TW202019976A - Dispersing auxiliary agent for suspension polymerization and method for producing vinyl resin - Google Patents
Dispersing auxiliary agent for suspension polymerization and method for producing vinyl resin Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/02—Monomers containing chlorine
- C08F14/04—Monomers containing two carbon atoms
- C08F14/06—Vinyl chloride
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
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- C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
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Abstract
Description
本發明係關於一種懸浮聚合用分散助劑,尤其係關於一種適於乙烯系化合物、特別是氯乙烯之懸浮聚合之懸浮聚合用分散助劑。The present invention relates to a dispersion aid for suspension polymerization, in particular to a dispersion aid for suspension polymerization suitable for suspension polymerization of vinyl compounds, especially vinyl chloride.
關於氯乙烯系樹脂等乙烯系聚合物之製造,於工業上廣泛地實施懸浮聚合法,該懸浮聚合法係於水溶性介質中於分散劑之存在下使乙烯系化合物分散,使用油溶性觸媒進行聚合。作為通常決定該樹脂之品質之主要因素,可列舉聚合率、水-單體比、聚合溫度、聚合起始劑之量或饋入時期、聚合槽之形式、攪拌速度或分散劑之種類、量等,該主要因素中亦可謂分散劑之影響大。Regarding the production of vinyl polymers such as vinyl chloride resins, a suspension polymerization method is widely carried out industrially. This suspension polymerization method is to disperse a vinyl compound in the presence of a dispersant in a water-soluble medium and use an oil-soluble catalyst Perform polymerization. The main factors that generally determine the quality of the resin include polymerization rate, water-to-monomer ratio, polymerization temperature, amount or feed period of polymerization initiator, type of polymerization tank, stirring speed, or type and amount of dispersant And so on, the main factor can also be said that the influence of the dispersant is great.
作為對乙烯系化合物之懸浮聚合用分散劑所要求之性能,可列舉:(1)少量使用且懸浮聚合穩定性明顯優異,有可使所得之乙烯系聚合物粒子之粒徑分佈儘可能狹窄之作用;(2)增大塑化劑朝聚合物粒子之吸收速度而使聚合物之加工性容易,使殘存於聚合物粒子中之氯乙烯等單體之去除容易,且為了防止成形品中之魚眼(fish eye)等之生成而有調整為多孔性之作用;(3)有形成容積比重大之聚合物粒子之作用;(4)操作性良好等。Examples of the performance required for the dispersant for suspension polymerization of vinyl compounds include: (1) Use in a small amount and the suspension polymerization stability is remarkably excellent, and the particle size distribution of the obtained vinyl polymer particles can be as narrow as possible Function; (2) increase the absorption rate of the plasticizer towards the polymer particles to make the processability of the polymer easy, make the removal of monomers such as vinyl chloride remaining in the polymer particles easy, and in order to prevent The formation of fish eyes has the effect of adjusting to porosity; (3) the function of forming polymer particles with a large volume ratio; (4) the operability is good.
對該等性能(1)至(4)之要求水準日益提高。尤其於上述(2)所記載之單體成分之去除性方面,就環境之觀點而言,殘存單體量之限制成為非常高之水準。另外,於聚氯乙烯聚合結束後之乾燥步驟中難以去除殘存於粒子中之氯乙烯單體之情形時,為了去除殘存單體,需要長時間或高溫條件之乾燥,但同時亦擔心聚氯乙烯樹脂變質。另外,關於上述(4)所記載之操作性,於環境問題上,近年來不樂於使用甲醇等有機溶劑,而期望可將懸浮聚合用分散劑以水性液之形態使用。The level of requirements for these properties (1) to (4) is increasing day by day. In particular, in terms of the removability of the monomer components described in (2) above, from the environmental point of view, the limit of the amount of residual monomers becomes a very high level. In addition, when it is difficult to remove the vinyl chloride monomer remaining in the particles in the drying step after the polymerization of polyvinyl chloride, in order to remove the residual monomer, a long time or high temperature drying is required, but at the same time, there is also concern about polyvinyl chloride The resin deteriorated. In addition, regarding the operability described in the above (4), in terms of environmental issues, in recent years, it has been reluctant to use organic solvents such as methanol, but it is desired that the dispersant for suspension polymerization can be used in the form of an aqueous liquid.
作為該懸浮聚合用分散劑,主要可使用聚乙烯醇系樹脂(以下有時簡稱為PVA)之主分散劑。其中,可使用皂化度為65莫耳%至99莫耳%之PVA作為主分散劑,另外,皂化度小於65莫耳%之PVA多被用作分散助劑。主分散劑係主要期待(1)或(3)之性能而使用,分散助劑係期待(2)之性能而使用。另外,(4)之性能係對於所使用之所有分散劑要求。As the dispersant for suspension polymerization, a main dispersant of a polyvinyl alcohol-based resin (hereinafter sometimes simply referred to as PVA) may be used. Among them, PVA with a saponification degree of 65 mol% to 99 mol% can be used as the main dispersant. In addition, PVA with a saponification degree of less than 65 mol% is often used as a dispersion aid. The main dispersant is mainly used in anticipation of the performance of (1) or (3), and the dispersion aid is used in anticipation of the performance of (2). In addition, the performance of (4) is required for all dispersants used.
作為該分散助劑,提出有於單末端具有離子性基且皂化度為10莫耳%至85莫耳%之聚乙烯醇系聚合物(專利文獻1)、將由乙酸乙烯酯及不飽和羧酸所構成之聚合物皂化而成之聚乙烯醇系聚合物(專利文獻2)、或皂化度為35莫耳%以上至65莫耳%以下並且於末端具有碳數為6以上至12以下之脂肪族烴基之乙烯醇系聚合物(專利文獻3)等。 [先前技術文獻] [專利文獻]As the dispersing aid, a polyvinyl alcohol-based polymer (Patent Document 1) having an ionic group at one terminal and a saponification degree of 10 mol% to 85 mol% is proposed. Saponified polyvinyl alcohol-based polymer (Patent Document 2), or a saponification degree of 35 mol% or more to 65 mol% or less and a fat having a carbon number of 6 or more and 12 or less at the terminal A vinyl alcohol polymer of a hydrocarbon group (Patent Document 3) and the like. [Prior Technical Literature] [Patent Literature]
專利文獻1:日本特開平10-168128號公報。 專利文獻2:日本特開2013-203994號公報。 專利文獻3:國際公開第2015/019614號。Patent Document 1: Japanese Patent Laid-Open No. 10-168128. Patent Document 2: Japanese Patent Laid-Open No. 2013-203994. Patent Document 3: International Publication No. 2015/019614.
(發明所欲解決之課題)(Problems to be solved by the invention)
然而,對於近年來高漲之(1)至(4)之要求性能,包含使用了專利文獻1至專利文獻3所記載之PVA之分散助劑在內,難可謂存在充分滿足該等要求性能的乙烯系化合物之分散助劑。另外,習知之分散助劑係將乙烯酯系單體聚合而獲得乙烯酯系聚合物後,以鹼等進行皂化反應而製造,故而有下述缺點:擔心皂化反應時所用之溶劑殘存於製品中,或步驟長而耗費成本。However, it is difficult to say that there are ethylenes that fully satisfy the required performances including the dispersing aids using the PVA described in Patent Literatures 1 to 3, including the requirement performances (1) to (4) that have soared in recent years. It is a compound dispersion aid. In addition, conventional dispersion aids are produced by polymerizing vinyl ester-based monomers to obtain vinyl ester-based polymers, and then subjected to saponification reaction with an alkali or the like. Therefore, they have the following disadvantages: they worry that the solvent used during the saponification reaction may remain in the product , Or the steps are long and costly.
因此,本發明之一個課題在於提供一種懸浮聚合用分散助劑,該懸浮聚合用分散助劑係操作性優異,且於將該懸浮聚合用分散助劑用於乙烯系化合物之懸浮聚合之情形時,可獲得粗大粒子之形成少且塑化劑之吸收性高的乙烯系樹脂粒子。進而,本發明之另一課題在於提供一種乙烯系樹脂之製造方法,該乙烯系樹脂之製造方法使用此種懸浮聚合用分散助劑。 (用以解決課題之手段)Therefore, an object of the present invention is to provide a dispersion aid for suspension polymerization, which is excellent in handleability, and when the dispersion aid for suspension polymerization is used in the suspension polymerization of a vinyl compound It is possible to obtain vinyl resin particles with little formation of coarse particles and high plasticizer absorption. Furthermore, another object of the present invention is to provide a method for producing an ethylene-based resin using such a dispersion aid for suspension polymerization. (Means to solve the problem)
本發明人等為了解決上述課題而反覆潛心研究,結果發現將酸值(KOH mg/g)為5以上且小於100之乙烯酯系聚合物用作乙烯系化合物之懸浮聚合用分散助劑係有效。In order to solve the above-mentioned problems, the present inventors have repeatedly studied intensively and found that it is effective to use a vinyl ester polymer having an acid value (KOH mg/g) of 5 or more and less than 100 as a dispersion aid for suspension polymerization of a vinyl compound. .
因此,本發明於一方面係一種懸浮聚合用分散助劑,係含有酸值(KOH mg/g)為5以上且小於100之乙烯酯系聚合物。Therefore, in one aspect, the present invention is a dispersion aid for suspension polymerization, which contains a vinyl ester polymer having an acid value (KOH mg/g) of 5 or more and less than 100.
於本發明之懸浮聚合用分散助劑之一實施形態中,前述乙烯酯系聚合物為乙酸乙烯酯系聚合物。In one embodiment of the dispersion aid for suspension polymerization of the present invention, the vinyl ester polymer is a vinyl acetate polymer.
於本發明之懸浮聚合用分散助劑之另一實施形態中,前述乙烯酯系聚合物之黏度平均聚合度為100至1000。In another embodiment of the dispersion aid for suspension polymerization of the present invention, the viscosity average polymerization degree of the vinyl ester polymer is 100 to 1,000.
於本發明之懸浮聚合用分散助劑之進而另一實施形態中,前述乙烯酯系聚合物之皂化度為5莫耳%以下。In still another embodiment of the dispersion aid for suspension polymerization of the present invention, the saponification degree of the vinyl ester-based polymer is 5 mol% or less.
於本發明之懸浮聚合用分散助劑之進而另一實施形態中,含有60質量%以上之前述乙烯酯系聚合物。In still another embodiment of the dispersion aid for suspension polymerization of the present invention, the vinyl ester-based polymer is contained in an amount of 60% by mass or more.
於本發明之懸浮聚合用分散助劑之進而另一實施形態中,前述乙烯酯系聚合物之酸值(KOH mg/g)為10以上且小於40。In still another embodiment of the dispersion aid for suspension polymerization of the present invention, the acid value (KOH mg/g) of the vinyl ester polymer is 10 or more and less than 40.
本發明於另一方面係一種乙烯系樹脂之製造方法,係包括:使用本發明之懸浮聚合用分散助劑,使乙烯系化合物單體、或乙烯系化合物單體和可與該乙烯系化合物單體共聚合之單體之混合物分散於水中進行懸浮聚合。 (發明功效)Another aspect of the present invention is a method for producing an ethylene-based resin, comprising: using the dispersion aid for suspension polymerization of the present invention to make the vinyl compound monomer, or the vinyl compound monomer and the vinyl compound monomer The monomer mixture of bulk copolymerization is dispersed in water for suspension polymerization. (Effect of invention)
本發明可獲得一種懸浮聚合用分散助劑,該懸浮聚合用分散助劑係操作性優異,且於將該懸浮聚合用分散助劑用於乙烯系化合物之懸浮聚合之情形時,可製造粗大粒子之形成少且塑化劑之吸收性高的乙烯系樹脂粒子。The present invention can obtain a dispersion aid for suspension polymerization, which is excellent in handleability, and when the dispersion aid for suspension polymerization is used in suspension polymerization of an ethylene-based compound, coarse particles can be produced The vinyl resin particles with little formation and high plasticizer absorption.
以下,對本發明之實施方式進行詳細說明。再者,本發明不限定於以下說明之實施形態。Hereinafter, embodiments of the present invention will be described in detail. Furthermore, the present invention is not limited to the embodiments described below.
本發明之一實施形態之懸浮聚合用分散助劑所含有之乙烯酯系聚合物就水溶性及性能之觀點而言,重要的是酸值(KOH mg/g)為5以上且小於100。於酸值小於5mg/g之情形時,水溶性變得不充分,就操作方面而言於實用上成問題。因此,酸值必須為5mg/g以上,較佳為7mg/g以上,更佳為10mg/g以上。另外,若酸值成為100mg/g以上,則分散體系變得不穩定,所得之乙烯系樹脂粒子之粗大粒子生成等,於實用上成問題。因此,酸值必須小於100mg/g,較佳為小於90mg/g,更佳為小於80mg/g,進而更佳為小於70mg/g,又進一步更佳為小於60mg/g,再進一步更佳為小於50mg/g,特佳為小於40mg/g,尤佳為小於30mg/g。The vinyl ester polymer contained in the dispersion aid for suspension polymerization according to an embodiment of the present invention is important from the viewpoint of water solubility and performance in that the acid value (KOH mg/g) is 5 or more and less than 100. When the acid value is less than 5 mg/g, the water solubility becomes insufficient, which is a practical problem in terms of handling. Therefore, the acid value must be 5 mg/g or more, preferably 7 mg/g or more, and more preferably 10 mg/g or more. In addition, when the acid value becomes 100 mg/g or more, the dispersion system becomes unstable, and coarse particles of the obtained vinyl resin particles are generated, which is a problem in practical use. Therefore, the acid value must be less than 100 mg/g, preferably less than 90 mg/g, more preferably less than 80 mg/g, even more preferably less than 70 mg/g, still more preferably less than 60 mg/g, and even more preferably Less than 50mg/g, particularly preferably less than 40mg/g, particularly preferably less than 30mg/g.
酸值係依據JIS(Japanese Industrial Standard;日本工業標準) K0070:1992進行測定。亦即,由乙烯酯系聚合物之中和所需要的氫氧化鉀之量而求出。The acid value is measured in accordance with JIS (Japanese Industrial Standard) K0070:1992. That is, it is determined from the amount of potassium hydroxide required to neutralize the vinyl ester polymer.
本發明之一實施形態之懸浮聚合用分散助劑所含有之乙烯酯系聚合物係皂化度較佳為5莫耳%以下,更佳為2莫耳%以下,進而更佳為1莫耳%以下。亦可將皂化度設為0莫耳%。減小皂化度係可進行省略或縮短皂化之步驟,故而於經濟方面有利,對於提高酸值亦有利。The saponification degree of the vinyl ester-based polymer contained in the dispersion aid for suspension polymerization according to an embodiment of the present invention is preferably 5 mol% or less, more preferably 2 mol% or less, and still more preferably 1 mol% the following. The saponification degree can also be set to 0 mol%. Reducing the degree of saponification means that the steps of saponification can be omitted or shortened, so it is economically advantageous and is also beneficial for increasing the acid value.
乙烯酯系聚合物之皂化度係利用依據JIS K6726:1994之方法進行測定。亦即,由使用JIS K8951:2006所規定之N/10之硫酸及JIS K8576:2019所規定之N/10之氫氧化鈉溶液的反滴定而求出。The saponification degree of the vinyl ester-based polymer is measured by a method according to JIS K6726:1994. That is, it is determined by back titration using N/10 sulfuric acid specified in JIS K8951:2006 and N/10 sodium hydroxide solution specified in JIS K8576:2019.
本發明之一實施形態之懸浮聚合用分散助劑所含有之乙烯酯系聚合物之製造方法並無特別限制,但簡便的是於將乙烯酯系單體進行自由基聚合時,於不飽和羧酸之共存下進行聚合之方法。The production method of the vinyl ester-based polymer contained in the dispersion aid for suspension polymerization according to an embodiment of the present invention is not particularly limited, but it is convenient when the vinyl ester-based monomer is radically polymerized, The method of polymerization in the presence of acid.
作為用於本發明之不飽和羧酸,例如可列舉:丁烯酸、異丁烯酸、衣康酸、馬來酸、富馬酸、(甲基)丙烯酸等,但不限定於該等。不飽和羧酸可使用一種,亦可將兩種以上組合而使用。就與乙烯酯之反應性比或操作之容易度而言,最佳為使用丁烯酸。Examples of the unsaturated carboxylic acid used in the present invention include butenoic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, (meth)acrylic acid, and the like, but are not limited thereto. One type of unsaturated carboxylic acid may be used, or two or more types may be used in combination. In terms of reactivity ratio with vinyl ester or ease of operation, it is best to use crotonic acid.
作為乙烯酯系單體,並無限定,可列舉:乙酸乙烯酯、甲酸乙烯酯、丙酸乙烯酯、戊酸乙烯酯、癸酸乙烯酯、月桂酸乙烯酯、硬脂酸乙烯酯、苯甲酸乙烯酯、三甲基乙酸乙烯酯以及叔碳酸乙烯酯等。乙烯酯系單體可使用一種,亦可將兩種以上組合而使用。就獲取之容易度或操作、經濟性方面而言,最佳為使用乙酸乙烯酯。The vinyl ester monomer is not limited, and examples thereof include vinyl acetate, vinyl formate, vinyl propionate, vinyl valerate, vinyl caprate, vinyl laurate, vinyl stearate, and benzoic acid. Vinyl ester, trimethyl vinyl acetate, and tertiary vinyl carbonate. One type of vinyl ester monomer may be used, or two or more types may be used in combination. In terms of ease of acquisition, operation, and economy, it is best to use vinyl acetate.
關於懸浮聚合用分散助劑所含有之乙烯酯系聚合物之黏度平均聚合度,就將乙烯系化合物進行懸浮聚合時之分散穩定性或生產效率之觀點而言,較佳為100以上。於黏度平均聚合度小於100之情形時,於將乙烯系化合物進行懸浮聚合時分散體系容易變得不穩定,所得之乙烯系樹脂之粒度容易粗大化。另外,懸浮聚合用分散助劑之軟化溫度變低,故而於乾燥步驟中容易結塊而製造變困難。因此,黏度平均聚合度較佳為100以上,進而更佳為150以上,進一步更佳為200以上。另外,關於懸浮聚合用分散助劑所含有之乙烯酯系聚合物之黏度平均聚合度,為了防止水溶液黏度變高而處理變困難或提高將乙烯系化合物進行懸浮聚合時所得的粒子之孔隙度(porosity)從而提高塑化劑吸收性,較佳為1000以下,更佳為800以下,進而更佳為600以下。The viscosity average polymerization degree of the vinyl ester polymer contained in the dispersion aid for suspension polymerization is preferably 100 or more from the viewpoint of dispersion stability or production efficiency when the vinyl compound is subjected to suspension polymerization. When the average viscosity polymerization degree is less than 100, the dispersion system tends to become unstable when the ethylene-based compound is subjected to suspension polymerization, and the particle size of the resulting ethylene-based resin is likely to be coarsened. In addition, the softening temperature of the dispersion aid for suspension polymerization becomes low, so that it tends to agglomerate during the drying step, and manufacturing becomes difficult. Therefore, the average viscosity degree of polymerization is preferably 100 or more, more preferably 150 or more, and still more preferably 200 or more. In addition, with regard to the average viscosity degree of polymerization of the vinyl ester polymer contained in the dispersion aid for suspension polymerization, in order to prevent the viscosity of the aqueous solution from becoming high, the treatment becomes difficult or the porosity of the particles obtained when the vinyl compound is subjected to suspension polymerization ( porosity) to improve the absorbency of the plasticizer, preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less.
黏度平均聚合度係依據JIS K6725:1977進行測定。亦即,由對懸浮聚合用分散助劑所含有之乙烯酯系聚合物於30℃之丙酮中測定之極限黏度[η]而求出。The average polymerization degree of viscosity is measured in accordance with JIS K6725:1977. That is, it is determined from the limit viscosity [η] of the vinyl ester polymer contained in the dispersion aid for suspension polymerization measured in acetone at 30°C.
本發明之一實施形態之懸浮聚合用分散助劑所含有之乙烯酯系聚合物之聚合法並無特別限制,作為聚合方式,可為批次聚合、半批次聚合、連續聚合、半連續聚合之任一種。單體可一次性饋入,亦可分批饋入,或亦可連續地或間斷地添加。另外,可任意使用溶液、乳化、懸浮、塊狀聚合等公知之聚合方法,就製品中不殘留溶劑且容易進行乾燥之方面而言,於聚合後不殘留溶劑且以粒子而獲得聚合物之方法較合適,較佳為懸浮聚合法。The polymerization method of the vinyl ester polymer contained in the dispersion aid for suspension polymerization according to an embodiment of the present invention is not particularly limited, and the polymerization method may be batch polymerization, semi-batch polymerization, continuous polymerization, and semi-continuous polymerization. Any of them. The monomers can be fed at once, or in batches, or can be added continuously or intermittently. In addition, any known polymerization method such as solution, emulsification, suspension, and bulk polymerization can be used arbitrarily. In terms of no solvent remaining in the product and easy drying, a method of obtaining a polymer from particles without leaving a solvent after polymerization More suitable, preferably suspension polymerization.
此時,若為不損及本發明之功效之範圍,則亦可使其他單體進一步共聚合。作為其他單體,具體可列舉:乙烯、丙烯等烯烴類;馬來酸二烷基酯類;富馬酸二烷基酯類;烷基乙烯基醚類等。At this time, other monomers may be further copolymerized as long as the range of the present invention is not impaired. Specific examples of other monomers include olefins such as ethylene and propylene; dialkyl maleates; dialkyl fumarates; alkyl vinyl ethers, and the like.
將乙烯酯系單體進行自由基聚合時之聚合起始劑並無特別限定,可將下述化合物單獨使用或將兩種以上組合而使用:偶氮雙異丁腈、偶氮雙-2,4-二甲基戊腈、偶氮雙(4-甲氧基-2,4-二甲基戊腈)、偶氮雙二甲基戊腈、偶氮雙甲氧基戊腈等偶氮化合物;過氧化乙醯、過氧化苯甲醯、過氧化月桂醯、過氧化乙醯基環己基磺醯、2-過氧化苯氧基乙酸-2,4,4-三甲基戊酯等過氧化物;過氧化二碳酸二異丙酯、過氧化二碳酸二-2-乙基己酯、過氧化二碳酸二乙氧基乙酯等過碳酸酯化合物;過氧化新癸酸-α-異丙苯酯、過氧化新癸酸第三丁酯等過氧酸酯化合物等。The polymerization initiator when the vinyl ester monomer is subjected to radical polymerization is not particularly limited, and the following compounds may be used alone or in combination of two or more: azobisisobutyronitrile, azobis-2, Azo compounds such as 4-dimethylvaleronitrile, azobis (4-methoxy-2,4-dimethylvaleronitrile), azobisdimethylvaleronitrile, azobismethoxyvaleronitrile ; Peroxide, benzoyl peroxide, lauryl peroxide, ethoxycyclohexylsulfonyl peroxide, 2-peroxyphenoxyacetic acid-2,4,4-trimethylpentyl peroxide, etc. Substances; peroxycarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate; neodecanoic acid-α-isopropyl peroxide Peroxyester compounds such as phenyl ester and neobutyl decanoate.
另外,於以高溫度進行共聚合之情形時,有時可見到產生由乙烯酯系單體之氧化分解所引起的醛而生成縮合物導致著色等。於該情形時,亦可為了防止著色而於聚合體系中添加1ppm以上至100ppm以下(相對於乙烯酯系單體之總質量)之程度的檸檬酸般之抗氧化劑。In addition, when copolymerization is performed at a high temperature, aldehydes caused by the oxidative decomposition of vinyl ester-based monomers may be seen to form a condensate and cause coloring. In this case, in order to prevent coloring, a citric acid-like antioxidant may be added to the polymerization system to the extent of 1 ppm or more and 100 ppm or less (relative to the total mass of the vinyl ester-based monomer).
本發明之一實施形態之懸浮聚合用分散助劑就發揮所需性能之觀點而言,較佳為含有60質量%以上之酸值(KOH mg/g)為5以上且小於100之乙烯酯系聚合物,更佳為含有80質量%以上,進而更佳為含有90質量%以上。另外,本發明之懸浮聚合用分散助劑亦可於不損及本發明之主旨之範圍內含有各種添加劑。作為該添加劑,例如可列舉:醛類、鹵化烴類、硫醇類等聚合調整劑;酚化合物、硫化合物、N-過氧化物化合物等聚合抑制劑;pH調整劑;交聯劑;防腐劑;防黴劑、抗黏連劑;消泡劑等。The dispersion aid for suspension polymerization according to an embodiment of the present invention preferably contains a vinyl ester system having an acid value (KOH mg/g) of 60% by mass or more and 5 or more and less than 100 from the viewpoint of exhibiting desired performance. The polymer preferably contains 80% by mass or more, and more preferably contains 90% by mass or more. In addition, the dispersion aid for suspension polymerization of the present invention may contain various additives within a range not detracting from the gist of the present invention. Examples of the additives include polymerization regulators such as aldehydes, halogenated hydrocarbons, and thiols; polymerization inhibitors such as phenol compounds, sulfur compounds, and N-peroxide compounds; pH adjusters; crosslinking agents; preservatives ; Antifungal agent, anti-blocking agent; antifoaming agent, etc.
本發明之一實施形態之懸浮聚合用分散助劑可尤其合適地用於乙烯系化合物之懸浮聚合。作為乙烯系化合物,可列舉:氯乙烯等鹵化乙烯;乙酸乙烯酯、丙酸乙烯酯等乙烯酯;丙烯酸、甲基丙烯酸、該等之酯及鹽;馬來酸、富馬酸、該等之酯及酸酐;苯乙烯、丙烯腈、偏二氯乙烯、乙烯醚等。該等之中,本發明之懸浮聚合用分散助劑尤其合適地用於將氯乙烯單獨進行懸浮聚合時,或將氯乙烯與可與氯乙烯共聚合之單體一併進行懸浮聚合時。作為可與氯乙烯共聚合之單體,可列舉:乙酸乙烯酯、丙酸乙烯酯等乙烯酯;(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯等(甲基)丙烯酸酯;乙烯、丙烯等α-烯烴;馬來酸酐、衣康酸等不飽和二羧酸類;丙烯腈、苯乙烯、偏二氯乙烯、乙烯醚等。The dispersion aid for suspension polymerization according to an embodiment of the present invention can be particularly suitably used for suspension polymerization of vinyl compounds. Examples of the vinyl compounds include halogenated ethylene such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; acrylic acid, methacrylic acid, esters and salts of these; maleic acid, fumaric acid, and the like Ester and anhydride; styrene, acrylonitrile, vinylidene chloride, vinyl ether, etc. Among these, the dispersion aid for suspension polymerization of the present invention is particularly suitable for the suspension polymerization of vinyl chloride alone or the suspension polymerization of vinyl chloride and a monomer copolymerizable with vinyl chloride. Examples of monomers copolymerizable with vinyl chloride include vinyl esters such as vinyl acetate and vinyl propionate; (meth)acrylates such as methyl (meth)acrylate and ethyl (meth)acrylate; ethylene , Α-olefins such as propylene; unsaturated dicarboxylic acids such as maleic anhydride and itaconic acid; acrylonitrile, styrene, vinylidene chloride, vinyl ether, etc.
本發明之一實施形態之懸浮聚合用分散助劑於製造塑化劑吸收性優異之氯乙烯樹脂粒子之方面而言,適於軟質用氯乙烯樹脂之製造,但就脫單體性、粒度分佈等優異之方面而言,亦可應用於硬質用氯乙烯樹脂之製造。The dispersion aid for suspension polymerization according to an embodiment of the present invention is suitable for the production of vinyl chloride resins for soft plastics in terms of producing vinyl chloride resin particles with excellent plasticizer absorption, but in terms of demonomerization and particle size distribution In terms of excellence, it can also be used in the manufacture of rigid vinyl chloride resins.
本發明之一實施形態之懸浮聚合用分散助劑可單獨使用,但亦可與其他穩定劑之例如纖維素系衍生物、界面活性劑等併用。The dispersion aid for suspension polymerization according to an embodiment of the present invention can be used alone, but can also be used in combination with other stabilizers such as cellulose derivatives and surfactants.
本發明之一實施形態之懸浮聚合用分散助劑係塑化劑吸收量多,故而藉由使用該懸浮聚合用分散助劑,可始終獲得樹脂粒子為多孔性且魚眼少等物性非常優異之氯乙烯樹脂。以下,對乙烯系化合物之聚合法舉例進行具體說明,但不限定於該等。Since the dispersion aid for suspension polymerization according to one embodiment of the present invention has a large amount of plasticizer absorption, by using the dispersion aid for suspension polymerization, the resin particles are always porous and have very good physical properties such as few fish eyes. Vinyl chloride resin. Hereinafter, examples of the polymerization method of the ethylene-based compound will be specifically described, but not limited to these.
於製造氯乙烯樹脂粒子等乙烯系化合物之樹脂粒子之情形時,於一實施形態中,相對於乙烯系化合物單體100質量份,添加0.01質量份至0.3質量份、較佳為0.02質量份至0.10質量份之上述懸浮聚合用分散助劑。另外,乙烯系化合物與水之比可按質量比而設為乙烯系化合物:水=1:0.9至1:3,較佳為乙烯系化合物:水=1:1至1:1.5。In the case of producing resin particles of vinyl compounds such as vinyl chloride resin particles, in one embodiment, 0.01 to 0.3 parts by mass, preferably 0.02 parts by mass to 100 parts by mass of the vinyl compound monomer is added 0.10 parts by mass of the above-mentioned dispersion aid for suspension polymerization. In addition, the ratio of the vinyl compound to water can be set as the mass ratio of the vinyl compound: water = 1: 0.9 to 1: 3, preferably the vinyl compound: water = 1:1 to 1: 1.5.
聚合起始劑亦可為先前用於乙烯系化合物之聚合的聚合起始劑,關於該聚合起始劑,可將下述化合物單獨或組合使用:過氧化二碳酸二異丙酯、過氧化二碳酸二-2-乙基己酯、過氧化二碳酸二乙氧基乙酯等過碳酸酯化合物;過氧化新癸酸第三丁酯、過氧化新癸酸-α-異丙苯酯等過氧酸酯化合物;過氧化乙醯基環己基磺醯、2-過氧化苯氧基乙酸-2,4,4-三甲基戊酯等過氧化物;偶氮雙-2,4-二甲基戊腈、偶氮雙(4-甲氧基-2,4-二甲基戊腈)等偶氮化合物;進而過硫酸鉀、過硫酸銨、過氧化氫等。The polymerization initiator may also be a polymerization initiator previously used for the polymerization of ethylene-based compounds. With regard to the polymerization initiator, the following compounds may be used alone or in combination: diisopropyl peroxide dicarbonate, di peroxide Percarbonate compounds such as di-2-ethylhexyl carbonate, diethoxyethyl peroxydicarbonate; tertiary butyl peroxyneodecanoate, α-cumyl peroxyneodecanoate, etc. Oxygen acid ester compounds; peroxides such as ethoxycyclohexylsulfonyl peroxide, 2-peroxyphenoxyacetic acid-2,4,4-trimethylpentyl ester; azobis-2,4-dimethyl Azo compounds such as valeronitrile, azobis (4-methoxy-2,4-dimethylvaleronitrile); and further potassium persulfate, ammonium persulfate, hydrogen peroxide, etc.
進而,亦任意添加適宜用於乙烯系化合物之聚合的聚合調整劑、鏈轉移劑、膠化改良劑、抗靜電劑、pH調整劑等。Furthermore, a polymerization adjuster, a chain transfer agent, a gelation improver, an antistatic agent, a pH adjuster, etc. suitable for the polymerization of ethylene-based compounds are optionally added.
實施乙烯系化合物之聚合時的各成分之饋入比率、聚合溫度等只要依據先前用於乙烯系化合物之懸浮聚合之條件而設定即可,不存在特別限定之理由。 [實施例]The feed rate of each component, polymerization temperature, etc. at the time of carrying out the polymerization of the ethylene-based compound may be set according to the conditions previously used for the suspension polymerization of the ethylene-based compound, and there is no reason for particular limitation. [Example]
以下,列舉實施例對本發明進行更詳細說明。 另外,以下只要無特別說明,則「份」及「%」分別意指「質量份」及「質量%」。Hereinafter, the present invention will be described in more detail with examples. In addition, unless otherwise specified, "parts" and "%" mean "mass parts" and "mass %", respectively.
(實施例1) 〈懸浮聚合用分散助劑之製造〉將乙酸乙烯酯97份、水180份、分散劑之聚乙烯醇(電化(Denka)股份有限公司製造之W-20N)0.3份、鏈轉移劑之正丁醛(nBA)1.6份、丁烯酸3份及偶氮雙異丁腈0.9份饋入至聚合罐,加熱而於60℃進行聚合,聚合7小時。利用下述所示之方法來測定聚合結束時間點之聚合率。繼而藉由常法將未聚合之乙酸乙烯酯去除,將所得之乙烯酯系聚合物於40℃流動乾燥而獲得懸浮聚合用分散助劑A。該實施例中未添加添加劑,乙烯酯系聚合物自身構成懸浮聚合用分散助劑A。對於所得之懸浮聚合用分散助劑A,利用以下所示之方法來評價黏度平均聚合度、皂化度、酸值及水溶性,將評價結果示於表1。(Example 1) <Manufacture of dispersion aid for suspension polymerization> 97 parts of vinyl acetate, 180 parts of water, 0.3 parts of polyvinyl alcohol (W-20N manufactured by Denka Co., Ltd.) as dispersant, and n-butyl chain transfer agent 1.6 parts of aldehyde (nBA), 3 parts of crotonic acid and 0.9 parts of azobisisobutyronitrile were fed to a polymerization tank, heated and polymerized at 60°C, and polymerized for 7 hours. The polymerization rate at the end of polymerization was measured by the method shown below. Subsequently, the unpolymerized vinyl acetate was removed by an ordinary method, and the obtained vinyl ester polymer was flow-dried at 40° C. to obtain a dispersion aid A for suspension polymerization. In this embodiment, no additives are added, and the vinyl ester polymer itself constitutes the dispersion aid A for suspension polymerization. The obtained dispersion aid A for suspension polymerization was evaluated for the average viscosity degree of polymerization, saponification degree, acid value and water solubility by the method shown below. Table 1 shows the evaluation results.
[聚合率] 聚合率係於乙烯酯單體及乙烯酯系聚合物粒子均勻地分散於水中之狀態下少量取樣,使該所取樣之溶液於150℃乾燥30分鐘,由重量法而求出。[Polymerization rate] The polymerization rate is obtained by sampling a small amount in a state where the vinyl ester monomer and vinyl ester polymer particles are uniformly dispersed in water, and the sampled solution is dried at 150°C for 30 minutes and determined by gravimetry.
[黏度平均聚合度] 依據JIS K6725:1977,由對所得之懸浮聚合用分散助劑A於30℃之丙酮中測定之極限黏度[η]而求出。[Average viscosity polymerization degree] According to JIS K6725:1977, it was determined from the limiting viscosity [η] of the obtained dispersion aid A for suspension polymerization measured in acetone at 30°C.
[皂化度] 依據JIS K6726:1994,求出所得之懸浮聚合用分散助劑A之皂化度。[Saponification degree] According to JIS K6726:1994, the degree of saponification of the obtained dispersion aid A for suspension polymerization was determined.
[酸值] 依據JIS K0070:1992,由所得之懸浮聚合用分散助劑A之中和所需要的氫氧化鉀之量而求出。[Acid Value] According to JIS K0070:1992, it was determined from the amount of potassium hydroxide required to neutralize the obtained dispersion aid A for suspension polymerization.
[水溶性] 對水90份添加懸浮聚合用分散助劑A 10份後,以使pH值成為7.5至8.5之方式添加碳酸鈉並於室溫攪拌4小時後,停止攪拌,藉由目視而確認有無沈澱,依照以下之基準進行評價。 ○:成為均勻之溶液或分散液,未產生沈澱。 ×:產生沈澱。[Water Soluble] After adding 10 parts of dispersing aid A for suspension polymerization to 90 parts of water, sodium carbonate was added in such a way that the pH became 7.5 to 8.5 and after stirring at room temperature for 4 hours, the stirring was stopped, and the presence or absence of precipitation was visually confirmed according to Evaluation is based on the following criteria. ○: It became a uniform solution or dispersion, and no precipitation occurred. ×: Precipitation occurred.
〈氯乙烯之懸浮聚合〉於具備攪拌器之容量30L之不銹鋼製高壓釜中,於攪拌下饋入30℃之水14kg、作為主分散劑之皂化度為80莫耳%之聚乙烯醇(電化(Denka)股份有限公司製造之W-20N)12g、上述所得之懸浮聚合用分散助劑A 2g、作為聚合起始劑之過氧化新癸酸第三丁酯4.6g、及過氧化新癸酸-α-異丙苯酯1g。將高壓釜於真空進行脫氣後,添加氯乙烯單體10kg,於57℃聚合4小時。<Suspension polymerization of vinyl chloride> In a 30-liter stainless steel autoclave equipped with a stirrer, feed 14 kg of water at 30° C. under stirring, as the main dispersant, a polyvinyl alcohol with a saponification degree of 80 mole% (electrochemical (W-20N manufactured by Denka) Co., Ltd. 12g, 2g of the dispersion aid A for suspension polymerization obtained above, 4.6g of tertiary butyl neodecanoate as a polymerization initiator, and neodecanoic acid peroxide -α-Cumene ester 1g. After degassing the autoclave under vacuum, 10 kg of vinyl chloride monomer was added, and polymerized at 57°C for 4 hours.
〈氯乙烯樹脂之評價〉對於所得之氯乙烯樹脂,利用以下所示之方法來評價平均粒徑、粒度分佈、塑化劑吸收量及容積比重,將評價結果示於表1。<Evaluation of Vinyl Chloride Resin> The obtained vinyl chloride resin was evaluated for the average particle diameter, particle size distribution, plasticizer absorption and volume specific gravity by the method shown below. Table 1 shows the evaluation results.
[平均粒徑、粒度分佈] 依據JIS Z8815:1994,使用60網目(孔徑250μm)、80網目(孔徑180μm)、100網目(孔徑150μm)、150網目(孔徑106μm)、200網目(孔徑75μm)之篩將所得之氯乙烯樹脂分粒,將累積頻率50%之粒徑(D50)設為平均粒徑,將累積頻率80%之粒徑(D80)與累積頻率20%之粒徑(D20)之差設為粒度分佈。[Average particle size, particle size distribution] According to JIS Z8815:1994, the resulting vinyl chloride resin was separated using a sieve of 60 mesh (aperture 250 μm), 80 mesh (aperture 180 μm), 100 mesh (aperture 150 μm), 150 mesh (aperture 106 μm), 200 mesh (aperture 75 μm) For the granules, the particle diameter (D50) with a cumulative frequency of 50% is defined as the average particle diameter, and the difference between the particle diameter (D80) with a cumulative frequency of 80% and the particle diameter (D20) with a cumulative frequency of 20% is defined as the particle size distribution.
[塑化劑吸收量] 依據ISO(International Organization for Standardization;國際標準組織)4608:1998(E)進行測定。[Plasticizer absorption] The measurement was performed according to ISO (International Organization for Standardization) 4608:1998(E).
[容積比重] 依據JIS K6720-2:1999進行測定。[Volume specific gravity] Measured according to JIS K6720-2:1999.
[表1]
(實施例2至實施例3) 除了將正丁醛添加量及丁烯酸添加量變更為表1所記載之條件以外,以與實施例1相同之方式獲得懸浮聚合用分散助劑B及懸浮聚合用分散助劑C。繼而,除了使用所得之懸浮聚合用分散助劑B及懸浮聚合用分散助劑C以外,以與實施例1相同之條件實施氯乙烯之懸浮聚合。將懸浮聚合用分散助劑B及懸浮聚合用分散助劑C、以及使用該懸浮聚合用分散助劑B及懸浮聚合用分散助劑C所得之氯乙烯樹脂之評價結果示於表1。(Example 2 to Example 3) A dispersion aid for suspension polymerization B and a dispersion aid for suspension polymerization C were obtained in the same manner as in Example 1, except that the addition amount of n-butyraldehyde and the addition amount of crotonic acid were changed to the conditions described in Table 1. Next, the suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1, except that the obtained dispersion aid B for suspension polymerization and dispersion aid C for suspension polymerization were used. Table 1 shows the evaluation results of the vinyl chloride resin obtained by using the dispersion aid B for suspension polymerization, the dispersion aid C for suspension polymerization, and the dispersion aid B for suspension polymerization and the dispersion aid C for suspension polymerization.
(實施例4) 將乙酸乙烯酯97份、水180份、分散劑之聚乙烯醇(電化(Denka)股份有限公司製造之W-20N)0.3份、鏈轉移劑之正丁醛(nBA)1.4份及偶氮雙異丁腈0.9份饋入至聚合罐,加熱而達到60℃後,一邊以總添加量成為1.0份之方式連續6小時添加衣康酸一邊進行聚合,進而聚合1小時。將聚合結束時間點之聚合率示於表1。繼而藉由常法將未聚合之乙酸乙烯酯去除,將所得之乙烯酯系聚合物於40℃流動乾燥而獲得懸浮聚合用分散助劑D。該實施例中未添加添加劑,乙烯酯系聚合物自身構成懸浮聚合用分散助劑D。對於所得之懸浮聚合用分散助劑D,利用與實施例1相同之方法來評價黏度平均聚合度、皂化度、酸值及水溶性,將評價結果示於表1。(Example 4) 97 parts of vinyl acetate, 180 parts of water, 0.3 parts of polyvinyl alcohol (W-20N manufactured by Denka Co., Ltd.) as dispersant, 1.4 parts of n-butyraldehyde (nBA) of chain transfer agent and azobis 0.9 parts of isobutyronitrile was fed to a polymerization tank, and after heating to 60°C, polymerization was carried out while itaconic acid was continuously added for 6 hours so that the total addition amount became 1.0 part, and polymerization was further carried out for 1 hour. Table 1 shows the polymerization rate at the end of polymerization. Subsequently, the unpolymerized vinyl acetate was removed by a conventional method, and the obtained vinyl ester polymer was flow-dried at 40° C. to obtain a dispersion aid D for suspension polymerization. In this embodiment, no additives are added, and the vinyl ester polymer itself constitutes the dispersion aid D for suspension polymerization. For the obtained dispersion aid D for suspension polymerization, the average viscosity degree of polymerization, the degree of saponification, the acid value, and the water solubility were evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.
(比較例1) 除了不使用懸浮聚合用分散助劑以外,以與實施例1相同之條件實施氯乙烯之懸浮聚合。將氯乙烯樹脂之評價結果示於表1。(Comparative example 1) The suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1, except that the dispersion aid for suspension polymerization was not used. Table 1 shows the evaluation results of vinyl chloride resin.
(比較例2) 除了將丁烯酸添加量變更為表1所記載之條件以外,以與實施例1相同之方式獲得懸浮聚合用分散助劑E。所得之懸浮聚合用分散助劑E不顯示水溶性。繼而,除了使用所得之懸浮聚合用分散助劑E以外,以與實施例1相同之條件實施氯乙烯之懸浮聚合。將懸浮聚合用分散助劑E及使用該懸浮聚合用分散助劑E所得之氯乙烯樹脂之評價結果示於表1。(Comparative example 2) A dispersion aid E for suspension polymerization was obtained in the same manner as in Example 1, except that the addition amount of crotonic acid was changed to the conditions described in Table 1. The resulting dispersion aid E for suspension polymerization did not show water solubility. Next, the suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1, except that the obtained dispersion aid E for suspension polymerization was used. Table 1 shows the evaluation results of the dispersion aid E for suspension polymerization and the vinyl chloride resin obtained by using the dispersion aid E for suspension polymerization.
(比較例3) 除了將正丁醛添加量及丁烯酸添加量變更為表1所記載之條件以外,以與實施例1相同之方式獲得懸浮聚合用分散助劑F。所得之懸浮聚合用分散助劑F顯示水溶性。繼而,除了使用所得之懸浮聚合用分散助劑F以外,以與實施例1相同之條件實施氯乙烯之懸浮聚合,但氯乙烯於高壓釜中結塊,無法獲得氯乙烯粒子。將懸浮聚合用分散助劑F之評價結果示於表1。(Comparative example 3) A dispersion aid F for suspension polymerization was obtained in the same manner as in Example 1, except that the addition amount of n-butyraldehyde and the addition amount of crotonic acid were changed to the conditions described in Table 1. The resulting dispersion aid F for suspension polymerization showed water solubility. Next, the suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1 except that the obtained dispersion aid F for suspension polymerization was used, but vinyl chloride was agglomerated in an autoclave, and vinyl chloride particles could not be obtained. Table 1 shows the evaluation results of the dispersion aid F for suspension polymerization.
(比較例4) 將乙酸乙烯酯100份、甲醇150份(溶劑兼鏈轉移劑)及偶氮雙異丁腈(以1%甲醇溶液之形式)0.03份饋入至聚合罐,於氮氣氛圍下於60℃進行8小時聚合。將聚合結束時間點之聚合率示於表1。繼而藉由常法將未聚合之乙酸乙烯酯去除,藉由乾燥將乙烯酯系聚合物之溶劑去除而獲得懸浮聚合用分散助劑G。該比較例中未添加添加劑,乙烯酯系聚合物自身構成懸浮聚合用分散助劑G。所得之懸浮聚合用分散助劑G不顯示水溶性。繼而,除了使用所得之懸浮聚合用分散助劑G以外,以與實施例1相同之條件實施氯乙烯之懸浮聚合。將懸浮聚合用分散助劑G及使用該懸浮聚合用分散助劑G所得之氯乙烯樹脂之評價結果示於表1。(Comparative example 4) 100 parts of vinyl acetate, 150 parts of methanol (solvent and chain transfer agent) and 0.03 parts of azobisisobutyronitrile (in the form of a 1% methanol solution) were fed to the polymerization tank, which was carried out at 60°C under a nitrogen atmosphere 8 Hourly polymerization. Table 1 shows the polymerization rate at the end of polymerization. Then, the unpolymerized vinyl acetate was removed by a conventional method, and the solvent of the vinyl ester polymer was removed by drying to obtain a dispersion aid G for suspension polymerization. In this comparative example, no additives are added, and the vinyl ester polymer itself constitutes the dispersion aid G for suspension polymerization. The resulting dispersion aid G for suspension polymerization does not show water solubility. Next, the suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1, except that the obtained dispersion aid G for suspension polymerization was used. Table 1 shows the evaluation results of the dispersion aid G for suspension polymerization and the vinyl chloride resin obtained by using the dispersion aid G for suspension polymerization.
(比較例5) 將乙酸乙烯酯100份、甲醇22.5份(溶劑兼鏈轉移劑)、鏈轉移劑之3-MPA(3-巰基丙酸)0.23份及偶氮雙異丁腈(以1%甲醇溶液之形式)0.03份饋入至聚合罐並置換為氮氣氛圍。加熱而自達到60℃之時間點起,一邊以6小時全部加入完畢之方式固定地連續添加10%之巰基丙酸甲醇溶液1.81份,一邊進行6小時聚合。將聚合結束時間點之聚合率示於表1。繼而藉由常法將未聚合之乙酸乙烯酯去除,藉由乾燥將乙烯酯系聚合物之溶劑去除而獲得改性乙烯酯系聚合物。將所得之改性乙烯酯系聚合物溶解於甲醇,獲得甲醇中之聚合物之濃度為35%之甲醇溶液。利用氫氧化鈉於35℃將該改性乙烯酯系聚合物皂化90分鐘。氫氧化鈉之使用量係相對於所得之改性乙烯酯系聚合物之乙酸乙烯酯單元1莫耳而設為7毫莫耳當量。藉由過濾、乾燥而獲得懸浮聚合用分散助劑H。該比較例中未添加添加劑,乙烯酯系聚合物自身構成懸浮聚合用分散助劑H。所得之懸浮聚合用分散助劑H係依據JIS K6726:1994所測定之皂化度為43莫耳%。除了使用所得之懸浮聚合用分散助劑H以外,以與實施例1相同之條件實施氯乙烯之懸浮聚合。將懸浮聚合用分散助劑H及使用該懸浮聚合用分散助劑H所得之氯乙烯樹脂之評價結果示於表1。(Comparative example 5) Mix 100 parts of vinyl acetate, 22.5 parts of methanol (solvent and chain transfer agent), 0.23 parts of 3-MPA (3-mercaptopropionic acid) of the chain transfer agent and azobisisobutyronitrile (in the form of 1% methanol solution) 0.03 parts were fed to the polymerization tank and replaced with nitrogen atmosphere. From the time of heating to 60° C., while continuously adding 1.81 parts of a 10% mercaptopropionic acid methanol solution so as to complete the addition in 6 hours, polymerization was carried out for 6 hours. Table 1 shows the polymerization rate at the end of polymerization. Subsequently, the unpolymerized vinyl acetate was removed by a conventional method, and the solvent of the vinyl ester polymer was removed by drying to obtain a modified vinyl ester polymer. The obtained modified vinyl ester polymer was dissolved in methanol to obtain a methanol solution with a concentration of 35% of the polymer in methanol. This modified vinyl ester polymer was saponified with sodium hydroxide at 35°C for 90 minutes. The amount of sodium hydroxide used was 7 millimolar equivalents relative to 1 mole of vinyl acetate units of the resulting modified vinyl ester polymer. The dispersion aid H for suspension polymerization is obtained by filtration and drying. In this comparative example, no additives are added, and the vinyl ester polymer itself constitutes the dispersion aid H for suspension polymerization. The resulting dispersion aid H for suspension polymerization was 43 mol% measured according to JIS K6726:1994. The suspension polymerization of vinyl chloride was carried out under the same conditions as in Example 1, except that the obtained dispersion aid H for suspension polymerization was used. Table 1 shows the evaluation results of the dispersion aid H for suspension polymerization and the vinyl chloride resin obtained by using the dispersion aid H for suspension polymerization.
由表1所示之結果得知,本發明之懸浮聚合用分散助劑為水溶性故而操作性優異,使用該懸浮聚合用分散助劑進行懸浮聚合所得之乙烯系樹脂係塑化劑吸收性高,且粗大粒子之形成少。再者,比較例5中儘管酸值低但為水溶性之原因在於:進行皂化而導入有羥基。From the results shown in Table 1, it is known that the dispersion aid for suspension polymerization of the present invention is water-soluble and therefore has excellent operability, and the ethylene-based resin plasticizer obtained by suspension polymerization using the dispersion aid for suspension polymerization has high absorbency And less formation of coarse particles. In addition, the reason why Comparative Example 5 is water-soluble despite the low acid value is that saponification is carried out and hydroxyl groups are introduced.
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