１５０ｇと表１に示す重合開始剤を入れ
、窒素を毎分１００ｍｌの割合で導入しながら５０℃で
５時間重合させた。ガスクロマトグラフにより残存する
酢酸ビニルを定量した。その結果は表１の通りであった
。また得られた重合物の一部をメタノールで希釈し、石
油エーテルに注ぎ重合物を析出させた。重合物を乾燥後
、５ｇをシャーレに取り、１５０℃で ２４時間加熱し
た。加熱後の重合物について、日本電色工業（株）製色
差計Ｚ−１００１−ＤＰを用いて色差を測定した。その
結果は表１の通りであった。[Examples] The present invention will be specifically explained below using Examples, Reference Examples, and Comparative Examples. (Examples 1 to 9 and Comparative Examples 1 to 2) 150 g of vinyl acetate, 150 g of methanol, and the polymerization initiator shown in Table 1 were placed in a 500 ml four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube. and polymerization was carried out at 50° C. for 5 hours while introducing nitrogen at a rate of 100 ml per minute. The remaining vinyl acetate was determined by gas chromatography. The results were as shown in Table 1. Further, a part of the obtained polymer was diluted with methanol and poured into petroleum ether to precipitate the polymer. After drying the polymer, 5 g was placed in a Petri dish and heated at 150°C for 24 hours. The color difference of the heated polymer was measured using a color difference meter Z-1001-DP manufactured by Nippon Denshoku Kogyo Co., Ltd. The results were as shown in Table 1.
【００１３】[0013]
【表１】[Table 1]
【００１４】
（比較例３）
実施例１と同じ装置を用い重合開始剤としてラウロイル
ペルオキシド０．０５ｇを用い、重合温度を６５℃に変
えた他は実施例１と同じ操作を行った。酢酸ビニルの重
合転化率は９２％であった。また１５０℃、２４時間加
熱後の重合物の色差は２５．５であった。(Comparative Example 3) The same operation as in Example 1 was performed, except that the same apparatus as in Example 1 was used, 0.05 g of lauroyl peroxide was used as a polymerization initiator, and the polymerization temperature was changed to 65°C. The polymerization conversion rate of vinyl acetate was 92%. The color difference of the polymer after heating at 150° C. for 24 hours was 25.5.
【００１５】
（比較例４）
実施例１と同じ装置を用い、ポリビニルアルコール０．
３ｇを溶解したイオン交換水３００ｇ、ｌーアスコルビ
ン酸３０ｍｇ、硫酸第１鉄１ｍｇ 、エチレンジアミン
４酢酸ナトリウム３ｍｇおよび酢酸ビニル５０ｇを入れ
５０℃に調節した。その中にパラメンタンヒドロペルオ
キシド０．０３ｇを添加し、２時間反応を行なった。酢
酸ビニルの重合転化率は７５％であった。また１５０℃
、２４時間加熱後の重合物の色差は３６．５であった。(Comparative Example 4) Using the same apparatus as in Example 1, polyvinyl alcohol 0.
300 g of ion-exchanged water in which 3 g of ion-exchanged water had been dissolved, 30 mg of 1-ascorbic acid, 1 mg of ferrous sulfate, 3 mg of sodium ethylenediaminetetraacetate, and 50 g of vinyl acetate were added, and the temperature was adjusted to 50°C. 0.03 g of paramenthane hydroperoxide was added thereto, and the reaction was carried out for 2 hours. The polymerization conversion rate of vinyl acetate was 75%. Also 150℃
The color difference of the polymer after heating for 24 hours was 36.5.
【００１６】
（参考例１〜１３）
実施例１〜９及び比較例１〜４で得られた酢酸ビニル重
合体のエタノール溶液１００ｇを、それぞれ減圧下で濃
縮しメタノールと酢酸ビニル単量体を除いた後、０．４
ｍｏｌ／ｌの水酸化ナトリウムのメタノール溶液８００
ｇを加え、攪拌しながら５０℃で１時間ケン化を行った
。その後、生成したケン化物を濾別し、メタノール洗浄
し、９０℃で１０時間乾燥し、ポリビニルアルコールを
得た。得られたポリビニルアルコール５ｇをシゃーレに
とり、１３０℃で２４時間加熱した。加熱後のポリビニ
ルアルコールについて、実施例１と同様に色差を測定し
た。その結果表２の通りであった。(Reference Examples 1 to 13) 100 g of the ethanol solutions of vinyl acetate polymers obtained in Examples 1 to 9 and Comparative Examples 1 to 4 were concentrated under reduced pressure to remove methanol and vinyl acetate monomers. After that, 0.4
mol/l sodium hydroxide methanol solution 800
g was added thereto, and saponification was carried out at 50° C. for 1 hour while stirring. Thereafter, the generated saponified product was filtered, washed with methanol, and dried at 90°C for 10 hours to obtain polyvinyl alcohol. 5 g of the obtained polyvinyl alcohol was placed in a Petri dish and heated at 130° C. for 24 hours. The color difference of the polyvinyl alcohol after heating was measured in the same manner as in Example 1. The results were as shown in Table 2.
【００１７】[0017]
【表２】[Table 2]
【００１８】実施例及び比較例で明らかなように本発明
の重合開始剤を用いたものは、酢酸ビニル系の重合体の
耐熱性が良く加熱による変色の少ないことが分かる。ま
た参考例で明らかなように、それをケン化して得られる
ポリビニルアルコールは着色がなく耐熱性が良いことが
分かる。As is clear from the Examples and Comparative Examples, the vinyl acetate polymers using the polymerization initiator of the present invention have good heat resistance and little discoloration due to heating. Furthermore, as is clear from the reference examples, the polyvinyl alcohol obtained by saponifying it is not colored and has good heat resistance.
【００１９】[0019]
【本発明の効果】特定の重合開始剤を用いる本発明は、
以下に述べる特徴を有している。即ち本発明により、従
来より熱安定性が良く、高温において着色し難い酢酸ビ
ニル重合体が得られる。[Effects of the present invention] The present invention uses a specific polymerization initiator,
It has the characteristics described below. That is, according to the present invention, a vinyl acetate polymer can be obtained which has better thermal stability than conventional ones and is less likely to be colored at high temperatures.
Claims (1)
重合可能なビニル単量体との混合物を重合させる際に重
合開始剤として、一般式 （式中Ｒは炭素数３〜１０のアルキル基あるいはア
ルコキシアルキル基あるいはアルキルシクロヘキシル基
、ただし炭素数３のときはｎープロピル基である。）で
示される有機過酸化物、及び一般式 式中Ｒ１は炭素数３〜１０のα分岐のアルキル基を
表し、Ｒ２は炭素数４〜１０の３級アルキル基を表す。 ）で示される有機過酸化物からなる群から選ばれる１種
以上を使用することを特徴とする酢酸ビニル系単量体の
重合方法。Claim 1: When polymerizing a vinyl acetate monomer alone or a mixture thereof with a vinyl monomer copolymerizable with the vinyl acetate monomer, a polymerization initiator containing the general formula (wherein R is an alkyl group having 3 to 10 carbon atoms or an alkoxyalkyl group or an alkylcyclohexyl group, however, when the number of carbon atoms is 3, it is an n-propyl group. , R2 represents a tertiary alkyl group having 4 to 10 carbon atoms. 1. A method for polymerizing vinyl acetate monomers, characterized in that one or more selected from the group consisting of organic peroxides shown in ) are used.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11141690 | 1990-04-26 | ||
| JP2-111416 | 1990-04-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04213302A true JPH04213302A (en) | 1992-08-04 |
Family
ID=14560619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3136891A Pending JPH04213302A (en) | 1990-04-26 | 1991-02-01 | Polymerization of vinyl acetate monomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04213302A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5728788A (en) * | 1996-03-29 | 1998-03-17 | Kuraray Co., Ltd. | Process of producing vinyl acetate polymer |
| JP2008143961A (en) * | 2006-12-07 | 2008-06-26 | Nippon Synthetic Chem Ind Co Ltd:The | Carboxy group-containing polyvinyl alcohol-based resin |
| WO2010126041A1 (en) * | 2009-04-28 | 2010-11-04 | 日本合成化学工業株式会社 | Polyvinyl alcohol resin composition |
| JP2011241234A (en) * | 2009-04-28 | 2011-12-01 | Nippon Synthetic Chem Ind Co Ltd:The | Polyvinyl alcohol-based resin composition |
-
1991
- 1991-02-01 JP JP3136891A patent/JPH04213302A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5728788A (en) * | 1996-03-29 | 1998-03-17 | Kuraray Co., Ltd. | Process of producing vinyl acetate polymer |
| JP2008143961A (en) * | 2006-12-07 | 2008-06-26 | Nippon Synthetic Chem Ind Co Ltd:The | Carboxy group-containing polyvinyl alcohol-based resin |
| WO2010126041A1 (en) * | 2009-04-28 | 2010-11-04 | 日本合成化学工業株式会社 | Polyvinyl alcohol resin composition |
| JP2011241234A (en) * | 2009-04-28 | 2011-12-01 | Nippon Synthetic Chem Ind Co Ltd:The | Polyvinyl alcohol-based resin composition |
| US8722782B2 (en) | 2009-04-28 | 2014-05-13 | The Nippon Synthetic Chemical Industry Co., Ltd. | Polyvinyl alcohol-based resin composition |
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