.201036994 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種使用具優越生產性的附回流冷凝器 聚合槽之藉由乙烯系化合物之懸浮聚合所得到的乙烯系樹 脂之製法。更詳言之’所得之氯乙烯系聚合物粒子爲均一 的，對於在聚合槽內之聚合中期〜後期所發生的乾泡具優 越消泡性的乙烯系樹脂之製法。 【先前技術】 最近’於聚氯乙烯等之乙烯系樹脂的生產中，正尋求 爲了使生產性提高而縮短聚合1批次所需要的時間，有人 提案爲了使聚合反應熱之去除速度增加而使用附回流冷凝 器聚合槽之方法，或是爲了縮短升溫時間而進料已預先加 熱的水性介質之方法（熱加料法）。然而，使用附回流冷凝 器聚合槽之情形下，由於隨著乙烯系化合物（單體）之氣體 將冷凝，回流冷凝器附近之壓力將降低，具有使濕泡或乾 泡變得激烈之問題點。所謂濕泡係指主要以起因於聚乙烯 醇之水爲主成分的發泡。另一方面，所謂乾泡係指以聚氯 乙烯（PVC)或氯乙烯單體（V CM)爲主成分的發泡，主要於聚 合之中期〜後期發生。所發生的乾泡係被覆進料混合物之 液層部表面而懸浮。由於此泡即使藉由攪拌也不易消失， 維持氣泡狀下而提供聚合。因此，具有：（1)積垢將附著於 氣泡所附著的氣相部與液相部之界面部分，·導致生產性之 降低’（2)藉由積垢附著而變得無法進行聚合槽之溫控，（3) 氣泡狀之聚合物將發生而導致產率之降低，（4)魚眼（小洞） .201036994 將生成而導致產品品質之降低，（5)藉由源自氣泡狀聚合物 之異型粒子的混入而無法得到均一之粒子等之問題；此等 之問題係具有隨著回流冷凝器之大型化而增大的傾向。還 有，不使用回流冷凝器之情形下，雖然乾泡不會發生，但 是具有聚合時間將變長、生產性爲低的問題。 此等之對策，於專利文獻1(日本專利特開平2- 1 80908 號公報）中揭示：於回流冷凝器中之聚合反應熱的去除量爲 全部聚合反應熱量之10%以下的時點，添加二甲基聚矽氧 烷等之矽氧烷或低皂化度聚乙烯醇等之方法。 於專利文獻2(日本專利特開平3-212409號公報）中揭 示：於回流冷凝器中之聚合反應熱的去除量不超過全部聚 合反應熱量之10%的時點，相對於氯乙烯單體100重量份 而言，添加巷化度2〇〜50莫耳％、聚合度200〜400之水 不溶性部分皂化聚乙烯醇0.002〜0.007重量份及二甲基聚 矽氧烷等之消泡劑0.00 1〜0.01重量份之方法。 於專利文獻3 (日本專利特開昭5 5 - 1 3 7 1 0 5號公報）中揭 示：於聚合開始前，添加皂化度60〜80%之離子改性聚乙 烯醇。 於專利文獻4 (日本專利特開平7 - 1 7 9 5 0 7號公報）中揭 示：於聚合轉化率5〜50%之時點，添加皂化度70〜85莫 耳％及聚合度700〜3 000之水溶性聚乙烯醇，且於58〜 7〇°C之溫度範圍進行聚合之方法。 另外，於專利文獻5(日本專利特開平7- 5 3 607號公報） 中揭示：於聚合轉化率5〜5 0 %之時點，連續地或逐次地 201036994 添加皂化度70〜85莫耳％及聚合度700〜3000之水溶性聚 乙烯醇之方法。 於專利文獻6(日本專利特開平7- 1 8007號公報）中揭 示：於聚合轉化率30〜60%之時點，添加皂化度75〜85 莫耳％及聚合度1500〜2700之水溶性聚乙烯醇之方法。 於專利文獻7(日本專利特開平8-73512號公報）中揭 示：於聚合轉化率20〜60%之期間，添加皂化度20〜55 莫耳％、平均聚合度150〜600之部分皂化聚乙烯醇之方 G法。 於專利文獻8(日本專利特開平1 0- 1 503號公報）中揭 示：於聚合轉化率30〜90%之時點，添加皂化度85莫耳 %以下之乙烯醇系聚合物之方法。 於專利文獻9 (日本專利特開平1 1 - 1 1 6 6 3 0號公報）中揭 示：於聚合轉化率30〜90%之時點，連續地或分成2次以 上添加皂化度85莫耳％以下之乙烯醇系聚合物之方法。 於專利文獻1〇(日本專利特開2001-122910號公報）中 〇 - 揭示：於聚合轉化率3 0 %以上之時點，添加皂化度6 5莫 耳％以上、聚合度700以上、且符合0.0300<(3-Υ)/Χ20·03 3 0 之聚乙烯系樹脂之方法（X:皂化度、Υ:碘呈色度）。 於專利文獻11(日本專利特開200 1 -23 3 904號公報）中 揭示：從聚合轉化率3 %以下之時點起，添加於介電常數 32c.g.s.e.s.u.以下之溶劑存在下，皂化醋酸乙烯酯系聚合 物所得到、皂化度70莫耳％以下、且符合η-0·00005Υ2 + 0.0085YS0.80、在側鏈及/或末端具有離子性基、更含有 201036994 氧伸烷基之聚乙烯酯系聚合物之方法（Y:皂化度、η:塊字 元（block chacter)) ° 於專利文獻12(日本專利特昭59-15 5 40 8號公報）中揭 示：以皂化含有氧伸烷基之不飽和單體與醋酸乙烯酯的共 聚物爲特徵之改性PVA之製法。用於該改性PVA製造之不 飽和單體中之氧伸烷基，可列舉：重複單位數約1〜50之 聚伸氧乙基、聚伸氧丙基、聚伸氧丁基等。 然而，揭示於專利文獻1、2之方法中，具有乾泡發生 ^ 變得激烈、氯乙烯系樹脂之體比重容易降低的問題。另外， 揭示於專利文獻3、4、5、6、7之方法中，由於未使用回 流冷凝器，具有聚合時間變長、生產性低的問題。再者， 揭示於專利文獻8、9、10、11之方法中，雖然爲已使用附 回流冷凝器之聚合槽、生產性高的方法，關於抑制乾泡之 消泡性，不僅尙未達到滿足，仍殘留積垢將附著等之問題， 期望進一步之改良。於專利文獻12中，雖然已揭示含有氧 伸烷基之改性PVA之製法，但是完全未有針對乾泡抑制之 〇 記載或暗示。 專利文獻1 :日本專利特開平2- 1 80908號公報 專利文獻2 :日本專利特開平3 -2 1 2409號公報 專利文獻3 :日本專利特開昭5 5 - 1 3 7 1 0 5號公報 專利文獻4:日本專利特開平7-179507號公報 專利文獻5 :日本專利特開平7 - 5 3 6 07號公報 專利文獻6 :日本專利特開平7- 1 8007號公報 專利文獻7 :日本專利特開平8 -73 5 1 2號公報 201036994 獻.獻 文文 利利 專專 平平 開開 特特 利利 專專 本本 曰曰 幸 報公 公號 號 ο 5 3 專利文獻ι〇:日本專利特開200 1 _ 1229 1 0號公報 專利文獻11 :日本專利特開200 1 _23 3 904號公報 專利文獻12 :日本專利特開昭5 9- 1 5 5408號公報 【發明內容】 發明所欲解決之技術問題 本發明之目的在於提供一種乙烯系樹脂之製法，於使 用附回流冷凝器聚合槽之乙烯系化合物的懸浮聚合之際， 所得到的乙烯系聚合物粒子係均一，對聚合之中期〜後期 所發生的乾泡具優越消泡性的乙烯系樹脂之製法。 解決問題之技術手段 本發明人等爲了解決上述課題，不斷鑽硏之結果發 現：使用附回流冷凝器之聚合槽，於懸浮聚合用分散安定 劑之存在下，進行乙烯系化合物的懸浮聚合之際，於聚合 轉化率1 〇 %以上之時點，相對於該乙烯系化合物1 0 0重量 份而言’在側鏈上含有下列通式（I)所示之聚氧伸烷基之乙 烯醇系聚合物；藉由添加0.001〜5重量份之聚氧伸烷基改 性量爲0.0 1〜1 〇莫耳％之聚伸氧烷改性乙烯醇系聚合物（A) 而解決上述課題，於是完成本發明。 (I) 201036994 c2h5 mBACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing an ethylene-based resin obtained by suspension polymerization of a vinyl compound using a reflux condenser polymerization vessel having superior productivity. More specifically, the obtained vinyl chloride polymer particles are uniform, and are excellent in defoaming properties of the dry foam which occurs in the middle to the middle of the polymerization in the polymerization tank. [Prior Art] Recently, in the production of a vinyl-based resin such as polyvinyl chloride, it has been proposed to shorten the time required for the polymerization of one batch in order to improve the productivity, and it has been proposed to increase the removal rate of the polymerization heat. A method of refluxing a condenser polymerization tank, or a method of feeding a preheated aqueous medium in order to shorten the heating time (hot charging method). However, in the case of using a reflux condenser polymerization tank, since the gas of the ethylene compound (monomer) will condense, the pressure in the vicinity of the reflux condenser will decrease, and there is a problem that the wet foam or the dry bulb becomes intense. . The term "wet foam" refers to foaming mainly composed of water derived from polyvinyl alcohol. On the other hand, the term "dry foam" refers to foaming mainly composed of polyvinyl chloride (PVC) or vinyl chloride monomer (V CM), which occurs mainly in the middle to late stages of polymerization. The resulting dry foam is suspended by coating the surface of the liquid layer portion of the feed mixture. Since this bubble does not easily disappear even by stirring, the polymerization is maintained while maintaining the bubble shape. Therefore, (1) the scale adheres to the interface portion between the gas phase portion and the liquid phase portion to which the gas bubbles adhere, and causes a decrease in productivity. (2) The polymerization tank cannot be formed by the adhesion of the scale. Temperature control, (3) bubble-like polymer will occur and lead to lower yield, (4) fisheye (small hole) .201036994 will be produced resulting in a decrease in product quality, (5) by bubble-like polymerization The problem of uniform particles or the like is not obtained by the incorporation of the heterogeneous particles of the object; such problems tend to increase as the size of the reflux condenser increases. Further, in the case where a reflux condenser is not used, although dry bubbles do not occur, there is a problem that the polymerization time becomes long and the productivity is low. In the above-mentioned Japanese Patent Application Laid-Open No. Hei No. Hei-2-18090, it is disclosed that when the amount of removal of the polymerization heat in the reflux condenser is 10% or less of the total heat of the polymerization reaction, A method such as a decane or a low saponification polyvinyl alcohol such as methyl polyoxyalkylene. It is disclosed in the patent document 2 (Japanese Patent Laid-Open No. Hei 3-212409) that the removal amount of the polymerization heat in the reflux condenser does not exceed 10% of the total heat of the polymerization reaction, and the weight of the monomer relative to the vinyl chloride monomer is 100%. For the portion, a water-insoluble partial saponified polyvinyl alcohol having a degree of addition of 2 〇 to 50 mol%, a degree of polymerization of 200 to 400, 0.002 to 0.007 parts by weight, and a defoaming agent such as dimethyl polyoxyalkylene are added. 0.01 parts by weight of the method. It is disclosed in Patent Document 3 (Japanese Laid-Open Patent Publication No. SHO-55-1763) that ion-modified polyvinyl alcohol having a degree of saponification of 60 to 80% is added before the start of polymerization. It is disclosed in the patent document 4 (Japanese Patent Laid-Open Publication No. Hei 7-7779) that the degree of saponification is 70 to 85 mol% and the degree of polymerization is 700 to 3 000 at a polymerization conversion ratio of 5 to 50%. The water-soluble polyvinyl alcohol is polymerized at a temperature ranging from 58 to 7 ° C. In addition, in the case of the polymerization conversion ratio of 5 to 50%, the degree of saponification is 70 to 85 mol% and is continuously or sequentially 201036994, as disclosed in Japanese Laid-Open Patent Publication No. Hei 7-53-607. A method of water-soluble polyvinyl alcohol having a polymerization degree of 700 to 3,000. In the case of the polymerization conversion ratio of 30 to 60%, a water-soluble polyethylene having a degree of saponification of 75 to 85 mol% and a polymerization degree of 1500 to 2700 is disclosed in Patent Document 6 (Japanese Patent Laid-Open Publication No. Hei 7-108007). The method of alcohol. It is disclosed in the patent document 7 (Japanese Patent Laid-Open No. Hei 8-73512) that a partially saponified polyethylene having a degree of saponification of 20 to 55 mol% and an average degree of polymerization of 150 to 600 is added during a polymerization conversion ratio of 20 to 60%. Alcohol method G method. A method of adding a vinyl alcohol-based polymer having a degree of saponification of 85 mol% or less at a polymerization conversion ratio of 30 to 90% is disclosed in Patent Document 8 (Japanese Laid-Open Patent Publication No. Hei No. Hei. In the case of the polymerization conversion ratio of 30 to 90%, the degree of saponification is 85 or less and the saponification degree is 85 or less at a time of 30 to 90%. A method of a vinyl alcohol polymer. In the patent document 1 (Japanese Patent Laid-Open Publication No. 2001-122910), it is disclosed that when the polymerization conversion ratio is 30% or more, the degree of saponification is 65 mol% or more, the degree of polymerization is 700 or more, and 0.0300 is satisfied. <(3-Υ)/Χ20·03 3 0 method of polyethylene resin (X: degree of saponification, enthalpy: iodine is chromaticity). It is disclosed in Patent Document 11 (JP-A No. 200 1-23 3 904) that saponified vinyl acetate is added in the presence of a solvent having a dielectric constant of 32 c.gsesu or less at a polymerization conversion ratio of 3% or less. A polyvinyl ester obtained by a polymer having a degree of saponification of 70 mol% or less and conforming to η-0·00005Υ2 + 0.0085YS0.80, having an ionic group at a side chain and/or a terminal, and further containing an alkyl group of 201036994 The method of polymerizing (Y: degree of saponification, η: block chacter) is disclosed in Patent Document 12 (Japanese Patent Publication No. 59-15 5 40 8): saponification containing an oxygen-containing alkyl group A process for modifying a PVA characterized by a copolymer of an unsaturated monomer and vinyl acetate. The oxygen-extension alkyl group used in the unsaturated monomer produced by the modified PVA may, for example, be a polyoxyalkylene group, a polyextended oxypropyl group or a polyextended oxybutyl group having a repeating unit number of about 1 to 50. However, in the methods disclosed in Patent Documents 1 and 2, there is a problem that the occurrence of dry foam becomes intense and the specific gravity of the vinyl chloride resin is likely to decrease. Further, in the methods disclosed in Patent Documents 3, 4, 5, 6, and 7, since the reflux condenser is not used, there is a problem that the polymerization time becomes long and the productivity is low. Further, in the methods disclosed in Patent Documents 8, 9, 10, and 11, the polymerization tank with a reflux condenser has been used, and the productivity is high, and the suppression of the defoaming property of the dry bulb is not satisfied. There is still a problem that the scale remains attached, and further improvement is desired. In Patent Document 12, although a process for producing a modified PVA containing an oxygen-extended alkyl group has been disclosed, there has been no description or suggestion against dry-bubble suppression. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open No. Hei 7-179507 Patent Document 5: Japanese Patent Laid-Open Publication No. Hei No. Hei. 8 -73 5 1 2 Bulletin 201036994 Offer. Dedicated Wenli Lily Specialized Open Tetrali Specialized Book Ben Hao Xinggong Gong Gong No. ο 5 3 Patent Literature ι〇: Japanese Patent Special Open 200 1 _ Japanese Patent Laid-Open Publication No. JP-A No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. It is an object of the invention to provide a method for producing a vinyl resin, which is obtained by suspension polymerization of a vinyl compound having a reflux condenser polymerization tank, and the obtained ethylene polymer particles are uniform, and the polymerization occurs in the middle to late stages of polymerization. Superior bubble Method ethylene-based resin foam properties. In order to solve the above problems, the present inventors have found that the suspension polymerization of a vinyl compound is carried out in the presence of a dispersion stabilizer for suspension polymerization using a polymerization tank equipped with a reflux condenser. When the polymerization conversion ratio is 1% by weight or more, the vinyl alcohol-based polymerization of the polyoxyalkylene group represented by the following formula (I) is contained in the side chain with respect to 100 parts by weight of the ethylene compound. The above problem is solved by adding 0.001 to 5 parts by weight of a polyoxyalkylene-modified vinyl alcohol-based polymer (A) having a polyoxyalkylene group-modified amount of 0.01 to 1 mol% of a polyoxyalkylene group, thereby completing this invention. (I) 201036994 c2h5 m
R1R1
I c一ό—o h2 h 式中’ R1係表示氫原子或甲基，R2係表示氫原子或 碳數1〜8之烷基；！!1與η係表示各個的伸氧烷單位之重複 單位數，Bm^lO、3^η<20。於此，設定將以重複單位數m 所示之單位稱爲單位1、以重複單位數η所示之單位稱爲 單位2°單位1與單位2之配置也可以成爲無規狀、嵌段 狀中任一形態。 【實施方式】 發明之效果 若根據本發明之乙烯系樹脂之製法，對聚合之中期〜 後期所發生的乾泡具優越之消泡性，能夠提高乙烯系樹脂 之生產性。另外’由於可以得到具有均一粒徑之乙烯系聚 合物粒子，提供烏品質之乙烧系樹脂。 發明之實施形態 以下’詳細說明本發明。於本發明中，回流冷凝器係 爲了有效去除藉由乙烯系化合物之懸浮聚合所產生的聚合 反應熱所使用。從聚合槽中之懸浮液所發生的未反應之乙 烯系化合物（單體）的氣體係藉由回流冷凝器，予以液化而 流回聚合槽中，使聚合熱去除。回流冷凝器之冷卻水的溫 度通常約爲1〇〜50 °c。通常，除了藉由回流冷凝器所進行 的除熱之外，聚合槽之溫控係倂用藉由聚合槽之夾套或線 圈所進行的溫控。針對回流冷凝器中之聚合反應熱的去除 量，雖然並無特別之限制，較佳爲全部聚合反應熱量之10 201036994 〜8 0 %、更佳爲2 0〜6 0 %。 乙烯系化合物之懸浮聚合係於懸浮聚合用分散安定 之存在下所進行。雖然作爲懸浮聚合用分散安定劑並無 別之限制’例如’可列舉：甲基溶纖素、羥丙基溶纖素 羥丙基甲基溶纖素、羧基甲基溶纖素等之溶纖素衍生物 明膠、聚乙烯醇或聚乙烯吡咯烷酮等之水溶性高分子等 其中，適合使用皂化度60〜95莫耳％、較佳爲68〜93 耳％，聚合度200〜3500、較佳爲500〜2500之聚乙烯围 〇 於本發明中，相對於乙烯系化合物100重量份而言 懸浮聚合用分散安定劑之用量較佳爲0.0 1〜5重量份、 佳爲0.02〜2重量份、進一步更佳爲0.02〜1重量份。低 0.01重量份之情形下，於懸浮聚合乙烯系化合物之際， 有聚合安定性將降低之情形；超過5重量份之情形下， 有懸浮聚合後之廢液將白濁、化學需氧量（C Ο D)將變高之 形。 於本發明中，使用附回流冷凝器之聚合槽，於懸浮 〇 入 η用分散安定劑之存在下而懸浮聚合乙烯系化合物之際 於聚合轉化率1 〇 %以上之時點，添加聚氧伸烷基改性乙 醇系聚合物（Α)(以下，將聚氧伸烷基改性乙烯醇系聚合 也簡稱爲ΡΟΑ改性PVA)’其係在側鏈上含有上述通式 所示之聚氧伸烷基的乙烯醇系聚合物（以下，將乙烯醇系 合物也簡稱爲PVA)’且聚氧伸烷基改性量爲〇〇1〜1〇 耳％。 ΡΟΑ改性PVA(A)係聚氧伸烷基（ρ〇Α)基改性量必須 劑 特 莫 更 於 具 具 情 聚 ， 烯 物 (I) 聚 莫 爲 -10- 201036994 0.01〜10莫耳％。若POA基改性量超過10莫耳％時，具 有POA改性PVA(A)每一分子中所含之疏水基的比例將變 高、該PVA之水溶性將降低之情形。另一方面，POA基改 性量低於0.01莫耳％之情形，雖然P0A改性PVA(A)之水 溶性係優異的，具有該PVA中所含之P0A基的數目爲少 的、基於POA改性之物性並未發現之情形。 所謂POA基改性量係以POA基對PVA主鏈亞甲基的 莫耳分率所示。例如，P〇A改性PVA(A)之POA基改性量 ^ 能夠由爲該PVA前驅物之POA改性聚乙烯酯，具體之一例 係POA改性聚醋酸乙烯酯（POA改性PVAc)之質子NMR而 求出。具體而言，利用正己烷/丙酮而3次以上充分地進行 POA改性PVAc之再沉澱精製之後，於50°C之減壓下進行 2天的乾燥，作成分析用之POA改性PVAc。使該PVAc溶 解於 CDC13 中，使用 5 00MHz 之質子 NMR(JEOL GX-5 00) 而於室溫下測定。由源自乙烯酯之主鏈亞甲基的波峰α(4.7 〜5.2ppm)與源自POA基之伸氧丁基單位（單位2)之末端甲 〇 W 基的波峰β(0·8〜1.0 ppm)，利用下式而算出POA基改性量： POA基改性量（莫耳％ ) = {(β之質子數/3η)/(α之質子 數+ (β之質子數/3η))} X 1〇〇。 η係伸氧烷單位（單位2)之數目。 ΡΟΑ改性 PVA(A)之黏度平均聚合度（Ρ)係遵照 JIS-K6726所測出。亦即，進行該PVA之再皂化、精製之 後’由30°C之水中所測出的極限黏度〔η〕，藉由下式所 求出： -11- 201036994 P = (〔 η〕χ 1 03/8·2 9)(1/0.62)。 ΡΟΑ改性PVA(A)之聚合度較佳爲200以上、更佳爲 200〜3000、進一步更佳爲300〜2500。若聚合度低於200 時，具有乾泡之抑制效果將不足，相反地濕泡變得激烈之 情形；若超過3000時，具有所得之乙烯系樹脂的可塑劑吸 收性將降低之情形。 於本發明中，P0A改性PVA(A)可以單獨使用，或是也 可以混合特性不同的2種以上而使用。 ^ POA改性PVA(A)之皂化度較佳爲50〜99莫耳％、更 佳爲60〜98莫耳％、進一步更佳爲65〜95莫耳％。若皂 化度低於5 0莫耳％時，具有無法得到乾泡之抑制效果而發 泡之情形；若超過99%時，具有所得之乙烯系樹脂的可塑 劑吸收性將降低之情形。 通式（I)所示之P0A基單位1的重複單位數m必須爲 l<mS10、較佳爲l<m<5、更佳爲l<m<3、尤以lSm<2特別 理想。另外，單位2(聚伸氧丁基）的重複單位數n必須爲 〇 3<nS20、較佳爲5SnSl 8、尤以8^n^l 5特別理想。n小於3 之情形’具有POA基彼此之相互作用並未被發現、p〇a改 性P V A水溶液之黏度爲低的情形；n超過2 0之情形，具有 POA基之疏水性將變高、POA改性PVA(A)之水溶性將降低 之情形。 針對本發明中製造POA改性PVA(A)，較佳爲如下之 方法：於醇系溶劑中或無溶劑中進行具有通式⑴所示之 P〇 A基的不飽和單體與乙烯酯系單體之共聚合，皂化所得 -12- 201036994 之POA改性乙烯酯系共聚物。於進行具有POA基的不飽和 單體與乙烯酯系單體的共聚合之際所採用的溫度較佳爲0 〜200°C、更佳爲30〜140°C。進行共聚合之溫度較0°C爲 低之情形，由於充分之聚合速度無法得到而不佳。另外， 進行聚合之溫度較2 0 0 °C爲高之情形，由於得到具有作爲 目的之POA基改性量的POA改性PVA(A)變得困難而不 佳。將進行共聚合之際所採用的溫度控制於〇〜200°C之方 法，例如，可列舉：藉由控制聚合速度而取得經由聚合所 〇 生成的放熱、與從反應器表面放熱的均衡性之方法'，或是 藉由使用適當之熱媒的外部夾套而控制之方法等，基於安 全性方面，較佳爲後者之方法。 針對進行具有P〇 A基的不飽和單體與乙烯酯系單體之 共聚合所用之聚合方式可以爲分批聚合、半分批聚合、連 續聚合、半連續聚合中任一種。聚合方法能夠使用塊狀聚 合法、溶液聚合法、懸浮聚合法、乳化聚合法等習知之任 意方法。其中，於無溶劑或醇系溶劑中進行聚合之塊狀聚 0 合法或溶液聚合法適合被採用；以高聚合度之共聚物製造 作爲目的之情形，乳化聚合法將被採用。醇系溶劑能夠使 用甲醇、乙醇、丙醇等，但是並不受此等醇系溶劑所限定。 另外，此等之溶劑能夠混合2種或2種以上之種類而使用。 共聚合所使用的引發劑係按照聚合方法而適當選擇習 知之偶氮系引發劑、過氧化物系引發劑、氧化還原系引發 劑等。偶氮系引發劑可列舉：2,2’-偶氮二異丁腈、2,2’-偶 氮（2,4-二甲基戊腈）、2,2’-偶氮（4-甲氧基-2,4-二甲基戊腈） -13- 201036994 等。過氧化物系引發劑可列舉：二異丙基過氧二碳酸酯、 二-2-乙基己基過氧二碳酸酯、二乙氧乙基過氧二碳酸酯等 之過碳酸酯化合物；三級丁基過氧新癸酯、茴香過氧新 癸酯、三級丁基過氧癸酯等之過酯化合物；乙醯基環己基 過氧化磺醯；2，4,4-三甲基苄基-2-過氧苯氧基醋酸酯等。 再者，也能夠將過硫酸鉀、過硫酸銨、過氧化氫等與上述 引發劑相組合而作爲引發劑。另外，氧化還原系引發劑可 列舉：組合上述之過氧化物與亞硫酸氫鈉、碳酸氫鈉、酒 Ο 石酸、L-抗壞血酸、漂白粉等之還原劑。 另外，於高溫下進行具有Ρ〇 Α基之不飽和單體與乙烯 酯系單體的共聚合之情形，由於觀察到起因於乙烯酯系單 體分解之PV A著色等，此情形下，以防止著色之目的下， 將例如約1〜lOOppm(相對於乙烯酯系單體而言）之酒石酸 的抗氧化劑添加於聚合系中也無妨。 乙烯酯系單體，可列舉：甲酸乙烯酯、醋酸乙烯酯、 丙酸乙烯酯、丁酸乙烯酯、異丁酸乙烯酯、三甲基乙酸乙 ^ 烯酯、叔碳酸（versatic acid)乙烯酯、己酸乙烯酯、辛酸乙 烯酯、月桂酸乙烯酯、棕櫚酸乙烯酯、硬脂酸乙烯酯、油 酸乙烯酯、安息香酸乙烯酯等，其中，最好爲醋酸乙烯酯。 於具有POA基之不飽和單體與乙烯酯系單體的共聚合 之際，於不損害本發明主旨之範圍內，進行其他單體之共 聚合也無妨。作爲可使用之單體’例如，可列舉：乙烯、 丙烯、正丁烯、異丁烯等之α-烯烴；丙烯酸及其鹽；丙烯 酸甲酯、丙烯酸乙酯、丙烯酸正丙酯、丙烯酸異丙酯、丙 -14- 201036994 烯酸正丁酯、丙烯酸異丁酯、丙烯酸三級丁酯、丙烯酸-2-乙基己酯、丙烯酸十二烷酯、丙烯酸十八烷酯等之丙烯酸 酯類；甲基丙烯酸及其鹽；甲基丙烯酸甲酯、甲基丙烯酸 乙酯、甲基丙烯酸正丙酯、甲基丙烯酸異丙酯、甲基丙烯 酸正丁酯、甲基丙烯酸異丁酯、甲基丙烯酸三級丁酯、甲 基丙烯酸-2-乙基己酯、甲基丙烯酸十二烷酯、甲基丙烯酸 十八烷酯等之甲基丙烯酸酯類；丙烯醯胺；N-甲基丙烯醯 胺、N-乙基丙烯醯胺、N，N-二甲基丙烯醯胺、二丙酮丙烯 ^ 醯胺、丙烯醯胺丙烷磺酸及其鹽、丙烯醯胺丙基二甲基胺 及其鹽或其4級鹽、N-羥甲基丙烯醯胺及其衍生物等之丙 烯醯胺衍生物；甲基丙烯醯胺、N-甲基甲基丙烯醯胺、N-乙基甲基丙烯醯胺、甲基丙烯醯胺丙烷磺酸及其鹽、甲基 丙烯醯胺丙基二甲基胺及其鹽或其4級鹽、N-羥甲基甲基 丙烯醯胺及其衍生物等之甲基丙烯醯胺衍生物；甲基乙烯 醚、乙基乙烯醚、正丙基乙烯醚、異丙基乙烯醚、正丁基 乙烯醚、異丁基乙烯醚、三級丁基乙烯醚、十二烷基乙烯 〇 w 醚、硬脂醯基乙烯醚等之乙烯醚類；丙烯腈、甲基丙烯腈 等之腈類；氯乙烯、氟化乙烯等之鹵化乙烯類；偏氯乙烯、 偏氟乙烯等之偏鹵乙烯類；醋酸烯丙酯、氯丙烯等之烯丙 基化合物；順丁烯二酸、衣康酸、反丁烯二酸等之不飽和 二竣酸及其鹽或其酯；乙烯三甲氧基矽烷等之乙烯矽基化 合物；異丙烯醋酸酯等。 於本發明中所用之POA改性PVA(A)也可以在末端具 有離子性官能基。針對此等之離子性官能基可列舉：羧基、 -15- 201036994 磺酸基等，此等離子性基之中，較佳爲羧基。於此等離子 性基中也包含其鹽，基於POA改性PVA(A)較佳爲水分散 性之觀點，更佳爲鹼金屬鹽。將離子性官能基導入PO A改 性PVA(A)之末端部的手法，能夠利用如下之方法：於硫醇 醋酸、锍基丙酸、锍基-1-丙烷磺酸鈉鹽等之硫醇化合物 的存在下，使醋酸乙烯酯等之乙烯酯系單體聚合、皂化所 得之聚合物等。 另外，於具有POA基之不飽和單體與乙烯酯系單體的 〇 共聚合之際，以調節..所得之共聚物的聚合度等作爲目的， 於不損害本發明之主旨的範圍內，即使於鏈轉移劑之存在 下進行共聚合也無妨。鏈轉移劑適合使用：乙醛、丙醛等 之醛類；丙酮、甲基乙基酮等之酮類；2 -羥基乙烷硫醇等 之硫醇類；三氯乙烯、過氯乙烯等之鹵化烴類，其中，適 合使用醛類與酮類。鏈轉移劑之添加量係按照所添加的鏈 轉移劑之鏈轉移常數及作爲目的之乙烯酯系聚合物的聚合 度所決定，一般而言’相對於乙烯酯系單體而言，鏈轉移 〇 w 劑之添加量期望爲〇」〜ίο重量％。 共聚合具有PO Α基之不飽和單體與乙烯酯系單體而所 得之Ρ Ο A改性P V A c之皂化反應中，能夠採行使用習知之 氫氧化鈉、氫氧化鉀、甲醇鈉等之鹼性觸媒或對甲苯磺酸 等之酸性觸媒的醇解反應或水解反應。可使用於此反應之 溶劑，可列舉：甲醇、乙醇等之醇類：醋酸甲酯、醋酸乙 酯等之酯類；丙酮、甲基乙基酮等之酮類；苯、甲苯等之 芳香族烴等，此等溶劑能夠單獨使用或組合2種以上而使 -16- .201036994 用。其中，較佳將甲醇或是甲醇/醋酸甲酯混合溶液作爲溶 劑，並將氫氧化鈉用於觸媒而進行皂化反應爲簡便的。 具有通式（I)所示之POA基的不飽和單體，可列舉：下 列通式（Π)所示之不飽和單體。 X 4 R——C 一一 3 CIR Η R1 I ~c_c一〇 h2 h 〒2h5•c-c-o· h2 h R2 (II) 0 R1係氫原子或甲基，R2係氫原子或碳數1〜8之烷 基，R3係氫原子或_ COOM。於此，Μ係氫原子、鹼金屬 或銨基。R4係氫原子、甲基或—CH2— COOM，於此，Μ係 如上述定義所市。X係—0—、— CH2— 0—、— C0-、一 C0— 0 -或—CO— NR5—，於此，R5係表示氫原子或碳數 1〜4之飽和烷基。m與η係表示各個的伸氧烷單位之重複 單位數，l<m<10 > 通式（Π)所示之不飽和單體R2較佳爲氫原子、甲基或 〇 丁基，更佳爲氫原子或甲基。再者，尤其通式（II)所示之不 飽和單體R1爲氫，R2爲氫原子或甲基，R3爲氫原子特別 理想。 例如，通式（Π)之R1爲氫原子、R2爲氫原子、R3爲 氫原子之情形，通式（Π)所示之不飽和單體，具體而言，適 合使用聚伸氧乙基聚伸氧丁基單丙烯酸酯、聚伸氧乙基聚 伸氧丁基單甲基丙烯酸酯、聚伸氧乙基聚伸氧丁基單丙烯 酸醯胺、聚伸氧乙基聚伸氧丁基單甲基丙烯酸醯胺、聚伸 -17- 201036994 氧乙基聚伸氧丁基單烯丙基醚、聚伸氧乙基聚伸氧丁基單 甲基烯丙基醚、聚伸氧乙基聚伸氧丁基單乙烯醚等。其中， 適合使用聚伸氧乙基聚伸氧丁基單丙烯酸醯胺、聚伸氧乙 基聚伸氧丁基單甲基丙烯酸醯胺、聚伸氧乙基聚伸氧丁基 單乙烯醚，尤其聚伸氧乙基聚伸氧丁基單甲基丙烯酸醯 胺、聚伸氧乙基聚伸氧丁基單乙烯醚特別適合使用。 通式（II)之R2爲碳數1〜8之烷基之情形，作爲通式（II) 所示之不飽和單體，具體而言，以通式（II)之R1爲氫原子、 O R2爲氫原子、R3爲氫原子之情形爲例，可列舉：上述所 例示的不飽和單體末端之OH基被碳數1〜8之烷氧基所取 代之物。其中，適合使用聚伸氧乙基聚伸氧丁基單甲基丙 烯酸醯胺、聚伸氧乙基聚伸氧丁基單乙烯醚之末端的OH 基被甲氧基所取代的不飽和單體，特別適合使用聚伸氧乙 基聚伸氧丁基單甲基丙烯酸醯胺之末端的OH基被甲氧基 所取代的不飽和單體。 於乙烯系化合物之懸浮聚合中，POA改性PVA(A)之添 〇 w 加時期係乙烯系化合物之聚合轉化率爲1 〇 %以上之時點， 較佳爲15%〜90%、更佳爲18%〜87%、尤以20%〜85 %特別理想。另外，於聚合槽之內壓即將開始降低之前或 是於聚合槽之內壓開始降低之後，發生因乾泡所造成的發 泡之情形下，較佳爲於此時點進行添加。針對POA改性 PVA(A)之添加方法並無特別之限制，可列舉：於水溶液、 水性分散液、甲醇等之有機溶劑溶液、甲醇/水混合溶液等 之形態下而添加之方法。POA改性PVA(A)之溶液濃度通常 -18- 201036994 爲0.01〜30重量％。POA改性PVA (A)之溶液溫度並無特 別之限制，不論室溫或是升溫直到聚合溫度皆可。相對於 懸浮聚合所提供的乙烯系化合物100重量份而言，POA改 性PVA(A)之添加量爲0.001〜5重量份、較佳爲0.001〜0.5 重量份、更佳爲0.01〜0.1重量份。POA改性PVA(A)之添 加量低於0·001重量份之情形，乾泡之抑制效果不足，若 ΡΟΑ改性PVA(A)之添加量超過5重量份時，基於所得之氯 乙烯樹脂的體比重變得過高之觀點而不佳。 提供懸浮聚合之乙烯系化合物，可列舉：氯乙烯等之 鹵乙烯；醋酸乙烯酯、丙酸乙烯酯等之乙烯酯；丙烯酸、 甲基丙烯酸、此等之酯及鹽；順丁烯二酸、反丁烯二酸、 此等之酯及酸酐；苯乙烯、丙烯腈、偏氯乙烯、乙烯醚等。 此等之乙烯系化合物之中，尤以氯乙烯特別適合。氯乙烯 之懸浮聚合可以爲單獨聚合，也可以爲共聚合。能夠與氯 乙烯進行共聚合之單體，可列舉：醋酸乙烯酯、丙酸乙烯 酯等之乙烯酯；（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯等之 (甲基）丙烯酸酯；乙烯、丙烯等之α-烯烴；順丁烯二酸酐、 衣康酸等之不飽和二羧酸類；丙烯腈、苯乙烯、偏氯乙烯、 乙烯醚等。 能夠使用於乙烯系化合物懸浮聚合之聚合引發劑，也 能夠使用習知氯乙烯單體等之聚合所使用的任一種油溶性 觸媒或水溶性觸媒。例如，油溶性觸媒可列舉：二異丙基 過氧二碳酸酯、二-2-乙基己基過氧二碳酸酯、二乙氧基乙 基過氧二碳酸酯等之過碳酸酯化合物；三級丁基過氧新癸 -19- 201036994 酯、三級丁基過氧三甲基乙酯、三級己基過氧三甲基乙酯、 α-茴香過氧新癸酯等之過酯化合物；過氧化乙醯基環己基 磺醯、2,4,4-三甲基戊基-2-過氧苯氧基醋酸酯、過氧化 -3，5,5-三甲基己醯、過氧化月桂醯等之過氧化物；偶氮二 -2，4-二甲基戊腈、偶氮雙（4 ·2，4·二甲基戊腈）等之偶氮化合 物等。例如，作爲水溶性觸媒可列舉：過硫酸鉀、過硫酸 銨、過氧化氫、氫過氧化枯烯等。此等之油溶性觸媒或水 溶性觸媒也能夠單獨使用或是混合2種以上而使用。 〇 於乙烯系化合物懸浮聚合之際，必要時，能夠將其他 之各種添加劑加入聚合反應系中。例如，作爲添加劑可列 舉：醛類、鹵化烴類、硫醇類等之聚合調節劑、酚化物、 硫化物、Ν-氧化物等之聚合抑制劑等。另外，添加pH調整 劑、交聯劑等也爲任意的，倂用複數種上述之添加劑也無 於乙烯系化合物懸浮聚合之際，也可以將皂化度60莫 耳％以下之部分皂化乙烯醇系聚合物作爲分散安定助劑使 ^ 用。相對於懸浮聚合用分散安定劑100重量份而言，其添 加量較佳爲0.1〜120重量份、更佳爲0.5〜110重量份、尤 以1〜1 00重量份特別理想。除了無改性之部分皂化乙烯醇 系聚合物之外’作爲分散安定助劑使用的部分皂化乙烯醇 系聚合物可列舉：在側鏈或末端含有10莫耳％以下之羧基 等之離子性基或氧伸烷基的部分皂化乙烯醇系聚合物等。 另外’於本發明中，於乙烯系化合物懸浮聚合之際， 也可以使用：山梨醇酐單月桂酸酯、山梨醇酐三油酯、甘 -20- 201036994 油三硬脂酸酯、環氧乙烷環氧丙烷嵌段共聚物等之油溶性 乳化劑；聚伸氧乙基山梨醇酐單月桂酸酯、聚伸氧乙基甘 油油酯、月桂酸鈉等之水溶性乳化劑等。針對其添加量， 雖然並無特別之限制，乙烯系化合物每1 00重量份’添加 量較佳爲〇.〇1〜1.0重量份。 [實施例] 以下，藉由實施例而更詳細說明本發明。以下之實施 例與比較例中，無特別申明之情形，份及％分別表示各自 的重量份及重量％。 氯乙烯聚合物粒子與乾泡發生狀態之評估係如下方式 所進行。 (氯乙烯聚合物粒子之評估） 針對氯乙烯聚合物粒子，依照以下之方法而測定粒度 分布與積垢附著量。 (1) 粒度分布 以重量％表示JIS標準篩42篩孔上與通過200篩孔之 含量。含量越少，表示粗大粒子或微粉爲少的而可以得到 均一之粒子。 A :少於 0.5 %。 B : 0.5 %以上、少於1 %。 C : 1 %以上。 (2) 體比重 遵照JIS K6721而測定。 (乾泡發生狀態之評估） -21- 201036994 聚合槽內之乾泡發生狀態係利用下列之方法而評估。 (1) 起泡 聚合結束後，於沖洗未反應之氯乙烯單體之前，從高 壓釜側面之視窗而觀察聚合槽內之起泡狀態。評估基準係 如下所示： A :幾乎無起泡。 B :具有起泡。 C :明顯起泡。 (2) 積垢附著量 藉由目視觀察從聚合槽取出聚合物漿體之後的聚合槽 內壁上之積垢附著狀態而評估。評估基準係如下所示： A :幾乎無積垢附著。 B :具有積垢附著。 C :積垢明顯附著。 實施例1 (POA改性PVA(A)之製造） 〇 於具備攪拌機、回流冷卻管、氮氣導入管、共聚物滴 定口與引發劑之添加口的3L反應器中，進料醋酸乙烯酯 400g、甲醇600g、含有POA基之單體（單體A)3.3g’ 一面 冒氮氣氣泡，一面以氮氣取代系統內30分鐘。另外，將作 爲減速溶液之含有POA基的單體（單體A)溶解於甲醇中而 調製作成濃度20%之共單體溶液，藉由冒氮氣氣泡而進行 氮氣取代。開始反應器之升溫，於內溫成爲60 °C時，添加 2,2’-偶氮二異丁腈（AIBN)0.25g而開始聚合。一面滴下減 -22- 201036994 速溶液而使聚合溶液中之單體組成（醋酸乙烯酯與單體A 之比例）成爲一定的方式，一面於60 °C聚合3小時之後，冷 卻而停止聚合。直到停止聚合爲止所添加的共聚物溶液之 總量爲75ml。另外聚合停止時之固形物濃度爲24.4%。接 著’於30°C、減壓下，一面隨時添加甲醇，一面進行未反 應的醋酸乙烯酯單體之去除，得到POA改性PVAc之甲醇 溶液（濃度35%)。進一步將甲醇加入此溶液中而調製的 POA改性PVAc之甲醇溶液453.4g(溶液中之POA改性 ^ PVAc lOO.Og)中，添加2.7g之鹼溶液（氫氧化鈉之10%甲 醇溶液）而進行皂化（皂化溶液之POA改性PVAc濃度20 %、POA改性PVAc中之氫氧化鈉對醋酸乙烯酯單位之莫 耳比0.0055)。因爲於添加鹼溶液之後約20分鐘生成凝膠 狀物，因此利用粉碎器而粉碎此凝膠狀物，於40°C放置1 小時而使皂化進行之後，添加醋酸甲酯500g而中和所殘存 的鹼。使用酚酞指示劑而確認中和結束之後，過濾而得到 白色固體，於含此固體之容器中添加甲醇2000g而於室溫 〇 下放置洗淨3小時。重複3次上述之洗淨操作之後，進行 離心脫液後，於6 5 °C，將所得之白色固體放置於乾燥機中 2天之後，得到POA改性PVA(A)。POA改性PVA(A)之聚 合度爲5 20、皂化度爲70莫耳％、POA基改性量爲0.4莫 耳％。 (氯乙烯之懸浮聚合）I cό—o h2 h where R 1 represents a hydrogen atom or a methyl group, and R 2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; The !1 and η series indicate the number of repeating units of each of the oxyalkylene units, Bm^lO, 3^η<20. Here, the unit indicated by the number of repetition units m is referred to as a unit, and the unit indicated by the number of repetition units η is referred to as a unit 2°. Unit 1 and unit 2 may be arranged in a random shape or a block shape. Any form. [Embodiment] Advantageous Effects of Invention According to the method for producing an ethylene-based resin of the present invention, the dry foam generated in the middle to the middle of the polymerization has excellent defoaming properties, and the productivity of the vinyl resin can be improved. Further, since ethylene-based polymer particles having a uniform particle diameter can be obtained, an ethyl-based resin having a good quality can be provided. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the present invention, the reflux condenser is used for effectively removing the heat of polymerization generated by suspension polymerization of a vinyl compound. The gas system of the unreacted ethylene compound (monomer) generated from the suspension in the polymerization tank is liquefied by a reflux condenser, and is returned to the polymerization tank to remove the heat of polymerization. The temperature of the cooling water of the reflux condenser is usually about 1 Torr to 50 °C. Typically, in addition to the heat removal by the reflux condenser, the temperature control of the polymerization tank uses temperature control by the jacket or coil of the polymerization tank. The removal amount of the polymerization heat in the reflux condenser is not particularly limited, but is preferably 10 201036994 to 80%, more preferably 20 to 60%, of the total heat of polymerization. The suspension polymerization of the vinyl compound is carried out in the presence of dispersion stability in suspension polymerization. Although it is not limited as a dispersion stabilizer for suspension polymerization, for example, methylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellosolvin, carboxymethylcellosolve, etc. The water-soluble polymer such as gelatin, polyvinyl alcohol or polyvinylpyrrolidone is preferably a saponification degree of 60 to 95% by mole, preferably 68 to 93% by volume, and a polymerization degree of 200 to 3,500, preferably In the present invention, the polyethylene terpene of 500 to 2,500 is preferably used in an amount of from 0.01 to 5 parts by weight, preferably from 0.02 to 2 parts by weight, based on 100 parts by weight of the ethylene compound. More preferably, it is 0.02 to 1 part by weight. When the amount is 0.01 parts by weight, the polymerization stability may be lowered upon suspension polymerization of the vinyl compound; in the case of more than 5 parts by weight, the waste liquid after suspension polymerization will be cloudy, chemical oxygen demand (C) Ο D) will become higher. In the present invention, a polymerization tank having a reflux condenser is used, and a polyoxyalkylene is added at a time when the polymerization conversion ratio is 1% or more at the time of suspension polymerization of the vinyl compound in the presence of a suspension of η with a dispersion stabilizer. A base-modified ethanol-based polymer (hereinafter, a polyoxyalkylene-modified vinyl alcohol-based polymerization, also referred to as a ruthenium-modified PVA), which contains a polyoxyalkylene represented by the above formula in a side chain The alkyl alcohol polymer (hereinafter, the vinyl alcohol compound is also abbreviated as PVA)' and the polyoxyalkylene modification amount is 〇〇1 to 1 〇%. ΡΟΑModified PVA(A)-based polyoxyalkylene (ρ〇Α)-based modified amount must be more specific than eigen, olefin (I) poly- -10-201036994 0.01~10 mol %. When the amount of modification of the POA group exceeds 10 mol%, the ratio of the hydrophobic group contained in each molecule of the POA-modified PVA (A) will become high, and the water solubility of the PVA will be lowered. On the other hand, in the case where the POA-based modification amount is less than 0.01 mol%, although the water solubility of the P0A-modified PVA (A) is excellent, the number of POA groups contained in the PVA is small, based on POA. The physical properties of the modification were not found. The POA-based modification amount is represented by the molar fraction of the POA group to the PVA main chain methylene group. For example, the POA group modification amount of the P〇A modified PVA (A) can be modified from the POA modified polyvinyl ester of the PVA precursor, and a specific example is POA modified polyvinyl acetate (POA modified PVAc). The proton NMR was determined. Specifically, the reprecipitation purification of POA-modified PVAc was carried out three times or more with n-hexane/acetone, and then dried under reduced pressure of 50 ° C for 2 days to prepare POA-modified PVAc for analysis. This PVAc was dissolved in CDC13 and measured at room temperature using a proton NMR (JEOL GX-5 00) at 500 MHz. The peak α (4.7 to 5.2 ppm) derived from the methylene group of the main chain derived from the vinyl ester and the peak β (0·8 to 1.0) of the terminal onyrene W group derived from the exomethoxybutyl unit (unit 2) derived from the POA group. Ppm), the POA-based modification amount is calculated by the following formula: POA-based modification amount (mol%) = {(proton number of β/3η)/(number of protons of α + (number of protons of β/3η)) } X 1〇〇. The number of η-based oxyroxane units (unit 2). The viscosity average degree of polymerization (Ρ) of ΡΟΑ modified PVA (A) was measured in accordance with JIS-K6726. That is, after the resaponification and refining of the PVA, the ultimate viscosity [η] measured by water at 30 ° C is obtained by the following formula: -11 - 201036994 P = ([ η ] χ 1 03 /8·2 9) (1/0.62). The degree of polymerization of the cerium-modified PVA (A) is preferably 200 or more, more preferably 200 to 3,000, still more preferably 300 to 2,500. When the degree of polymerization is less than 200, the effect of suppressing dry foaming will be insufficient, and conversely, the wet foam will become intense. When it exceeds 3,000, the plasticizer absorbability of the obtained vinyl resin will be lowered. In the present invention, the P0A-modified PVA (A) may be used singly or in combination of two or more kinds having different mixing characteristics. The degree of saponification of the POA-modified PVA (A) is preferably from 50 to 99 mol%, more preferably from 60 to 98 mol%, still more preferably from 65 to 95 mol%. When the degree of saponification is less than 50% by mole, there is a case where foaming is not obtained by suppressing the effect of dry foaming; and when it exceeds 99%, the plasticizer absorbability of the obtained vinyl-based resin is lowered. The number of repeating units m of the POL unit 1 of the formula (I) must be l < mS10, preferably l < m < 5, more preferably l < m < 3, especially lSm < 2 is particularly preferred. Further, the number n of repeating units n of the unit 2 (polyoxybutylene) must be 〇 3 < nS20, preferably 5SnSl 8, especially 8^n^l 5 is particularly preferable. In the case where n is less than 3, the interaction between the POA groups is not found, and the viscosity of the p〇a-modified PVA aqueous solution is low; when n exceeds 20, the hydrophobicity of the POA group becomes high, POA The water solubility of the modified PVA (A) will be lowered. In order to produce the POA-modified PVA (A) in the present invention, it is preferred to carry out the method of carrying out an unsaturated monomer having a P〇A group represented by the formula (1) and a vinyl ester in an alcohol solvent or in a solvent-free manner. The monomer is copolymerized to saponify the resulting POA-modified vinyl ester copolymer of -12-201036994. The temperature at which the copolymerization of the unsaturated monomer having a POA group and the vinyl ester monomer is carried out is preferably from 0 to 200 ° C, more preferably from 30 to 140 ° C. When the temperature at which the copolymerization is carried out is lower than 0 °C, it is not preferable because a sufficient polymerization rate cannot be obtained. Further, in the case where the temperature at which polymerization is carried out is higher than 200 °C, it is difficult to obtain a POA-modified PVA (A) having a desired POA-based modification amount. The method of controlling the temperature used for the copolymerization to 〇200 ° C, for example, by controlling the polymerization rate, obtaining the heat generation generated by the polymerization and the balance of the heat release from the surface of the reactor The method 'is a method of controlling by using an external jacket of a suitable heat medium, etc., based on safety, the latter method is preferred. The polymerization method for carrying out the copolymerization of the unsaturated monomer having a P 〇 A group and the vinyl ester monomer may be any one of batch polymerization, semi-batch polymerization, continuous polymerization, and semi-continuous polymerization. The polymerization method can be any conventional method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method. Among them, a bulk polymerization or solution polymerization method in which polymerization is carried out in a solvent-free or alcohol-based solvent is suitably employed; and in the case of producing a copolymer having a high degree of polymerization, an emulsion polymerization method will be employed. The alcohol solvent can be methanol, ethanol, propanol or the like, but is not limited by such an alcohol solvent. In addition, these solvents can be used by mixing two or more types. The initiator to be used in the copolymerization is appropriately selected from a conventional azo initiator, a peroxide initiator, a redox initiator, and the like according to the polymerization method. Examples of the azo initiator include 2,2'-azobisisobutyronitrile, 2,2'-azo (2,4-dimethylvaleronitrile), and 2,2'-azo (4-A). Oxy-2,4-dimethylvaleronitrile) -13- 201036994 et al. Examples of the peroxide-based initiator include peroxycarbonate compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, and diethoxyethyl peroxydicarbonate; a perester compound such as butyl peroxy neodecyl ester, fenthyl peroxy neodecyl ester or tert-butyl peroxy decyl ester; acetamyl cyclohexyl sulfonate; 2,4,4-trimethylbenzyl Alkyl-2-peroxyphenoxyacetate or the like. Further, potassium persulfate, ammonium persulfate, hydrogen peroxide or the like may be combined with the above initiator to form an initiator. Further, examples of the redox initiator include a combination of the above-mentioned peroxide and a reducing agent such as sodium hydrogen sulfite, sodium hydrogencarbonate, tartaric acid, L-ascorbic acid, and bleaching powder. Further, in the case where copolymerization of a mercapto group-containing unsaturated monomer and a vinyl ester monomer is carried out at a high temperature, since PV A coloring due to decomposition of a vinyl ester monomer is observed, in this case, For the purpose of preventing coloring, for example, an antioxidant of tartaric acid of about 1 to 100 ppm (relative to the vinyl ester monomer) may be added to the polymerization system. Examples of the vinyl ester monomer include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, ethyl methacrylate, versatic acid vinyl ester. And vinyl hexanoate, vinyl octanoate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate, vinyl benzoate, etc., among which vinyl acetate is preferred. In the case of copolymerization of a POA group-containing unsaturated monomer and a vinyl ester monomer, it is also possible to carry out copolymerization of another monomer within the range not impairing the gist of the present invention. Examples of the usable monomer' include, for example, α-olefins such as ethylene, propylene, n-butene, and isobutylene; acrylic acid and salts thereof; methyl acrylate, ethyl acrylate, n-propyl acrylate, and isopropyl acrylate. C-14-201036994 Acrylates of n-butyl acrylate, isobutyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate, etc. Acrylic acid and its salts; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid a methacrylate such as butyl ester, 2-ethylhexyl methacrylate, dodecyl methacrylate or octadecyl methacrylate; acrylamide; N-methyl acrylamide, N -ethyl acrylamide, N,N-dimethyl decylamine, diacetone propylene phthalamide, acrylamide propylene sulfonic acid and salts thereof, acrylamidopropyl dimethylamine and salts thereof or 4 thereof Acrylamide derivatives such as grade salts, N-methylol acrylamide and its derivatives Methyl acrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, methacrylamide sulfonic acid and salts thereof, methacrylamide propyl dimethylamine and a methacrylamide derivative of a salt thereof or a 4-stage salt thereof, N-methylol methacrylamide and a derivative thereof; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl Vinyl ethers such as vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl butyl ether, lauryl vinyl hydrazine ether, stearyl hydroxy vinyl ether, etc.; acrylonitrile, methacryl Nitriles such as nitrile; halogenated vinyls such as vinyl chloride and fluorinated ethylene; vinylidene halides such as vinylidene chloride and vinylidene fluoride; allyl compounds such as allyl acetate and chloropropene; An unsaturated dinonanoic acid such as an acid, itaconic acid or fumaric acid, or a salt thereof or an ester thereof; an ethylene mercapto compound such as ethylene trimethoxydecane; isopropenyl acetate or the like. The POA-modified PVA (A) used in the present invention may also have an ionic functional group at the terminal. Examples of the ionic functional group include a carboxyl group, a -15-201036994 sulfonic acid group, and the like, and among these ionic groups, a carboxyl group is preferred. The salt is also contained in the ionic group, and the PVA (A) is preferably an alkali metal salt from the viewpoint of water dispersibility. The method of introducing an ionic functional group into the terminal portion of the PO A-modified PVA (A) can be carried out by using a thiol such as mercaptan acetate, mercaptopropionic acid or mercapto-1-propanesulfonic acid sodium salt. A polymer obtained by polymerizing and saponifying a vinyl ester monomer such as vinyl acetate in the presence of a compound. In addition, when the copolymerization of the POA group-containing unsaturated monomer and the vinyl ester monomer is carried out, the polymerization degree of the obtained copolymer is adjusted, and the like, within the range not impairing the gist of the present invention, It is possible to carry out copolymerization even in the presence of a chain transfer agent. The chain transfer agent is suitably used: an aldehyde such as acetaldehyde or propionaldehyde; a ketone such as acetone or methyl ethyl ketone; a thiol such as 2-hydroxyethane thiol; or a trichloroethylene or perchloroethylene; Halogenated hydrocarbons, among which aldehydes and ketones are suitably used. The amount of the chain transfer agent added is determined according to the chain transfer constant of the added chain transfer agent and the degree of polymerization of the intended vinyl ester polymer. Generally, the chain transfer is relative to the vinyl ester monomer. The amount of the agent added is desirably 〇"~ίο% by weight. In the saponification reaction of the fluorene-modified PVA c obtained by copolymerizing an unsaturated monomer having a PO fluorenyl group and a vinyl ester-based monomer, conventional sodium hydroxide, potassium hydroxide, sodium methoxide or the like can be used. An alcoholysis reaction or a hydrolysis reaction of an alkaline catalyst or an acidic catalyst such as p-toluenesulfonic acid. The solvent to be used in the reaction may, for example, be an alcohol such as methanol or ethanol: an ester such as methyl acetate or ethyl acetate; a ketone such as acetone or methyl ethyl ketone; or an aromatic compound such as benzene or toluene; A hydrocarbon or the like can be used alone or in combination of two or more kinds to make -16-.201036994. Among them, a methanol or methanol/methyl acetate mixed solution is preferably used as a solvent, and sodium hydroxide is used for the catalyst to carry out a saponification reaction. The unsaturated monomer having a POA group represented by the formula (I) may, for example, be an unsaturated monomer represented by the following formula (?). X 4 R - C - 3 - 3 CIR Η R1 I ~ c_c - 〇 h2 h 〒 2h5 • cco · h2 h R2 (II) 0 R1 is a hydrogen atom or a methyl group, R2 is a hydrogen atom or a carbon number of 1 to 8 Alkyl, R3 is a hydrogen atom or _COOM. Here, the hydrazine is a hydrogen atom, an alkali metal or an ammonium group. R4 is a hydrogen atom, a methyl group or -CH2-COOM. Here, the lanthanide is as defined above. X is -0-, -CH2-0-, -C0-, -C0-0- or -CO-NR5-, wherein R5 represents a hydrogen atom or a saturated alkyl group having 1 to 4 carbon atoms. m and η represent the number of repeating units of each of the oxyalkylene units, and l<m<10> The unsaturated monomer R2 represented by the formula (Π) is preferably a hydrogen atom, a methyl group or a hydrazine butyl group. Preferably, it is a hydrogen atom or a methyl group. Further, in particular, the unsaturated monomer R1 represented by the formula (II) is hydrogen, R2 is a hydrogen atom or a methyl group, and R3 is particularly preferably a hydrogen atom. For example, when R1 of the formula (Π) is a hydrogen atom, R2 is a hydrogen atom, and R3 is a hydrogen atom, an unsaturated monomer represented by the formula (Π), specifically, a poly(extended oxygen) ethyl group is suitably used. Oxide butyl monoacrylate, polyoxyethylene ethyl poly(oxybutylene methacrylate), poly(extended oxygen)ethyl polyexetylene butyl methacrylate, poly(extended oxygen) poly(polybutylene oxide) Indole methacrylate, poly-strand -17- 201036994 oxyethyl polyexetylene butyl monoallyl ether, poly(extended oxygen) ethyl polyexetylene monomethyl allyl ether, poly(extended oxygen) ethyl poly Oxybutylene monovinyl ether and the like. Among them, it is suitable to use poly(extended oxyethyl) poly(polybutylene butyl methacrylate), poly(extended oxygen ethyl poly)oxybutyl methacrylate decylamine, poly(extended oxyethyl) poly(butylene oxide monobutyl ether), In particular, poly(oxyethylethyl)poly(terminated butyl) monodecyl methacrylate and poly(extended oxyethyl)polybutylene terephthalate are particularly suitable for use. When R2 of the formula (II) is an alkyl group having 1 to 8 carbon atoms, as an unsaturated monomer represented by the formula (II), specifically, R1 of the formula (II) is a hydrogen atom, O The case where R2 is a hydrogen atom and R3 is a hydrogen atom is exemplified, and the OH group at the terminal of the unsaturated monomer exemplified above is substituted with an alkoxy group having 1 to 8 carbon atoms. Among them, an unsaturated monomer which is substituted with a methoxy group at the terminal of poly(extended oxyethyl)polybutylene methacrylate decylamine or poly(extended oxyethyl)polybutylene terephthalate is suitably used. It is particularly suitable to use an unsaturated monomer in which the OH group at the terminal of the poly(extended oxyethyl)polybutylene methacrylate oxime is substituted with a methoxy group. In the suspension polymerization of the vinyl compound, when the polymerization conversion ratio of the vinyl compound of the POA-modified PVA (A) is 1% by weight or more, preferably 15% to 90%, more preferably 18% to 87%, especially 20% to 85% is particularly desirable. Further, in the case where the internal pressure of the polymerization tank is about to start to decrease or after the internal pressure of the polymerization tank starts to decrease, and the foaming due to the dry bulb occurs, it is preferable to add it at this point. The method of adding the POA-modified PVA (A) is not particularly limited, and examples thereof include a method of adding an aqueous solution, an aqueous dispersion, an organic solvent solution such as methanol, or a methanol/water mixed solution. The solution concentration of the POA-modified PVA (A) is usually from 0.01 to 30% by weight in the range of -18 to 201036994. The temperature of the solution of the POA-modified PVA (A) is not particularly limited, and it is acceptable at room temperature or temperature up to the polymerization temperature. The POA-modified PVA (A) is added in an amount of 0.001 to 5 parts by weight, preferably 0.001 to 0.5 part by weight, more preferably 0.01 to 0.1 part by weight, based on 100 parts by weight of the ethylene compound provided by suspension polymerization. . When the addition amount of the POA-modified PVA (A) is less than 0.0001 parts by weight, the effect of suppressing dry foam is insufficient, and if the amount of the ruthenium-modified PVA (A) is more than 5 parts by weight, based on the obtained vinyl chloride resin The view that the proportion of the body becomes too high is not good. Examples of the vinyl compound which provides suspension polymerization include vinyl halide such as vinyl chloride; vinyl esters such as vinyl acetate and vinyl propionate; acrylic acid, methacrylic acid, esters and salts thereof; maleic acid, Fumaric acid, such esters and anhydrides; styrene, acrylonitrile, vinylidene chloride, vinyl ether, and the like. Among these vinyl compounds, vinyl chloride is particularly suitable. The suspension polymerization of vinyl chloride may be either a single polymerization or a copolymerization. Examples of the monomer 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; An α-olefin such as ethylene or propylene; an unsaturated dicarboxylic acid such as maleic anhydride or itaconic acid; acrylonitrile, styrene, vinylidene chloride or vinyl ether. The polymerization initiator which can be used for suspension polymerization of a vinyl compound can be used, and any of an oil-soluble catalyst or a water-soluble catalyst used for polymerization of a conventional vinyl chloride monomer or the like can be used. For example, the oil-soluble catalyst may be a percarbonate compound such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate or diethoxyethyl peroxydicarbonate; Tert-butyl peroxy neosodium-19- 201036994 ester, tertiary butyl peroxytrimethylethyl ester, tertiary hexylperoxytrimethylethyl ester, α-anisperoxy neodecyl ester and other perester compounds Ethylcyclohexylsulfonyl peroxide, 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate, peroxy-3,5,5-trimethylhexanide, peroxidation A peroxide such as laurel; an azo compound such as azobis-2,4-dimethylvaleronitrile or azobis(4.2,4.dimethyl pentanenitrile). For example, examples of the water-soluble catalyst include potassium persulfate, ammonium persulfate, hydrogen peroxide, and cumene hydroperoxide. These oil-soluble catalysts or water-soluble catalysts can also be used singly or in combination of two or more. Further, when the vinyl compound is suspension-polymerized, other additives may be added to the polymerization reaction system as necessary. For example, as an additive, a polymerization regulator such as an aldehyde, a halogenated hydrocarbon or a mercaptan, a polymerization inhibitor such as a phenol compound, a sulfide or a ruthenium oxide, or the like can be mentioned. Further, a pH adjusting agent, a crosslinking agent, and the like may be added, and a plurality of the above additives may not be used in the suspension polymerization of the vinyl compound, and a partially saponified vinyl alcohol having a saponification degree of 60 mol% or less may be used. The polymer is used as a dispersion stabilizer. The amount of the dispersion stabilizer is preferably 0.1 to 120 parts by weight, more preferably 0.5 to 110 parts by weight, particularly preferably 1 to 100 parts by weight, based on 100 parts by weight of the dispersion stabilizer for suspension polymerization. In addition to the partially saponified vinyl alcohol polymer which is not modified, the saponified vinyl alcohol polymer used as the dispersion stabilizer may be an ionic group containing 10 mol% or less of a carboxyl group at a side chain or a terminal. Or a partially saponified vinyl alcohol polymer such as an alkylene group. Further, in the present invention, in the suspension polymerization of the vinyl compound, sorbitan monolaurate, sorbitan trioleate, gan-20-201036994 oil tristearate, epoxy B may also be used. An oil-soluble emulsifier such as an alkoxypropylene block copolymer; a water-soluble emulsifier such as polyoxyethylene ethyl sorbitan monolaurate, polyoxyethylene ethyl glyceride or sodium laurate; and the like. The amount of the vinyl compound added is preferably from 1.00 to 1.0 part by weight per 100 parts by weight of the ethylene compound. [Examples] Hereinafter, the present invention will be described in more detail by way of examples. In the following examples and comparative examples, the parts and % indicate the respective parts by weight and % by weight, respectively. The evaluation of the state of occurrence of the vinyl chloride polymer particles and the dry bubbles was carried out as follows. (Evaluation of vinyl chloride polymer particles) For the vinyl chloride polymer particles, the particle size distribution and the scale adhesion amount were measured in accordance with the following methods. (1) Particle size distribution The content of the JIS standard sieve 42 on the sieve opening and the passage through the 200 sieve was expressed in % by weight. The smaller the content, the smaller the coarse particles or the fine powder, and the uniform particles can be obtained. A : Less than 0.5%. B : 0.5% or more and less than 1%. C : 1% or more. (2) Body specific gravity Measured in accordance with JIS K6721. (Evaluation of the state of occurrence of dry foam) -21 - 201036994 The state of dry foam generation in the polymerization tank was evaluated by the following method. (1) Foaming After the completion of the polymerization, the foaming state in the polymerization tank was observed from the side of the autoclave before the unreacted vinyl chloride monomer was washed. The evaluation criteria are as follows: A: Almost no blistering. B: Has foaming. C: Significant foaming. (2) Accumulation adhesion amount The scale adhesion state on the inner wall of the polymerization tank after the polymer slurry was taken out from the polymerization tank was visually observed. The evaluation criteria are as follows: A: There is almost no fouling adhesion. B: has fouling adhesion. C: The scale is clearly attached. Example 1 (Production of POA-modified PVA (A)) In a 3 L reactor equipped with a stirrer, a reflux cooling tube, a nitrogen gas introduction tube, a copolymer titration port, and an initiator addition port, 400 g of vinyl acetate was fed. 600 g of methanol and a monomer containing POA group (monomer A) 3.3 g' were replaced with nitrogen gas while replacing the inside of the system with nitrogen for 30 minutes. Further, a POA group-containing monomer (monomer A) as a decelerating solution was dissolved in methanol to prepare a comonomer solution having a concentration of 20%, and nitrogen substitution was carried out by bubbling nitrogen gas. The temperature rise of the reactor was started, and when the internal temperature became 60 °C, 0.25 g of 2,2'-azobisisobutyronitrile (AIBN) was added to initiate polymerization. While reducing the monomer composition (the ratio of vinyl acetate to monomer A) in the polymerization solution by dropping the -22-201036994 solution, the polymerization was stopped after cooling at 60 ° C for 3 hours. The total amount of the copolymer solution added until the polymerization was stopped was 75 ml. Further, the solid concentration at the time of stopping the polymerization was 24.4%. Then, methanol was added at a temperature of 30 ° C under reduced pressure, and the unreacted vinyl acetate monomer was removed to obtain a methanol solution of POA-modified PVAc (concentration: 35%). Further, 453.4 g of a POA-modified PVAc methanol solution prepared by adding methanol to the solution was added to a solution of POA-modified PVAcOO.Og in a solution, and 2.7 g of an alkali solution (10% methanol solution of sodium hydroxide) was added. The saponification was carried out (the POA-modified PVAc concentration of the saponification solution was 20%, and the molar ratio of sodium hydroxide to vinyl acetate in the POA-modified PVAc was 0.0055). Since the gel was formed about 20 minutes after the addition of the alkali solution, the gel was pulverized by a pulverizer and allowed to stand at 40 ° C for 1 hour to cause saponification, and then 500 g of methyl acetate was added to neutralize the residue. Alkali. After confirming the completion of the neutralization using a phenolphthalein indicator, it was filtered to obtain a white solid, and 2000 g of methanol was added to the container containing the solid, and the mixture was allowed to stand at room temperature for 3 hours. After the above-described washing operation was repeated three times, the mixture was centrifuged and dehydrated, and the obtained white solid was placed in a dryer at 65 ° C for 2 days to obtain POA-modified PVA (A). The degree of polymerization of the POA-modified PVA (A) was 520, the degree of saponification was 70 mol%, and the amount of modification of the POA group was 0.4 mol%. (suspension polymerization of vinyl chloride)
使0.1份之聚合度2000、皂化度80莫耳％之PVA溶 解於去離子水（90L)中’調製分散安定劑，進料於容量200L -23- 201036994 之附回流冷凝器的聚合槽中。接著，進料三級丁基過氧新 庚酯〇_1份’使聚合槽內之壓力成爲〇.〇〇67MPa爲止，進 行脫氣而去除氧氣之後，進料氯乙烯1〇〇份，一面攪拌， —面將熱水通入夾套中’升溫至63 °C爲止而開始聚合。聚 合開始時之聚合槽內之壓力爲l.〇2MPa。接著繼續聚合而 使聚合轉化率成爲70%之時點，添加上述所合成的p0A改 性PVA(A)之水溶液10L(PVA(A)爲0.02份）。於聚合槽內 之壓力成爲0.5 MPa之時點，停止聚合，回收未反應單體， 取出聚合物漿體，於65 °C進行一晚乾燥，得到氯乙烯聚合 物粒子。針對所得之氯乙烯聚合物粒子與乾泡之發生狀 態，將評估結果顯示於表1。 實施例2〜1 4 除了變更醋酸乙烯酯與甲醇之進料量、於聚合時所使 用的POA共單體之種類或添加量等之聚合條件、皂化時之 PVAc之濃度、相對於醋酸乙烯單位之氫氧化鈉莫耳比等之 皂化條件以外，使用進行相同於實施例1之方式所合成的 POA改性PVA(A)，除了於表1所示之聚合轉化率之時點添 加POA改性PVA(A)以外，相同於實施例1之方式而進行 氯乙烯之懸浮聚合，得到氯乙烯聚合物粒子。將所用之共 單體構造顯示於表2,將所得POA改性PVA(A)與氯乙烯聚 合物粒子之評估結果顯示於表1。 比較例1 除了不添加ρ ο A改性P v A (A)以外’相同於實施例1 之方式而進行氯乙烯之懸浮聚合’得到氯乙嫌聚合物粒 -24- 201036994 子。將評估結果顯示於表1。粗大粒子爲多的， 均一之聚合物粒子，並且聚合後之起泡爲多的， 內壁面之積垢附著爲多的。 比較例2 除了合成POA改性量爲0.005莫耳％之物以 改性PVA(A)而使用以外，相同於實施例1之方式 乙烯之懸浮聚合，得到氯乙烯聚合物粒子。將評 示於表1。具有粗大粒子而無法得到均一之聚合 〇 且具有聚合後之起泡，具有對聚合槽內壁面之積 比較例3 除了合成POA改性量爲1 1莫耳％之物以取j 性PVA(A)而使用以外，相同於實施例1之方式而 烯之懸浮聚合，但是由於氯乙烯結塊化而無法進 故無法得到氯乙烯聚合物粒子。 比較例4 除了於聚合轉化率爲5%之時點，添加相同於 0 之方式所合成的POA改性PVA(A)以外，相同於 之方式而進行氯乙烯之懸浮聚合，得到氯乙烯 子。將評估結果顯示於表1。具有粗大粒子而無 —之聚合物粒子，並且聚合後之起泡爲多的，對 壁面之積垢附著爲多的。 比較例5、6 除了 POA改性PVA(A)使用於表2所示之POA單 外，相同於實施例1之方式而進行氯乙烯之懸浮 無法得到 對聚合槽 取代Ρ Ο A 而進行氯 估結果顯 物粒子， 垢附著。 ft POA 改 進行氯乙 行聚合， '實施例1 實施例1 聚合物粒 法得到均 聚合槽內 體種類以 聚合，得 -25- 201036994 到氯乙烯聚合物粒子。將評估結果顯示於表1。具有粗大 粒子，無法得到均一之聚合物粒子，並且具有聚合後之起 泡，且具有對聚合槽內壁面之積垢附著。0.1 part of PVA having a degree of polymerization of 2000 and a degree of saponification of 80 mol% was dissolved in deionized water (90 L) to prepare a dispersion stabilizer, which was fed into a polymerization tank equipped with a reflux condenser having a capacity of 200 L -23 to 201036994. Next, the third-stage butyl peroxy neoheptamate 〇 1 part was fed to make the pressure in the polymerization tank 〇.〇〇67 MPa, and degassing to remove oxygen, and then feeding the vinyl chloride one part. Stirring, the surface is heated into the jacket and the temperature is raised to 63 °C to start the polymerization. The pressure in the polymerization tank at the start of the polymerization was 1. 〇 2 MPa. Then, when the polymerization was continued and the polymerization conversion ratio was 70%, 10 L of an aqueous solution (PVA (A): 0.02 parts) of the above-mentioned synthesized pOA-modified PVA (A) was added. When the pressure in the polymerization tank was 0.5 MPa, the polymerization was stopped, unreacted monomers were recovered, and the polymer slurry was taken out and dried overnight at 65 ° C to obtain vinyl chloride polymer particles. The evaluation results are shown in Table 1 for the state of occurrence of the obtained vinyl chloride polymer particles and dry bulbs. Examples 2 to 1 4 The polymerization conditions such as the amount of vinyl acetate and methanol fed, the type or amount of POA comonomer used in the polymerization, the concentration of PVAc during saponification, and the unit of vinyl acetate. The POA-modified PVA (A) synthesized in the same manner as in Example 1 was used, except for the saponification conditions of sodium hydroxide molar ratio, etc., except that the POA-modified PVA was added at the time of the polymerization conversion shown in Table 1. Other than (A), suspension polymerization of vinyl chloride was carried out in the same manner as in Example 1 to obtain vinyl chloride polymer particles. The co-monomer structure used is shown in Table 2, and the evaluation results of the obtained POA-modified PVA (A) and vinyl chloride polymer particles are shown in Table 1. Comparative Example 1 Suspension polymerization of vinyl chloride was carried out in the same manner as in Example 1 except that ρ ο A modified P v A (A) was not added to obtain a chloroethylene polymer granule -24 - 201036994. The evaluation results are shown in Table 1. There are many coarse particles, uniform polymer particles, and there are many foaming after polymerization, and the scale of the inner wall surface adheres to a large amount. Comparative Example 2 Vinyl chloride polymer particles were obtained in the same manner as in Example 1 except that the amount of the POA-modified amount of 0.005 mol% was used to modify the PVA (A). It will be evaluated in Table 1. It has coarse particles and cannot obtain uniform polymerization enthalpy and has foaming after polymerization, and has a product of the inner wall surface of the polymerization tank. Comparative Example 3 In addition to the synthetic POA modification amount of 1 1 mol%, the J-type PVA (A) is obtained. In the same manner as in Example 1, the suspension polymerization of the alkene was carried out in the same manner as in Example 1, but the vinyl chloride polymer particles could not be obtained because the vinyl chloride was agglomerated. Comparative Example 4 In the same manner as in the case of the POA-modified PVA (A) synthesized in the same manner as in the case where the polymerization conversion ratio was 5%, the suspension polymerization of vinyl chloride was carried out in the same manner to obtain a vinyl chloride. The evaluation results are shown in Table 1. The polymer particles having coarse particles and no particles have a large amount of foaming after polymerization, and have a large amount of deposit on the wall surface. Comparative Examples 5 and 6 Except that the POA-modified PVA (A) was used in the POA sheet shown in Table 2, the suspension of vinyl chloride was carried out in the same manner as in Example 1 except that the polymerization tank was substituted for Ρ Ο A and the chlorine was estimated. As a result, the particles of the particles were attached to the scale. The ft POA was changed to carry out polymerization of chloroethylene, 'Example 1 Example 1 Polymer particle method to obtain a homopolymerization tank internal body type to be polymerized, and -25-201036994 to vinyl chloride polymer particles were obtained. The evaluation results are shown in Table 1. It has coarse particles, cannot obtain uniform polymer particles, and has foaming after polymerization, and has adhesion to the inner wall surface of the polymerization tank.
-26- 2000-26- 2000
【1撇】 乾泡發生狀·、· 積垢 附著量 < < < < < < < < < < < < < < U CP 1 u 〇 Ο 起泡 < < < < < < < < < < < < < < u u 1 CQ PQ CQ 氯乙烯 聚合物粒子 體比重 (g/cc) 0.54 0.53 0.53 0.54 1 0.53 0.55 0.54 0.54 0.53 0.53 0.55 0.55 0.54 0.55 0.44 0.45 1 1 0.50 0.45 0.48 粒度 分布 200篩孔 < < < < < < < < < < < < < < Ο o 1 U U U 42篩孔上， < < < < < < < < < < < C < < u u 1 u PQ u POA 改性 PVA(A) 添加時期 聚合添加率(％) 〇 〇 〇 κη ο 卜 ο 卜 ο 卜 ο 卜 〇 卜 〇 〇 卜 ο ο 卜 〇 〇 1 o ο 卜 in o o P0A基改性量 莫耳％ d 〇 Ο Ο ο 〇_ 寸 〇 〇_ ό ό 寸· ο 寸· 〇 寸· 〇 ό 1 0.005 Tt O’ 寸 o’ d 1共單體 型式 < < < CQ Ο Ω ω ϋ Κ ΗΗ 1—i Μ 1 < <ί s 皂化度 (莫耳％)； 〇 〇 ο ο ο ο 卜 〇 卜 〇 〇 卜 ο ο 卜 〇 〇 卜 ο 卜 1 o 卜 Ο 卜 o o 卜 o 卜 聚合度 520 1850 1 520 520 520 520 520 520 520 520 1 520 520 520 520 I 520 520 520 520 520 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 實施例10 實施例11 實施例12 實施例13 實施例14 比較例1 比較例2 比較例3 比較例4 比較例5 比較例6 201036994 單體 R1 R2 R3 R4 X m n A -Η 一 Η — Η -ch3 -CO-NH- 2 13 B -Η -Η -Η -ch3 -CO-NH- 2 9 C — Η 一 Η -Η -ch3 -CO-NH- 2 6 D -Η -Η — Η -ch3 -CO-NH- 2 4 E -Η — Η -Η -ch3 -CO-NH- 2 3 F -Η -Η -Η -ch3 -CO-NH- 2 16 G — Η -Η -Η -ch3 -CO-NH- 2 19 Η -Η -Η -Η 一 ch3 -CO-NH- 2 20 I -Η 一 Η 一 Η 一 H -0- 2 10 J 一 Η -Η -Η -CH2 — COONa -CO-NH- 2 12 κ -Η -Η -COONa -H -CO-NH- 2 13 L -Η -Η 一 Η -ch3 -CO-NH- 12 0 Μ /ιν> ~Η -Η 一 ch3 -CO-NH- 0 17 如實施例中所示，利用本發明之製造方法而製造乙烯 系樹脂之情形，由於對於在聚合之中期〜後期所發生的乾 泡具優越之消泡性，能夠提高乙烯系樹脂之生產性，另外 由於可以得到具有均一粒徑之乙烯系聚合物粒子，能夠提 Ο 供局品質之乙烯系樹脂等，其工業性之評價極高。 【圖式簡單說明】 4ττΐ 無。 【主要元件符號說明】 4bj: 挑0 -28-[1撇] Dry bubble occurrence ··· Scale deposit amount <<<<<<<<<<<<<< U CP 1 u 〇Ο Bubble <<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<<< 1 0.53 0.55 0.54 0.54 0.53 0.53 0.55 0.55 0.54 0.55 0.44 0.45 1 1 0.50 0.45 0.48 Particle size distribution 200 mesh <<<<<<<<<<<<<<; Ο o 1 UUU 42 on the screen, <<<<<<<<<<<<<<<<<<<<<<<<<<<<<> Period polymerization addition rate (%) 〇〇〇κη ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο寸〇〇 ό ό 寸 inch · ο inch · 〇 inch · 〇ό 1 0.005 Tt O' inch o' d 1 total monomer type <<< CQ Ο Ω ω ϋ Κ ΗΗ 1—i Μ 1 <<ί s saponification degree (mole%); 〇〇ο ο ο ο 〇卜 〇〇 ο ο 〇〇 ο ο o o oo oo o o 520 520 520 520 520 520 520 520 520 520 520 520 520 520 520 520 520 520 520 520 1 520 520 520 520 I 520 520 520 520 520 Embodiment 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Comparative Example 1 Comparative Example 2 Comparative Example 4 Comparative Example 4 Comparison Example 5 Comparative Example 6 201036994 Monomer R1 R2 R3 R4 X mn A -Η One Η - Η -ch3 -CO-NH- 2 13 B -Η -Η -Η -ch3 -CO-NH- 2 9 C - Η Η -Η -ch3 -CO-NH- 2 6 D -Η -Η - Η -ch3 -CO-NH- 2 4 E -Η - Η -Η -ch3 -CO-NH- 2 3 F -Η -Η - Η -ch3 -CO-NH- 2 16 G — Η -Η -Η -ch3 -CO-NH- 2 19 Η -Η -Η -Η a ch3 -CO-NH- 2 20 I -Η One Η One Η H -0- 2 10 J -Η -Η -CH2 - COONa -CO-NH- 2 12 κ -Η -Η -COONa -H -CO-NH- 2 13 L -Η -Η 一Η -ch3 - CO-NH- 12 0 Μ /ιν> ~Η -Η a ch3 -CO-NH- 0 17 As shown in the examples, the case of producing a vinyl resin by the production method of the present invention Since the defoaming property of the dry foam which occurs in the middle to the middle of the polymerization is excellent, the productivity of the ethylene resin can be improved, and since the ethylene polymer particles having a uniform particle diameter can be obtained, the supply can be improved. The quality of the vinyl resin and the like is extremely high in industrial evaluation. [Simple description of the figure] 4ττΐ None. [Main component symbol description] 4bj: Pick 0 -28-