JPH05125105A - Production of vinyl chloride resin - Google Patents
Production of vinyl chloride resinInfo
- Publication number
- JPH05125105A JPH05125105A JP28985191A JP28985191A JPH05125105A JP H05125105 A JPH05125105 A JP H05125105A JP 28985191 A JP28985191 A JP 28985191A JP 28985191 A JP28985191 A JP 28985191A JP H05125105 A JPH05125105 A JP H05125105A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- monomer
- polymerization
- resin
- specific gravity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229920005989 resin Polymers 0.000 title claims abstract description 33
- 239000011347 resin Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 42
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 32
- 239000002270 dispersing agent Substances 0.000 claims abstract description 31
- 238000010992 reflux Methods 0.000 claims abstract description 26
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 25
- 238000007127 saponification reaction Methods 0.000 claims abstract description 23
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 claims abstract description 16
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 9
- 239000012736 aqueous medium Substances 0.000 claims abstract description 7
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 claims abstract description 4
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 42
- 230000005484 gravity Effects 0.000 abstract description 26
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- 239000005977 Ethylene Substances 0.000 abstract 1
- 239000007870 radical polymerization initiator Substances 0.000 abstract 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 20
- 239000004800 polyvinyl chloride Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 18
- -1 polyoxyethylene Polymers 0.000 description 13
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 11
- 238000001879 gelation Methods 0.000 description 11
- 238000001125 extrusion Methods 0.000 description 7
- 239000002952 polymeric resin Substances 0.000 description 7
- 229920003002 synthetic resin Polymers 0.000 description 7
- 241000251468 Actinopterygii Species 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000005215 alkyl ethers Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 238000010558 suspension polymerization method Methods 0.000 description 3
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- UKDKWYQGLUUPBF-UHFFFAOYSA-N 1-ethenoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOC=C UKDKWYQGLUUPBF-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NXVGUNGPINUNQN-UHFFFAOYSA-N 2-phenylpropan-2-yl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C1=CC=CC=C1 NXVGUNGPINUNQN-UHFFFAOYSA-N 0.000 description 1
- UJTRCPVECIHPBG-UHFFFAOYSA-N 3-cyclohexylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C2CCCCC2)=C1 UJTRCPVECIHPBG-UHFFFAOYSA-N 0.000 description 1
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、懸濁重合法による塩
化ビニル系樹脂の製造方法に関する。さらに詳しくは、
還流凝縮器を付設した重合容器を用いて、嵩比重が高
く、かつゲル化しやすい高品質の塩化ビニル系樹脂を効
率よく懸濁重合できる塩化ビニル系樹脂の製造方法に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a vinyl chloride resin by a suspension polymerization method. For more details,
The present invention relates to a method for producing a vinyl chloride-based resin capable of efficiently suspension-polymerizing a high-quality vinyl chloride-based resin that has a high bulk specific gravity and is easily gelated by using a polymerization container equipped with a reflux condenser.
【０００２】[0002]
【従来の技術】塩化ビニル系樹脂の重合において、生産
性の向上や省エネルギーを図る目的で還流凝縮器がしば
しば用いられている。2. Description of the Related Art In polymerization of vinyl chloride resin, a reflux condenser is often used for the purpose of improving productivity and saving energy.
【０００３】ところで、還流凝縮器を付設した重合容器
で塩化ビニル単量体もしくはこれと共重合可能な他の単
量体との混合物を懸濁重合する場合には、分散剤の選択
と還流凝縮器の運転操作条件の選択が重要となる。When suspension polymerization of a vinyl chloride monomer or a mixture of the vinyl chloride monomer and another monomer copolymerizable with the vinyl chloride monomer is carried out in a polymerization vessel equipped with a reflux condenser, selection of a dispersant and reflux condensation are performed. It is important to select the operating conditions of the vessel.
【０００４】すなわち、分散剤の選択を誤ると、重合し
た塩化ビニル系樹脂が還流凝縮器内で沈殿、堆積して還
流凝縮器の性能を低下させるだけでなく、重合効率を低
下させ、さらに還流凝縮器内に沈殿、堆積した樹脂が時
には落下して水相中に入り、フィッシュアイを生じさせ
て成形品の品質を低下させることになる。That is, if the dispersant is selected incorrectly, the polymerized vinyl chloride resin will be precipitated and deposited in the reflux condenser to deteriorate the performance of the reflux condenser, as well as to reduce the polymerization efficiency and further reflux. The resin settled and deposited in the condenser sometimes drops and enters the water phase, causing fish eyes to deteriorate the quality of the molded product.
【０００５】また、還流凝縮器の使用を重合反応の初期
の段階から開始すると、得られる塩化ビニル系樹脂の粒
子が粗くなったり、はなはだしい場合には重合懸濁液が
一部塊状化してしまうので、重合反応がある程度進行し
た時点から初めて還流凝縮器の使用を開始せざるを得な
かった。Further, if the use of the reflux condenser is started from the initial stage of the polymerization reaction, the particles of the vinyl chloride resin obtained will become coarse, or in the worst case, the polymerization suspension will partly agglomerate. The use of the reflux condenser had to be started only when the polymerization reaction proceeded to some extent.
【０００６】還流凝縮器を付設して塩化ビニルを懸濁重
合するにあたり、使用される分散剤としては、ポリビニ
ルアルコールまたはポリビニルアルコールと他の分散剤
とを併用使用する方法が知られている。この方法を例示
すると次のとおりである。 （１）ケン化度の低いポリビニルアルコールと油溶性界
面活性剤または油溶性セルロースエーテルとを併用する
方法（特開昭６０−１５８２０６号公報）。As a dispersant used in suspension polymerization of vinyl chloride by providing a reflux condenser, polyvinyl alcohol or a method of using polyvinyl alcohol in combination with another dispersant is known. An example of this method is as follows. (1) A method in which polyvinyl alcohol having a low degree of saponification and an oil-soluble surfactant or oil-soluble cellulose ether are used in combination (JP-A-60-158206).
【０００７】この方法では、ポリビニルアルコールとし
てはケン化度が８０％以下、特に７０％以下のものが適
しているとされ、また、油溶性界面活性剤としてはポリ
オキシエチレンアルキルエーテル及びポリオキシエチレ
ンアルキルアリルエーテルが適しているとしている。 （２）ケン化度の高い、例えばケン化度が８５モル％以
上の部分ケン化ポリビニルアルコールを分散剤として使
用する方法（特開昭６１−１１５９０８号公報）。According to this method, polyvinyl alcohol having a saponification degree of 80% or less, particularly 70% or less is suitable, and the oil-soluble surfactant is polyoxyethylene alkyl ether or polyoxyethylene. Alkyl allyl ether is said to be suitable. (2) A method of using a partially saponified polyvinyl alcohol having a high degree of saponification, for example, a degree of saponification of 85 mol% or more as a dispersant (JP-A-61-115908).
【０００８】この方法では、部分ケン化ポリビニルアル
コールに、メチルビニルエーテルと無水マレイン酸との
共重合体のようなほとんど界面活性能のない高分子やポ
リオキシエチレンアルキルエーテルのようなノニオン界
面活性剤などを少量添加し得るとされている。 （３）部分ケン化ポリビニルアルコールと高分子量のポ
リエチレンオキサイドとを分散剤として使用する方法
（特開平１−２５６５０４号公報）。In this method, partially saponified polyvinyl alcohol is added to a polymer having almost no surface-active property such as a copolymer of methyl vinyl ether and maleic anhydride, or a nonionic surfactant such as polyoxyethylene alkyl ether. It is said that a small amount can be added. (3) A method in which partially saponified polyvinyl alcohol and high molecular weight polyethylene oxide are used as a dispersant (JP-A-1-256504).
【０００９】この方法では、ケン化度が６８〜７６モル
％の部分ケン化ポリビニルアルコールが適しているとさ
れ、また、高分子量のポリエチレンオキサイドとしては
分子量が１０万以上であることが必要とされている。 （４）分散剤として、部分ケン化ポリビニルアルコール
とポリビニルピロリドンを併用する方法（特開平１−２
６８７０２号公報）。According to this method, partially saponified polyvinyl alcohol having a saponification degree of 68 to 76 mol% is suitable, and it is required that the high molecular weight polyethylene oxide has a molecular weight of 100,000 or more. ing. (4) A method in which partially saponified polyvinyl alcohol and polyvinylpyrrolidone are used together as a dispersant (JP-A 1-2)
68702).
【００１０】この方法では、ケン化度が６８〜７６モル
％の部分ケン化ポリビニルアルコールが適しているとさ
れている。In this method, partially saponified polyvinyl alcohol having a saponification degree of 68 to 76 mol% is said to be suitable.
【００１１】[0011]
【発明が解決しようとする課題】しかし、上記の（１）
及び（２）の方法によれば、得られる重合体樹脂は嵩比
重が低下するという問題があった。また、上記（３）及
び（４）の方法によれば、上記方法（１）及び（２）よ
りも嵩比重の低下は多少は防げるものの、まだ十分では
なかった。[Problems to be Solved by the Invention] However, the above (1)
According to the methods (2) and (2), the obtained polymer resin has a problem that the bulk specific gravity is lowered. Further, according to the above methods (3) and (4), a decrease in bulk specific gravity can be prevented to some extent as compared with the above methods (1) and (2), but it is still insufficient.
【００１２】ところで、重合体樹脂の嵩比重が低いと、
この樹脂を成形する際の生産性がよくない。押出機によ
る押出成形を例にとれば、押出機への樹脂の供給は樹脂
の体積を基準としているので、嵩比重が低いとそれだけ
樹脂の供給重量が少なくなり押し出される樹脂重量が減
り、従って、生産性が低下するからである。By the way, when the bulk specific gravity of the polymer resin is low,
The productivity when molding this resin is not good. Taking extrusion molding by an extruder as an example, since the resin supply to the extruder is based on the volume of the resin, the lower the bulk specific gravity, the less the resin supply weight and the less the resin weight extruded, and therefore, This is because productivity is reduced.
【００１３】この発明は、上記の点に鑑み、重合反応の
初期段階から還流凝縮器を作動させても得られる重合体
樹脂が粗粒化したり、懸濁重合液が塊状化することがな
く、かつ、嵩比重が高く、ゲル化し易い良質の塩化ビニ
ル系樹脂を、効率よく得ることができる、塩化ビニル系
樹脂の製造方法を提供することを目的とする。In view of the above points, the present invention does not cause coarsening of the polymer resin obtained even when the reflux condenser is operated from the initial stage of the polymerization reaction and the suspension polymerization liquid does not agglomerate. Moreover, it is an object of the present invention to provide a method for producing a vinyl chloride resin, which can efficiently obtain a high-quality vinyl chloride resin having a high bulk specific gravity and easily gelling.
【００１４】[0014]
【課題を解決するための手段】この発明者は、前記の点
を考慮して種々検討した結果、懸濁重合法により塩化ビ
ニルなどの単量体を重合して塩化ビニル系樹脂を製造す
る場合、還流凝縮器を付設した重合容器を使用し、水性
媒体に、分散剤として、ケン化度が６８〜７６モル％の
部分ケン化ポリビニルアルコール（Ａ）、重量平均分子
量が２００万〜８００万のポリエチレンオキサイド
（Ｂ）及びヒドロキシプロピルメチルセルロース（Ｃ）
を併用添加して塩化ビニルなどの単量体を懸濁重合する
ことにより、重合がある程度進行した後に還流凝縮器を
稼働させる、重合中に還流凝縮器の除熱量を調節する、
といった還流凝縮器の操作条件の変更を必要とせず前記
目的を達成することを知見し、この発明を完成した。Means for Solving the Problems As a result of various studies in consideration of the above points, the present inventor found that when a vinyl chloride resin is produced by polymerizing a monomer such as vinyl chloride by a suspension polymerization method. Using a polymerization vessel equipped with a reflux condenser, a partially saponified polyvinyl alcohol (A) having a saponification degree of 68 to 76 mol% and a weight average molecular weight of 2 to 8 million is used as a dispersant in an aqueous medium. Polyethylene oxide (B) and hydroxypropyl methylcellulose (C)
Suspension polymerization of a monomer such as vinyl chloride by adding together, to operate the reflux condenser after the polymerization has progressed to a certain degree, adjust the heat removal amount of the reflux condenser during the polymerization,
The inventors have found that the above object can be achieved without changing the operating conditions of the reflux condenser, and completed the present invention.
【００１５】分散剤（Ａ）の部分ケン化ポリビニルアル
コール（以下、ポリビニルアルコールをＰＶＡという）
のケン化度が６８〜７６モル％とされるのは、ケン化度
が６８モル％未満であると、重合容器の内壁へのスケー
ルの付着が著しくなるばかりでなく、得られる重合体樹
脂の嵩比重が低下し、ケン化度が７６モル％を超えると
得られる重合体樹脂は嵩比重が低下したり、粒度分布が
広くなったり、ゲル化性が悪くなって加工性が低下する
からである。Partially saponified polyvinyl alcohol of the dispersant (A) (hereinafter, polyvinyl alcohol is referred to as PVA)
The degree of saponification of 68 to 76 mol% means that when the saponification degree is less than 68 mol%, not only the adhesion of scale to the inner wall of the polymerization container becomes remarkable, but also the obtained polymer resin When the bulk specific gravity decreases and the saponification degree exceeds 76 mol%, the resulting polymer resin has a low bulk specific gravity, a wide particle size distribution, and poor gelation properties, resulting in poor processability. is there.
【００１６】このような部分ケン化ＰＶＡは、ポリ酢酸
ビニルをアルカリ、酸などで部分的にケン化することに
よって得られるが、市販もされている。例えば、ゴーセ
ノールＫＺ−０６（日本合成社製）、ポバールＬ−８
（クラレ社製）、ポバールＬ−９（クラレ社製）などで
ある。Such partially saponified PVA can be obtained by partially saponifying polyvinyl acetate with an alkali, an acid or the like, but it is also commercially available. For example, Gohsenol KZ-06 (Nippon Gosei), Poval L-8
(Made by Kuraray Co., Ltd.), Poval L-9 (made by Kuraray Co., Ltd.) and the like.
【００１７】分散剤のもう一つの成分（Ｂ）は、上記の
とおり、重量平均分子量が２００万〜８００万のポリエ
チレンオキサイド（以下、ＰＥＯという）である。ＰＥ
Ｏはその重量平均分子量が２００万未満であると嵩比重
の高い重合体樹脂が得られず、８００万を超すものは市
販されていないからである。重量平均分子量が２００万
〜８００万のＰＥＯとしては、市販の、住友精化社製の
ＰＥＯ−１８、明成化学社製のアルコックスＥ−１０
０、Ｅ−２４０、ユニオン・カーバイト社製のポリオッ
クスなどがあげられる。The other component (B) of the dispersant is polyethylene oxide (hereinafter referred to as PEO) having a weight average molecular weight of 2 to 8 million as described above. PE
This is because if O has a weight average molecular weight of less than 2,000,000, a polymer resin having a high bulk specific gravity cannot be obtained, and if it exceeds 8,000,000, it is not commercially available. Examples of PEO having a weight average molecular weight of 2 to 8 million include commercially available PEO-18 manufactured by Sumitomo Seika and Alcox E-10 manufactured by Meisei Chemical.
0, E-240, Polyox manufactured by Union Carbite, and the like.
【００１８】なお、このようなＰＥＯは、ポリエチレン
オキサイドのアルキルエーテルまたはアルキルアリルエ
ーテルとは異なっている。すなわち、ポリエチレンオキ
サイドのアルキルエーテルまたはアルキルアリルエーテ
ルは炭素数が３以上のアルキル基やアリル基を含み、界
面活性が高く、分子量が２０００以下であるのに対し、
ＰＥＯは炭素数が３以上のアルキル基やアリル基を含ま
ず、従って、界面活性が非常に低いものである。Incidentally, such PEO is different from the alkyl ether or alkyl allyl ether of polyethylene oxide. That is, while the alkyl ether or alkyl allyl ether of polyethylene oxide contains an alkyl group or an allyl group having 3 or more carbon atoms, has high surface activity and a molecular weight of 2000 or less,
PEO does not contain an alkyl group or an allyl group having 3 or more carbon atoms, and therefore has a very low surface activity.
【００１９】分散剤の残りの成分（Ｃ）のヒドロキシプ
ロピルメチルセルロース（以下、ＨＰＭＣという）とし
ては、メトキシ基含有量が１９〜３０重量％、ヒドロキ
シプロポキシ基含有量が４〜１５重量％、そして、２０
℃における２重量％水溶液の粘度が５〜４０００ｃｐｓ
のものが好適に用いられるがこれに限定されない。The remaining component (C) of the dispersant, hydroxypropylmethylcellulose (hereinafter referred to as HPMC), has a methoxy group content of 19 to 30% by weight, a hydroxypropoxy group content of 4 to 15% by weight, and 20
Viscosity of 2% by weight aqueous solution at 5 ° C to 4000 cps
However, it is not limited to this.
【００２０】このＨＰＭＣは界面活性が高く、これを分
散剤として用いることにより、ポロシティ（空隙率）が
高くなり、嵩比重の高い重合体樹脂が得られないもので
あるといわれているにもかかわらず、上記分散剤（Ａ）
及び（Ｂ）と併用することにより嵩比重の高く、かつゲ
ル化し易い高品質の塩化ビニル系樹脂を得ることができ
る。This HPMC has a high surface activity, and by using it as a dispersant, the porosity (porosity) becomes high, and it is said that a polymer resin having a high bulk specific gravity cannot be obtained. No, the above dispersant (A)
By using in combination with (B) and (B), it is possible to obtain a high-quality vinyl chloride resin having a high bulk specific gravity and being easily gelled.
【００２１】これらの分散剤（Ａ）及び（Ｃ）の使用量
は、通常、単量体として仕込む塩化ビニルまたは塩化ビ
ニルとその他の単量体との混合物１００重量部に対し、
それぞれ０．００５〜０．２重量部、好ましくは０．０
１〜０．１重量部とされる。また、分散剤（Ｂ）の使用
量は、その使用量が少なすぎるとその添加効果が得られ
ず粒子が粗粒化し、多すぎても著しい効果が得られず経
済的でないので、単量体として仕込む塩化ビニルまたは
塩化ビニルとその他の単量体との混合物１００重量部に
対し、０．００５〜０．０８重量部であり、好ましく
０．０１〜０．０５重量部とされる。そして、分散剤
（Ａ）及び（Ｃ）の使用量に対する分散剤（Ｂ）の使用
量の割合は０．０５〜１．０、好ましくは０．１〜０．
５とするのがよい。なお、この発明においては、上記の
分散剤（Ａ）、（Ｂ）及び（Ｃ）とともに、これ以外の
分散剤を添加してもよい。そのような分散剤としては、
例えば、ケン化度が６８〜７６モル％以外の部分ケン化
ＰＶＡ、ＨＰＭＣ以外のセルロール誘導体、ポリアクリ
ル酸ソーダ、ポリエチレンオキサイドのアルキルエーテ
ル、ソルビタン脂肪酸エステル、ポリメチルビニルエー
テルなどがあげられる。The amount of these dispersants (A) and (C) used is usually 100 parts by weight of vinyl chloride charged as a monomer or 100 parts by weight of a mixture of vinyl chloride and another monomer.
0.005-0.2 parts by weight, preferably 0.0
The amount is 1 to 0.1 part by weight. Further, the amount of the dispersant (B) used is too small, the effect of its addition cannot be obtained, and the particles become coarse particles. The amount is 0.005 to 0.08 parts by weight, and preferably 0.01 to 0.05 parts by weight, per 100 parts by weight of vinyl chloride or a mixture of vinyl chloride and other monomers charged as. The ratio of the amount of the dispersant (B) used to the amount of the dispersants (A) and (C) used is 0.05 to 1.0, preferably 0.1 to 0.
A value of 5 is recommended. In the present invention, other dispersants may be added together with the above-mentioned dispersants (A), (B) and (C). As such a dispersant,
Examples thereof include partially saponified PVA having a saponification degree other than 68 to 76 mol%, cellulose derivatives other than HPMC, sodium polyacrylate, alkyl ether of polyethylene oxide, sorbitan fatty acid ester, polymethyl vinyl ether and the like.
【００２２】この発明において、塩化ビニル単量体と共
重合し得る他の単量体としては、例えば、エチレン、プ
ロピレン、ブチレン等のオレフィン類、酢酸ビニルやス
テアリン酸ビニル等のビニルエステル類、アクリル酸メ
チルやメタクリル酸メチル等の（メタ）アクリル酸エス
テル類、フマル酸やマレイン酸のエステル類及びその無
水物、フェニルマレイミド、シクロヘキシルマレイミド
等の窒素置換マレイミド類、セチルビニルエーテルなど
のビニルエーテル類、アクリロニトリルなどのニトリル
化合物、塩化ビニリデンなどのビニリデン化合物等があ
げられ、その一種又は二種以上が使用される。In the present invention, examples of other monomers copolymerizable with the vinyl chloride monomer include olefins such as ethylene, propylene and butylene, vinyl esters such as vinyl acetate and vinyl stearate, and acrylic. (Meth) acrylic acid esters such as methyl acidate and methyl methacrylate, esters of fumaric acid and maleic acid and their anhydrides, nitrogen-substituted maleimides such as phenylmaleimide and cyclohexylmaleimide, vinyl ethers such as cetyl vinyl ether, and acrylonitrile. And vinylidene compounds such as vinylidene chloride and the like, and one kind or two or more kinds thereof are used.
【００２３】この発明において用いられる還流凝縮器
は、液相から気化したガスを冷却して凝縮して液化さ
せ、重合容器内の液相へ戻すことによって重合を効率よ
く行わせるためのものであり、重合容器内の気相部分に
連通するように設けることが必要とされる。そして、還
流凝縮器内で気体を凝縮するために、還流凝縮器には冷
媒が通されるが、その冷媒としては水が使用されるのが
普通であり、その温度は０℃以上、重合温度以下とされ
るが、通常は４０〜８０℃である。The reflux condenser used in the present invention is for cooling the vaporized gas from the liquid phase, condensing it to liquefy it, and returning it to the liquid phase in the polymerization vessel to carry out the polymerization efficiently. , It is required to be provided so as to communicate with the gas phase portion in the polymerization container. Then, in order to condense the gas in the reflux condenser, a refrigerant is passed through the reflux condenser, and water is usually used as the refrigerant, and the temperature is 0 ° C. or higher, the polymerization temperature It is as follows, but it is usually 40 to 80 ° C.
【００２４】また、この還流凝縮器の冷却能力は、重合
容器内で発生する重合反応熱の４０〜８０％を冷却する
に十分な冷却能力を有することが好ましい。通常、５０
〜７０％とされる。この還流凝縮器の稼働は、所定冷却
能力のもと、重合開始直後から開始される。The reflux condenser preferably has a cooling capacity sufficient to cool 40 to 80% of the heat of polymerization reaction generated in the polymerization vessel. Usually 50
~ 70%. The operation of this reflux condenser is started immediately after the start of polymerization under a predetermined cooling capacity.
【００２５】この発明における水懸濁重合方法として
は、従来の塩化ビニルの水懸濁重合の際に行われている
方法、例えば、重合容器内に水性媒体、分散剤及び重合
開始剤を供給し、重合容器内の空気を排除した後、攪拌
しながら塩化ビニル単量体（及びその他の単量体）を圧
入し、加熱して重合する方法などがあげられる。As the water suspension polymerization method in the present invention, a conventional method used in water suspension polymerization of vinyl chloride, for example, an aqueous medium, a dispersant and a polymerization initiator are fed into a polymerization vessel. After removing the air in the polymerization vessel, a method in which a vinyl chloride monomer (and other monomer) is press-fitted with stirring and heated to perform polymerization, and the like.
【００２６】なお、分散剤の添加時期は、上記のとお
り、通常の分散剤の添加時期と同様に重合開始前とされ
るが、必要に応じて、重合途中に追加して加えてもよ
い。また、その他の単量体は、水と共に最初に供給して
もよいし、塩化ビニル単量体に溶解して塩化ビニル単量
体と共に圧入してもよい。また、その他の単量体が、塩
化ビニルより重合速度が早い場合には、重合初期から後
期にかけて分割添加したり、少量ずつ連続して添加する
のが好ましい。その方が均一な共重合体が得られるので
好ましい。As described above, the dispersant is added before the start of the polymerization as in the case of adding the usual dispersant, but it may be added during the polymerization if necessary. Further, the other monomer may be first supplied together with water, or may be dissolved in the vinyl chloride monomer and then injected together with the vinyl chloride monomer. When the polymerization rate of the other monomer is higher than that of vinyl chloride, it is preferable to add them in portions from the initial stage to the latter stage of the polymerization, or to add them in small amounts continuously. This is preferable because a uniform copolymer can be obtained.
【００２７】上記重合開始剤としては、懸濁重合におい
て通常使用されている油溶性ラジカル開始剤であれば特
に限定されず、例えば、アゾビス−２、４−ジメチルバ
レロニトリル、アゾビスイソブチロニトリル等のアゾ化
合物、ベンゾイルパーオキサイド、ラウロイルパーオキ
サイド、ｔ−ブチルパーオキシピバレート、ジ−２−エ
チルヘキシルパーオキシジカーボネート、α−クミルパ
ーオキシネオデカネート等の有機過酸化物があげられ、
その一種又は二種以上が使用される。The above-mentioned polymerization initiator is not particularly limited as long as it is an oil-soluble radical initiator usually used in suspension polymerization, and examples thereof include azobis-2,4-dimethylvaleronitrile and azobisisobutyronitrile. And other organic peroxides such as azo compounds such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, di-2-ethylhexyl peroxy dicarbonate and α-cumyl peroxyneodecanate.
One or more of them are used.
【００２８】また、この発明では、得られる塩化ビニル
系樹脂の重合度を調整するために、例えば、メルカプト
エタノール、ドデシルメルカプタン等の重合度調整剤を
使用することができる。Further, in the present invention, in order to adjust the degree of polymerization of the obtained vinyl chloride resin, a degree of polymerization modifier such as mercaptoethanol or dodecyl mercaptan can be used.
【００２９】そして、塩化ビニル単量体（及びその他の
単量体）の重合温度は、通常４０〜８５℃とされ、重合
時間は通常２〜２０時間とされる。なお、得られる塩化
ビニル系樹脂の重合度を調整するため、前記したとおり
の重合度調整剤を重合の際に添加するのが好ましい。The polymerization temperature of the vinyl chloride monomer (and other monomers) is usually 40 to 85 ° C., and the polymerization time is usually 2 to 20 hours. In addition, in order to adjust the degree of polymerization of the obtained vinyl chloride resin, it is preferable to add the above-mentioned degree of polymerization adjusting agent during the polymerization.
【００３０】重合終了後、重合容器から未反応の塩化ビ
ニル単量体などを除去した後、重合体スラリーを取り出
し、洗浄、脱水、乾燥などの処理を行って粒子状の塩化
ビニル系樹脂を得る。After completion of the polymerization, unreacted vinyl chloride monomer and the like are removed from the polymerization vessel, and then the polymer slurry is taken out and subjected to treatments such as washing, dehydration and drying to obtain a particulate vinyl chloride resin. ..
【００３１】[0031]
【実施例】以下、この発明の実施例を説明する。なお、
部とあるのは重量部を意味する。以下の実施例及び比較
例において、重合された樹脂の物性の評価は、下記の方
法によって測定した。 （１）嵩比重 ＪＩＳ−Ｋ−６７２１に準拠して測定。 （２）ゲル化性 得られた塩化ビニル系樹脂に安定剤等を加えて、次の組
成の配合物を作り、この配合物（６４ｇ）をブラベンダ
ー・プラストグラフに投入し、ヒーター温度２１５℃、
投入時温度１９０℃、回転数５０回転／分でゲル化する
までの時間（秒）を測定。Embodiments of the present invention will be described below. In addition,
Parts means parts by weight. In the following Examples and Comparative Examples, the physical properties of the polymerized resin were evaluated by the following methods. (1) Bulk specific gravity Measured according to JIS-K-6721. (2) Gelation property A stabilizer and the like are added to the obtained vinyl chloride resin to prepare a composition having the following composition, and this composition (64 g) is put into a Brabender plastograph and the heater temperature is 215 ° C. ,
The time (seconds) until gelation was measured at a temperature of 190 ° C. at the time of input and a rotation speed of 50 rotations / minute.
【００３２】 塩化ビニル系樹脂 １００部 ジオクチル錫メルカプト（ＴＵＳ−８８３１、日本化学社製） ２部 ステアリン酸カルシウム（ＳＣ−１００、堺化学社製） ０．５部 エステル系ワックス（Ｗａｘ−ＯＰ、ヘキスト社製） ０．５部 ポリエチレンワックス（ＰＥ−５２０、ヘキスト社製） ０．７５部 （実施例１）伝熱面積０．５ｍ2 の還流凝縮器を付設し
た６００ｌの重合容器に、ケン化度７２モル％の部分ケ
ン化ＰＶＡ（ゴーセノールＫＺ−０６、日本合成化学社
製）０．０８部、重量平均分子量４３０万のＰＥＯ（Ｐ
ＥＯ−１８、住友精化社製）０．０２部、ＨＰＭＣ（メ
トロース６５ＳＨ５０、信越化学社製）０．０５部及び
水１４０部を仕込み、攪拌して均一の溶液とした。Vinyl chloride resin 100 parts Dioctyltin mercapto (TUS-8831, manufactured by Nippon Kagaku Co., Ltd.) 2 parts Calcium stearate (SC-100, manufactured by Sakai Chemical Co., Ltd.) 0.5 part Ester wax (Wax-OP, Hoechst Co.) 0.5 parts Polyethylene wax (PE-520, manufactured by Hoechst) 0.75 parts (Example 1) A 600 l polymerization container equipped with a reflux condenser having a heat transfer area of 0.5 m 2 was used, and the degree of saponification was 72. Molar% partially saponified PVA (Gohsenol KZ-06, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) 0.08 part, PEO with a weight average molecular weight of 4.3 million (P
EO-18, manufactured by Sumitomo Seika) 0.02 part, HPMC (Metrose 65SH50, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.05 part and water 140 parts were charged and stirred to obtain a uniform solution.
【００３３】この溶液に重合開始剤としてジ−２−エチ
ルヘキシルパーオキシジカーボネート０．０８部を添加
し、次いで、重合容器内の空気を除いて塩化ビニル単量
体１００部を仕込み、５８℃に昇温して重合を開始さ
せ、その直後に還流凝縮器を稼働させ、４時間後に重合
容器の内圧が７．５ｋｇ／ｃｍ2 （ゲージ圧）となった
とき、未反応の塩化ビニル単量体などを回収し、水相か
ら重合体を濾別してポリ塩化ビニル（以下、ＰＶＣとい
う）を得た。重合の間、還流凝縮器における除熱は、２
０℃の水を循環させて、重合反応熱の６０％を除去する
ような条件で行った。To this solution was added 0.08 part of di-2-ethylhexyl peroxydicarbonate as a polymerization initiator, then the air in the polymerization vessel was removed and 100 parts of vinyl chloride monomer was charged, and the mixture was heated to 58 ° C. When the temperature was raised to start the polymerization, and immediately after that, the reflux condenser was operated, and after 4 hours, when the internal pressure of the polymerization container reached 7.5 kg / cm 2 (gauge pressure), unreacted vinyl chloride monomer Etc. were collected and the polymer was filtered off from the aqueous phase to obtain polyvinyl chloride (hereinafter referred to as PVC). During the polymerization, the heat removal in the reflux condenser is 2
Circulation of water at 0 ° C. was carried out under conditions such that 60% of heat of polymerization reaction was removed.
【００３４】得られたＰＶＣは、嵩比重が０．５５１、
ゲル化時間が２８０秒であって加工性に優れ、フィッシ
ュアイのない無色透明な溶融物が得られたことから、良
質な樹脂であると認められた。 （実施例２）部分ケン化ＰＶＡとしてケン化度７６モル
％の部分ケン化ＰＶＡ（ポバールＬ−８、クラレ社製）
を使用し、その使用量を０．０５部とし、ＰＥＯの使用
量を０．０１部とし、ＨＰＭＣの使用量を０．０３部と
したこと以外は実施例１と同様にしてＰＶＣを得た。The obtained PVC has a bulk specific gravity of 0.551,
Since the gelling time was 280 seconds, the processability was excellent, and a colorless and transparent melt having no fish eyes was obtained, it was recognized as a good resin. (Example 2) Partially saponified PVA having a saponification degree of 76 mol% as partially saponified PVA (Poval L-8, manufactured by Kuraray Co., Ltd.)
PVC was obtained in the same manner as in Example 1 except that the used amount was 0.05 part, the used amount of PEO was 0.01 part, and the used amount of HPMC was 0.03 part. ..
【００３５】得られたＰＶＣは、嵩比重が０．５７０と
高く、ゲル化時間が２９０秒であって加工性に優れ、フ
ィッシュアイのない無色透明な溶融物が得られたことか
ら、良質な樹脂であると認められた。 （実施例３）部分ケン化ＰＶＡとしてケン化度７１モル
％の部分ケン化ＰＶＡ（ＫＰ−０８、日本合成化学社
製）を使用し、その使用量を０．０５部とし、ＰＥＯと
して重量平均分子量４５０万のアルコックスＥ−２４０
（明成化学社製）を使用し、その使用量を０．０１部と
し、ＨＰＭＣとしてメトロース６０ＳＨ４０００（信越
化学社製）を使用したこと以外は実施例１と同様にして
ＰＶＣを得た。The obtained PVC has a high bulk specific gravity of 0.570, a gelation time of 290 seconds, is excellent in processability, and is a colorless transparent melt without fish eyes. It was recognized as a resin. (Example 3) Partially saponified PVA having a saponification degree of 71 mol% (KP-08, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was used as the partially saponified PVA, the amount used was 0.05 parts, and the weight average as PEO. Alcox E-240 with a molecular weight of 4.5 million
PVC (manufactured by Meisei Chemical Co., Ltd.) was used in the same manner as in Example 1 except that the amount used was 0.01 part and Metroth 60SH4000 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used as HPMC.
【００３６】得られたＰＶＣは、嵩比重が０．５８２と
高く、ゲル化時間が２８５秒であって加工性に優れ、フ
ィッシュアイのない無色透明な溶融物が得られたことか
ら、良質な樹脂であると認められた。 （実施例４）部分ケン化ＰＶＡとしてケン化度７１モル
％の部分ケン化ＰＶＡ（ポバールＬ８、クラレ社製）を
使用し、その使用量を０．０７部とし、ＰＥＯとして重
量平均分子量２５０万のアルコックスＥ−１００（明成
化学社製）を使用し、その使用量を０．０１部とし、Ｈ
ＰＭＣとしてメトロース９０ＳＨ４００（信越化学社
製）を使用し、その使用量を０．０３部としたこと以外
は実施例１と同様にしてＰＶＣを得た。The obtained PVC has a high bulk specific gravity of 0.582, a gelation time of 285 seconds, is excellent in processability, and a colorless and transparent melt having no fish eyes is obtained. It was recognized as a resin. (Example 4) Partially saponified PVA having a saponification degree of 71 mol% (Poval L8, manufactured by Kuraray Co., Ltd.) was used as the partially saponified PVA, the amount used was 0.07 parts, and the weight average molecular weight was 2.5 million as PEO. Alcox E-100 (manufactured by Meisei Chemical Co., Ltd.) is used, and the amount used is 0.01 part, and H
PVC was obtained in the same manner as in Example 1 except that Metrose 90SH400 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used as PMC and the amount used was 0.03 part.
【００３７】得られたＰＶＣは、嵩比重が０．５７５と
高く、ゲル化時間が２９０秒であって加工性に優れ、フ
ィッシュアイのない無色透明な溶融物が得られたことか
ら、良質な樹脂であると認められた。 （実施例５）部分ケン化ＰＶＡとしてケン化度７１モル
％の部分ケン化ＰＶＡ（ＫＰー０６、日本合成社製）を
使用し、その使用量を０．０７部とし、ＰＥＯとして重
量平均分子量５００万のポリオックス−Ｃｏａｇｕｌａ
ｎｔ（ユニオン・カーバイト社製）を使用し、その使用
量を０．０１部とし、ＨＰＭＣとしてメトロース６０Ｓ
Ｈ５０（信越化学社製）を使用し、その使用量を０．０
３部としたこと以外は実施例１と同様にしてＰＶＣを得
た。The obtained PVC has a high bulk specific gravity of 0.575, a gelation time of 290 seconds, excellent processability, and a colorless and transparent melt having no fish eyes was obtained. It was recognized as a resin. (Example 5) Partially saponified PVA having a saponification degree of 71 mol% (KP-06, manufactured by Nippon Gosei Co., Ltd.) was used as the partially saponified PVA, and the amount thereof was set to 0.07 part, and the weight average molecular weight as PEO. 5 Million Polyox-Coagula
nt (manufactured by Union Carbide Co., Ltd.) and its usage amount is 0.01 part, and HPMC is Metrose 60S.
H50 (manufactured by Shin-Etsu Chemical Co., Ltd.) is used, and the amount used is 0.0
PVC was obtained in the same manner as in Example 1 except that 3 parts were used.
【００３８】得られたＰＶＣは、嵩比重が０．５６５、
ゲル化時間が２８０秒であって加工性に優れ、フィッシ
ュアイのない無色透明な溶融物が得られたことから、良
質な樹脂であると認められた。 （比較例１）分散剤として、ＰＥＯを用いることなく、
ケン化度７１モル％の部分ケン化ＰＶＡ（ポバールＬ−
８、クラレ社製）を使用し、その使用量を０．０３部と
し、ＨＰＭＣの使用量を０．０６部としたこと以外は実
施例１と同様にしてＰＶＣを得た。The obtained PVC has a bulk specific gravity of 0.565,
Since the gelling time was 280 seconds, the processability was excellent, and a colorless and transparent melt having no fish eyes was obtained, it was recognized as a good resin. (Comparative Example 1) Without using PEO as a dispersant,
Partially saponified PVA with a saponification degree of 71 mol% (Poval L-
(8, manufactured by Kuraray Co., Ltd.) was used, the amount thereof was set to 0.03 part, and the amount of HPMC used was set to 0.06 part to obtain a PVC in the same manner as in Example 1.
【００３９】得られたＰＶＣは、ゲル化時間が２５０秒
であってゲル化し易いものであったが、嵩比重が０．５
０５と低いため押出生産性が低く、加工する際の生産性
が良好でなかった。 （比較例２）分散剤として、ＨＰＭＣを用いることな
く、ケン化度７１モル％の部分ケン化ＰＶＡ（ポバール
Ｌ−８、クラレ社製）を使用し、その使用量を０．０６
部とし、ＰＥＯとして重量平均分子量４３０万のＰＥＯ
−１８（住友精化社製）を使用し、その使用量を０．０
１部としたこと以外は実施例１と同様にしてＰＶＣを得
た。The obtained PVC had a gelation time of 250 seconds and was easy to gel, but had a bulk specific gravity of 0.5.
Since it was as low as 05, the extrusion productivity was low and the productivity during processing was not good. (Comparative Example 2) As a dispersant, partially saponified PVA (Poval L-8, manufactured by Kuraray Co., Ltd.) having a saponification degree of 71 mol% was used without using HPMC, and the amount thereof was 0.06.
Parts, PEO having a weight average molecular weight of 4.3 million as PEO
-18 (manufactured by Sumitomo Seika Co., Ltd.) is used, and the amount used is 0.0
PVC was obtained in the same manner as in Example 1 except that 1 part was used.
【００４０】得られたＰＶＣは、ゲル化時間が２８０秒
であってゲル化し易いものであったが、嵩比重が０．５
３４と低いため押出生産性が低く、加工する際の生産性
が良好でなかった。 （比較例３）分散剤として、ケン化度８８モル％の部分
ケン化ＰＶＡ（ゴーセノールＧＨ−２０、日本合成化学
社製）を使用し、その使用量を０．１部とし、ＰＥＯと
してＰＥＯ−１８（住友精化社製）を使用し、その使用
量を０．０１部とし、ＨＰＭＣとしてメトロース９０Ｓ
Ｈ４０００（信越化学社製）を使用し、その使用量を
０．０３部としたこと以外は実施例１と同様にしてＰＶ
Ｃを得た。The obtained PVC had a gelation time of 280 seconds and was easy to gel, but had a bulk specific gravity of 0.5.
Since it was as low as 34, the extrusion productivity was low and the productivity during processing was not good. (Comparative Example 3) As a dispersant, partially saponified PVA having a saponification degree of 88 mol% (Gohsenol GH-20, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) was used, and the used amount was 0.1 part, and PEO-as PEO- 18 (manufactured by Sumitomo Seika Co., Ltd.) was used, the amount used was 0.01 parts, and Metrose 90S was used as HPMC.
PV was used in the same manner as in Example 1 except that H4000 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used and the amount used was 0.03 part.
I got C.
【００４１】得られたＰＶＣは、ゲル化時間が３４０秒
と長く、成形性が悪く、嵩比重が０．５２５と低いため
押出生産性も低く、成形性及び成形する際の生産性がと
もに良好でなかった。 （比較例４）分散剤として、ケン化度７１モル％の部分
ケン化ＰＶＡ（ポバールＬ−８、クラレ社製）を使用
し、その使用量を０．０５部とし、ＰＥＯとして重量平
均分子量４０万のＰＥＯ−１（住友精化社製）を使用
し、ＨＰＭＣとしてメトロース６０ＳＨ４０００（信越
化学社製）を使用し、その使用量を０．０３部としたこ
と以外は実施例１と同様にしてＰＶＣを得た。The obtained PVC has a long gelation time of 340 seconds, poor moldability, and low bulk specific gravity of 0.525, resulting in low extrusion productivity and good moldability and productivity during molding. It wasn't. (Comparative Example 4) As a dispersant, partially saponified PVA (Poval L-8, manufactured by Kuraray Co., Ltd.) having a saponification degree of 71 mol% was used, the amount used was 0.05 parts, and PEO had a weight average molecular weight of 40. Ten thousand PEO-1 (manufactured by Sumitomo Seika) was used, and Metrose 60SH4000 (manufactured by Shin-Etsu Chemical Co., Ltd.) was used as HPMC, except that the amount used was 0.03 parts, and the same procedure as in Example 1 was performed. PVC was obtained.
【００４２】得られたＰＶＣは、ゲル化時間が２７０秒
であってゲル化し易いものであったが、嵩比重が０．５
３１と低いため押出生産性が低く、加工する際の生産性
が良好でなかった。 （比較例５）分散剤として、ケン化度４５モル％の部分
ケン化ＰＶＡ（ポバールＬＭ−１０−Ｈ、クラレ社製）
を使用し、その使用量を０．０５部とし、ＰＥＯの使用
量を０．０１部とし、ＨＰＭＣとしてメトロース６５Ｓ
Ｈ５０（信越化学社製）を使用し、その使用量を０．０
６部としたこと以外は実施例１と同様にしてＰＶＣを得
た。The obtained PVC had a gelation time of 270 seconds and was easy to gel, but had a bulk specific gravity of 0.5.
Since it was as low as 31, the extrusion productivity was low and the productivity during processing was not good. (Comparative Example 5) As a dispersant, partially saponified PVA with a saponification degree of 45 mol% (Poval LM-10-H, manufactured by Kuraray Co., Ltd.)
Is used, the amount used is 0.05 part, the amount used PEO is 0.01 part, and Metrose 65S is used as HPMC.
H50 (manufactured by Shin-Etsu Chemical Co., Ltd.) is used, and the amount used is 0.0
PVC was obtained in the same manner as in Example 1 except that 6 parts were used.
【００４３】得られたＰＶＣは、ゲル化時間が２９０秒
であってゲル化し易いものであったが、嵩比重が０．５
０４と低いため押出生産性が低く、加工する際の生産性
が良好でなかった。The obtained PVC had a gelation time of 290 seconds and was easy to gel, but had a bulk specific gravity of 0.5.
Since it was as low as 04, the extrusion productivity was low and the productivity during processing was not good.
【００４４】[0044]
【発明の効果】以上のとおり、この発明方法によれば、
嵩比重が高く、且つゲル化性のよい塩化ビニル系樹脂を
懸濁重合により効率よく製造することができる。こうし
て得られた塩化ビニル系樹脂は、ゲル化性がよいため成
形性がよく、また嵩比重が高く押出成形法等による高生
産性に寄与するものとなる。As described above, according to the method of the present invention,
A vinyl chloride resin having a high bulk specific gravity and a good gelling property can be efficiently produced by suspension polymerization. The vinyl chloride-based resin thus obtained has good gelling property and thus good moldability, and also has a high bulk specific gravity and contributes to high productivity by an extrusion molding method or the like.
Claims (1)
性媒体と、塩化ビニル単量体、または塩化ビニル単量体
とこの塩化ビニル単量体と共重合可能な他の単量体との
混合物を入れて懸濁重合するにあたり、水性媒体中に、
分散剤として、ケン化度が６８〜７６モル％の部分ケン
化ポリビニルアルコール（Ａ）、重量平均分子量が２０
０万〜８００万のポリエチレンオキサイド（Ｂ）及びヒ
ドロキシプロピルメチルセルロース（Ｃ）を添加するこ
とを特徴とする塩化ビニル系樹脂の製造方法。1. A polymerization vessel equipped with a reflux condenser, comprising an aqueous medium, a vinyl chloride monomer, or a vinyl chloride monomer and another monomer copolymerizable with the vinyl chloride monomer. In putting the mixture and carrying out suspension polymerization, in an aqueous medium,
As a dispersant, a partially saponified polyvinyl alcohol (A) having a saponification degree of 68 to 76 mol% and a weight average molecular weight of 20.
A method for producing a vinyl chloride resin, which comprises adding 0,000 to 8 million polyethylene oxide (B) and hydroxypropylmethyl cellulose (C).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3289851A JP3068684B2 (en) | 1991-11-06 | 1991-11-06 | Method for producing vinyl chloride resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3289851A JP3068684B2 (en) | 1991-11-06 | 1991-11-06 | Method for producing vinyl chloride resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05125105A true JPH05125105A (en) | 1993-05-21 |
| JP3068684B2 JP3068684B2 (en) | 2000-07-24 |
Family
ID=17748590
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3289851A Expired - Lifetime JP3068684B2 (en) | 1991-11-06 | 1991-11-06 | Method for producing vinyl chloride resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3068684B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006322013A (en) * | 2006-09-08 | 2006-11-30 | Sekisui Chem Co Ltd | Method for producing chlorinated vinyl chloride resin |
| EP0802201B2 (en) † | 1996-04-19 | 2009-05-27 | Kuraray Co., Ltd. | Process for producing vinyl resin |
| DE102014210643A1 (en) | 2013-06-06 | 2015-04-16 | Nidec Corporation | ENGINE |
| KR20190124551A (en) * | 2018-04-26 | 2019-11-05 | 공주대학교 산학협력단 | Method for forming pattern on high strength metal surface |
| WO2023191506A1 (en) * | 2022-03-31 | 2023-10-05 | 한화솔루션 주식회사 | Method for preparing chlorinated polyvinyl chloride resin composition |
-
1991
- 1991-11-06 JP JP3289851A patent/JP3068684B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0802201B2 (en) † | 1996-04-19 | 2009-05-27 | Kuraray Co., Ltd. | Process for producing vinyl resin |
| JP2006322013A (en) * | 2006-09-08 | 2006-11-30 | Sekisui Chem Co Ltd | Method for producing chlorinated vinyl chloride resin |
| DE102014210643A1 (en) | 2013-06-06 | 2015-04-16 | Nidec Corporation | ENGINE |
| KR20190124551A (en) * | 2018-04-26 | 2019-11-05 | 공주대학교 산학협력단 | Method for forming pattern on high strength metal surface |
| WO2023191506A1 (en) * | 2022-03-31 | 2023-10-05 | 한화솔루션 주식회사 | Method for preparing chlorinated polyvinyl chloride resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3068684B2 (en) | 2000-07-24 |
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