JPH0539308A - Polymerization method - Google Patents
Polymerization methodInfo
- Publication number
- JPH0539308A JPH0539308A JP3197895A JP19789591A JPH0539308A JP H0539308 A JPH0539308 A JP H0539308A JP 3197895 A JP3197895 A JP 3197895A JP 19789591 A JP19789591 A JP 19789591A JP H0539308 A JPH0539308 A JP H0539308A
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- electrode
- polymerization reactor
- reactor
- wall
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims description 27
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 230000015556 catabolic process Effects 0.000 claims abstract description 5
- 239000003990 capacitor Substances 0.000 claims abstract description 4
- 239000011810 insulating material Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 2
- 239000003989 dielectric material Substances 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 abstract description 4
- 239000000615 nonconductor Substances 0.000 abstract description 4
- 238000010557 suspension polymerization reaction Methods 0.000 abstract description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 12
- 239000002609 medium Substances 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000012736 aqueous medium Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012777 electrically insulating material Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000010558 suspension polymerization method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-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
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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 compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- CMMUKUYEPRGBFB-UHFFFAOYSA-L dichromic acid Chemical compound O[Cr](=O)(=O)O[Cr](O)(=O)=O CMMUKUYEPRGBFB-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 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
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 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
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 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
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/002—Avoiding undesirable reactions or side-effects, e.g. avoiding explosions, or improving the yield by suppressing side-reactions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymerisation Methods In General (AREA)
Abstract
(57)【要約】
【構成】 重合反応器の内壁を一方の電極とし、重合反
応器内の液体媒質中に他方の電極を配置し、一方若しく
は双方の電極に電気絶縁体で被覆したものを用い、両電
極間に絶縁破壊の生じない直流電圧を印加してコンデン
サー回路を形成した状態で乳化重合または懸濁重合を行
う。
【効果】 重合反応時における反応器の内壁へのスケー
ルの付着が大幅に抑制される。
(57) [Summary] [Structure] The inner wall of the polymerization reactor is used as one electrode, the other electrode is placed in the liquid medium in the polymerization reactor, and one or both electrodes are covered with an electrical insulator. Emulsion polymerization or suspension polymerization is performed in a state where a DC voltage that does not cause dielectric breakdown is applied between both electrodes to form a capacitor circuit. [Effect] The adhesion of scale to the inner wall of the reactor during the polymerization reaction is significantly suppressed.
Description
【０００１】[0001]
【産業上の利用分野】本発明は、重合反応器の内壁への
スケール等の付着防止を可能にする重合方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymerization method which makes it possible to prevent scales and the like from adhering to the inner wall of a polymerization reactor.
【０００２】[0002]
【従来の技術】高分子重合体は、乳化重合法、懸濁重合
法等の各種重合法により工業的に製造されている。乳化
重合法や懸濁重合法の一つの問題点として、重合反応器
の内壁への生成重合体の付着物の形成がある。この様な
付着物の形成は、重合体収率、重合熱除去能力が低下す
るという不利益のみならず、剥離した付着物（スケー
ル）の製品重合体中への混入により、フィッシュアイ等
種々の製品欠陥が発生する原因となる。また、この付着
物を除去するために過大な労力と時間を要し、生産性低
下を来たすのみならず、近年においては付着物の除去作
業は３Ｋ作業の１つとみなされ、これら重合法を用いる
生産方式自体の存立が危ぶまれる状況にある。2. Description of the Related Art High molecular polymers are industrially produced by various polymerization methods such as emulsion polymerization and suspension polymerization. One of the problems of the emulsion polymerization method and the suspension polymerization method is the formation of deposits of the produced polymer on the inner wall of the polymerization reactor. The formation of such deposits is not only disadvantageous in that the polymer yield and the ability to remove the heat of polymerization are reduced, but also the peeled deposits (scale) are mixed into the product polymer to cause various problems such as fish eyes. This may cause product defects. In addition, it takes an excessive amount of labor and time to remove the deposits, which not only causes a decrease in productivity, but in recent years, the deposit removal work is regarded as one of the 3K works, and the production using these polymerization methods is not performed. The existence of the method itself is in jeopardy.
【０００３】従って、乳化重合法、懸濁重合法に依る高
分子重合体の製造に際して、重合反応器内の付着物を減
少させ、あるいはこれを防止する研究が絶えず行われて
きた。従来の防止法としては、極性化合物を、重合反応
器内壁に塗布又は水性媒体中に添加する方法（特公昭４
５−３０３４３号公報）、染料及び／又は顔料を塗布す
る方法（特公昭４５−３０８３５号公報）、水酸化マグ
ネシウムを反応分散液に添加する方法（オランダ特許６
９１４０５９）、あるいは過マンガン酸、クロム酸、重
クロム酸等の無機酸化剤を添加する方法（特公昭４６−
２０８２１号公報）等が提案されている。しかし、これ
らの方法はスケール防止効果が不満足であったり、薬剤
の塗布や製品の乾燥方法が極めて煩雑で長時間を要し、
工業的な実施が困難であったり、添加物の製品中への混
入により、着色、物性低下等が生じたり、あるいは、水
性媒体中の添加物が工場排水中に流出するため、公害の
問題を発生したりするという種々の欠点を有していた。
他方、乳化重合、懸濁重合において、金属性重合反応器
内壁と重合系液体媒質中の不溶性電極間に、外部電源に
より電気回路を形成させた状態で重合を行う方法（特開
昭４８−６９８８６号公報）が提案されているが、この
方法は水性媒体の電気分解による水素と酸素が爆発混合
気を形成するため、極めて危険であつた。従って、本発
明者らは、重合反応器内部、特に重合機内部壁面、攪拌
機、バッフルプレートなどへのスケール付着を防止する
方法、特に容易に工業化可能な方法に関して鋭意研究を
重ねた結果、本発明に到達した。Therefore, in the production of high molecular weight polymers by the emulsion polymerization method and the suspension polymerization method, researches for reducing or preventing the deposits in the polymerization reactor have been continuously conducted. As a conventional prevention method, a polar compound is applied to the inner wall of the polymerization reactor or added to an aqueous medium (Japanese Patent Publication No.
No. 5-30343), a method of applying a dye and / or a pigment (Japanese Patent Publication No. 45-30835), and a method of adding magnesium hydroxide to a reaction dispersion (Dutch Patent 6).
914059), or a method of adding an inorganic oxidizing agent such as permanganic acid, chromic acid or dichromic acid (Japanese Patent Publication No. 46-46-
No. 20821) has been proposed. However, these methods are unsatisfactory in the scale prevention effect, and the method of applying the drug and the method of drying the product are extremely complicated and require a long time,
It is difficult to carry out industrially, or the additives are mixed in the product, resulting in coloration, deterioration of physical properties, etc. It had various drawbacks such as occurrence.
On the other hand, in emulsion polymerization and suspension polymerization, a method of carrying out the polymerization in a state where an electric circuit is formed between the inner wall of the metallic polymerization reactor and the insoluble electrode in the polymerization liquid medium by an external power source (JP-A-48-69886). However, this method was extremely dangerous because hydrogen and oxygen formed an explosive mixture by electrolysis of an aqueous medium. Therefore, the inventors of the present invention have conducted extensive studies as to a method for preventing scale adhesion to the inside of the polymerization reactor, particularly the inner wall surface of the polymerization machine, a stirrer, a baffle plate, etc. Reached
【０００４】[0004]
【課題を解決するための手段】すなわち、本発明の重合
方法は、重合反応器内で重合性単量体を乳化重合または
懸濁重合するに際して、重合反応器の内壁及び攪拌翼等
の反応器内配設物の金属部分を一方の電極とし、重合反
応器内の液体媒質中に配置した少なくとも１個の不溶性
導電体を他方の電極とし、これら電極のいずれか一方若
しくは双方を電気絶縁材で被覆されたものを用い、重合
反応器内の液体媒質及び被覆電気絶縁体を複合誘電体と
し、両電極間に絶縁破壊電圧未満の直流電圧を印加して
コンデンサー回路を生成させた状態で重合を実施するこ
とを特徴とする。[Means for Solving the Problems] That is, in the polymerization method of the present invention, when emulsion-polymerizing or suspension-polymerizing a polymerizable monomer in a polymerization reactor, a reactor such as an inner wall of the polymerization reactor and a stirring blade is used. The metal part of the internal arrangement serves as one electrode, at least one insoluble conductor arranged in the liquid medium in the polymerization reactor serves as the other electrode, and one or both of these electrodes are made of an electrically insulating material. Use the coated one, and use the liquid medium in the polymerization reactor and the coated electrical insulator as a composite dielectric, and apply a DC voltage less than the dielectric breakdown voltage between both electrodes to carry out the polymerization in a state where a capacitor circuit is generated. It is characterized by carrying out.
【０００５】[0005]
【作用】本発明の重合方法は、重合反応器の液体媒質中
に電極を配置し、この電極と重合反応器の内壁等で構成
されるもう一方の電極との間に直流電圧を印加し、コン
デンサー回路を生成せしめた状態、すなわち電場の中に
置かれた複合誘電体である重合反応器中の液体媒質及び
一方若しくは双方の電極の被覆電気絶縁材の各界面に電
気分極現象をけん起させた状態で重合を行う方法であ
る。In the polymerization method of the present invention, an electrode is arranged in the liquid medium of the polymerization reactor, and a DC voltage is applied between this electrode and the other electrode composed of the inner wall of the polymerization reactor, In the state where the capacitor circuit is generated, that is, the electric polarization phenomenon is caused at each interface of the liquid medium and the coating electric insulating material of one or both electrodes in the polymerization reactor which is a composite dielectric placed in an electric field. It is a method of carrying out polymerization in a closed state.
【０００６】本発明の方法においては、重合反応器の内
壁および攪拌翼等の重合反応器内配設物から構成される
一方の電極または重合反応器内の液体媒質中に配置した
他方の電極のいずれか一方又は双方の電極に、電気絶縁
材で被覆されたものを使用する。例えば重合反応容器の
内壁がグラスライニングされたものであれば、攪拌機や
バッフルプレート等の金属製の重合反応容器内配設物に
も電気絶縁材料で被覆されたものを使用し、液体媒質中
の配置電極については電気絶縁材で被覆されていないも
のを使用する。逆に液体媒質中の配置電極に電気絶縁材
で被覆されたものを使用した場合には、重合反応器内壁
等については電気絶縁材で被覆されていないものを使用
する等である。In the method of the present invention, one electrode composed of the inner wall of the polymerization reactor and the internal arrangement of the polymerization reactor such as a stirring blade or the other electrode arranged in the liquid medium in the polymerization reactor is used. One or both electrodes coated with an electrical insulating material are used. For example, if the inner wall of the polymerization reaction vessel is glass-lined, use a metal polymerization reaction vessel such as a stirrer or a baffle plate that is also coated with an electrically insulating material in a liquid medium. For the placement electrode, use one that is not covered with an electrical insulating material. On the contrary, when the placement electrode in the liquid medium is coated with an electrical insulating material, the inner wall of the polymerization reactor is not coated with the electrical insulating material.
【０００７】本発明において使用される不溶性電極と
は、塩類水溶液を電気分解する際に陽極として使用した
時に金属イオンを溶出しないし、かつそれ自体陽極酸化
状態において著しい変化をしない電極を意味する。この
ような不溶性電極としては、例えば炭素、チタン、白
金、金、又は鉄、クロム、亜鉛等の金属にチタン、白
金、金等をメッキしたもの等公知のいわゆる不溶性電極
が包含される。これらの不溶性電極の形状、大きさ、
数、重合装置に配置する位置は、重合系の攪拌効果、電
界の強度、重合反応器本体の大きさ、重合処法等により
任意に選択することができる。不溶性電極の形状は、円
柱、角柱、平板、角板、格子あるいはラセン状であって
よい。The insoluble electrode used in the present invention means an electrode which does not elute metal ions when it is used as an anode in electrolyzing a salt solution and does not itself significantly change in anodized state. Examples of such an insoluble electrode include known so-called insoluble electrodes such as carbon, titanium, platinum, gold, or a metal such as iron, chromium, or zinc plated with titanium, platinum, gold, or the like. The shape, size of these insoluble electrodes,
The number and the position to be placed in the polymerization apparatus can be arbitrarily selected depending on the stirring effect of the polymerization system, the strength of the electric field, the size of the main body of the polymerization reactor, the polymerization method, and the like. The shape of the insoluble electrode may be a cylinder, a prism, a flat plate, a square plate, a lattice, or a spiral shape.
【０００８】本発明において使用される、電気絶縁材と
しては、ガラス、セラミック等の無機質材料のみならず
ポリテトラフルオロエチレン、ポリプロピレン、ポリエ
チレンテレフタレート等の有機高分子材料を使用するこ
ともできる。As the electric insulating material used in the present invention, not only inorganic materials such as glass and ceramics but also organic polymer materials such as polytetrafluoroethylene, polypropylene and polyethylene terephthalate can be used.
【０００９】電極を覆う電気絶縁材料の厚みとしては、
被覆の不完全性によって絶縁破壊が生じない程度の厚み
を有していればよく、通常は０．０１mm以上とされる。
一方、被覆層の厚みが厚過ぎる場合には、電気分極現象
を発生させるのに必要な電圧が大きくなるので、電気絶
縁材料の誘電率によっても影響されるが５mm以下の厚み
とするのがよい。The thickness of the electrically insulating material covering the electrodes is
It suffices that the thickness is such that dielectric breakdown does not occur due to the imperfections of the coating, and is usually 0.01 mm or more.
On the other hand, if the thickness of the coating layer is too thick, the voltage required to generate the electric polarization phenomenon increases, so the thickness is preferably 5 mm or less, although it is affected by the dielectric constant of the electric insulating material. ..
【００１０】本発明の方法が適用される重合方法は、乳
化重合や懸濁重合のように水性媒体中で重合性単量体の
重合を行う方法である。The polymerization method to which the method of the present invention is applied is a method of polymerizing a polymerizable monomer in an aqueous medium, such as emulsion polymerization and suspension polymerization.
【００１１】好適な重合性単量体としては、エチレン、
プロピレン、ブタジエン、クロロプレンなどのオレフィ
ン類；塩化ビニルなどのハロゲン化ビニル；塩化ビニリ
デンなどのハロゲン化ビニリデン；酢酸ビニルなどのビ
ニルエステル；スチレン等の芳香族ビニル；アクリロニ
トリルなどのニトリル；（メタ）アクリル酸およびそれ
らのエステル類；マレイン酸、クロトン酸などの不飽和
カルボン酸が例示される。また、これらの重合に使用さ
れる分散剤としては、ポリビニルアルコール、水溶性セ
ルロース誘導体、ポリアクリル酸、ポリビニルピロリド
ン、酢酸ビニル−無水マレイン酸共重合体、ビニルピロ
リドン−酢酸ビニル共重合体、ゼラチン、澱粉、あるい
はアルキルベンゼンスルホン酸ソーダ、アルキル硫酸ソ
ーダ、ジアルキルスルホコハク酸ソーダ等の各種アニオ
ン性、非イオン性若しくはカチオン性の界面活性剤；タ
ルク、ベントナイト、硫酸カルシウム、炭酸マグネシウ
ム等が用いられる。また、重合触媒としては、ラウロイ
ルパーオキシドのようなアシルパーオキシド、ｔ−ブチ
ルパーオキシピパレートのような有機酸のパーオキシエ
ステル、アゾビスイソブチロニトリルのようなアゾ化合
物、ジイソプロピルパーオキシジカーボネートのような
パーオキシジカーボネート等の油溶性触媒、過硫酸カリ
ウム等の水溶性触媒、あるいは、酸化成分としての過硫
酸と還元成分としての亜硫酸等からなるレドックス触媒
等が用いられる。Suitable polymerizable monomers include ethylene,
Olefins such as propylene, butadiene and chloroprene; vinyl halides such as vinyl chloride; vinylidene halides such as vinylidene chloride; vinyl esters such as vinyl acetate; aromatic vinyls such as styrene; nitriles such as acrylonitrile; (meth) acrylic acid And esters thereof; unsaturated carboxylic acids such as maleic acid and crotonic acid. Further, as the dispersant used in these polymerizations, polyvinyl alcohol, water-soluble cellulose derivative, polyacrylic acid, polyvinylpyrrolidone, vinyl acetate-maleic anhydride copolymer, vinylpyrrolidone-vinyl acetate copolymer, gelatin, Starch or various anionic, nonionic or cationic surfactants such as sodium alkylbenzenesulfonate, sodium alkylsulfate and sodium dialkylsulfosuccinate; talc, bentonite, calcium sulfate, magnesium carbonate and the like are used. As the polymerization catalyst, an acyl peroxide such as lauroyl peroxide, a peroxy ester of an organic acid such as t-butyl peroxypiperate, an azo compound such as azobisisobutyronitrile, a diisopropyl peroxy diester, and the like. An oil-soluble catalyst such as peroxydicarbonate such as carbonate, a water-soluble catalyst such as potassium persulfate, or a redox catalyst composed of persulfuric acid as an oxidizing component and sulfurous acid as a reducing component is used.
【００１２】本発明において加えられる直流電圧は、不
溶性電極の形状、大きさ、種類、重合装置本体の大き
さ、液体媒質および被覆電気絶縁体の誘電率等によって
も左右され、一律には規定できないが、少なくとも両電
極間に絶縁破壊が生じない範囲の電圧であり、通常１０
０〜５０００Ｖ程度の電圧が加えられる。The DC voltage applied in the present invention depends on the shape, size and type of the insoluble electrode, the size of the main body of the polymerization apparatus, the dielectric constant of the liquid medium and the coated electrical insulator, and cannot be uniformly defined. Is a voltage within a range in which at least dielectric breakdown does not occur between both electrodes,
A voltage of about 0 to 5000 V is applied.
【００１３】[0013]
【発明の効果】本発明の重合方法により、重合反応器の
内壁や攪拌機等へのスケール等の付着を殆どなくすこと
が可能になった。EFFECTS OF THE INVENTION The polymerization method of the present invention makes it possible to almost eliminate the adhesion of scale or the like to the inner wall of a polymerization reactor or a stirrer.
【００１４】[0014]
実施例１ 厚さ２mmのポリエステル樹脂でライニングされた内壁及
び攪拌機を有する５０ｌの鉄製オートクレーブ中に下記
成分を添加した。Example 1 The following components were added to a 50 l iron autoclave having an inner wall and a stirrer lined with a 2 mm thick polyester resin.
【００１５】[0015]
【表１】 重合反応容器中には陰極として白金電極を有し、容器壁
金属部に陽極を接続した。重合反応中は３００Ｖの電圧
を印加しつつ、折曲圧力５kg／cm2 Ｇ、温度５８℃にて
７時間重合を行った。重合終了後冷却しオートクレーブ
の圧力を開放し、重合物を排出した後オートクレーブの
上蓋を開いた。重合反応器内壁面及び攪拌機には一切重
合付着物は見られなかった。また同様の重合操作を１０
回繰返した後も、オートクレーブ内の付着物は皆無であ
った。 比較例 外部電源による電圧を印加しなかったことを除いては、
実施例１と全く同様にして重合を行った。[Table 1] A platinum electrode was provided as a cathode in the polymerization reaction vessel, and an anode was connected to the metal portion of the vessel wall. During the polymerization reaction, while applying a voltage of 300 V, the polymerization was carried out at a bending pressure of 5 kg / cm 2 G and a temperature of 58 ° C. for 7 hours. After completion of the polymerization, the autoclave was cooled, the pressure in the autoclave was released, the polymer was discharged, and the upper lid of the autoclave was opened. No polymer deposit was found on the inner wall surface of the polymerization reactor or on the stirrer. In addition, the same polymerization operation was performed 10
After repeating the cycle, there were no deposits in the autoclave. Comparative Example Except that the voltage from the external power supply was not applied,
Polymerization was carried out in exactly the same manner as in Example 1.
【００１６】第１回目の重合反応の後にはオートクレー
ブ内面にはわずかに白色不透明の付着物が生成されてい
た。内部の内清浄化を行うことなく、１０回上記の重合
反応を繰返したところ、オートクレーブ内壁面全体に１
mm厚以上の白色付着物が形成されており、内壁の気液界
面及び攪拌羽根取付中心部は特に付着量が大であった。After the first polymerization reaction, a slight white opaque deposit was formed on the inner surface of the autoclave. When the above polymerization reaction was repeated 10 times without cleaning the inside, 1
White deposits with a thickness of mm or more were formed, and the attached amount was particularly large at the gas-liquid interface of the inner wall and the center part of the stirring blade attachment.
【図１】本発明の重合方法の一実施態様例を示す模式図
である。FIG. 1 is a schematic diagram showing an embodiment of a polymerization method of the present invention.
【図２】本発明の重合方法の他の実施態様例を示す模式
図である。FIG. 2 is a schematic view showing another embodiment example of the polymerization method of the present invention.
１ 重合反応器本体 ２ 被覆電気絶縁体 ３ 外部電極 ４ 不溶性電極 1 Polymerization reactor body 2 Coated electrical insulator 3 External electrode 4 Insoluble electrode
Claims (1)
または懸濁重合するに際して、重合反応器の内壁及び攪
拌翼等の反応器内配設物の金属部分を一方の電極とし、
重合反応器内の液体媒質中に配置した少なくとも１個の
不溶性導電体を他方の電極とし、これら電極のいずれか
一方若しくは双方に電気絶縁材で被覆されたものを用
い、重合反応器内の液体媒質及び被覆電気絶縁体を複合
誘電体とし、両電極間に絶縁破壊電圧未満の直流電圧を
印加してコンデンサー回路を生成させた状態で重合を実
施することを特徴とする重合方法。1. When emulsion-polymerizing or suspension-polymerizing a polymerizable monomer in a polymerization reactor, a metal portion of an inner wall of the polymerization reactor and a reactor internal arrangement such as a stirring blade is used as one electrode,
At least one insoluble conductor disposed in a liquid medium in the polymerization reactor is used as the other electrode, and one or both of these electrodes coated with an electric insulating material is used. A polymerization method, wherein the medium and the coated electric insulator are composite dielectrics, and a polymerization is carried out in a state where a DC voltage lower than the dielectric breakdown voltage is applied between both electrodes to form a capacitor circuit.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3197895A JPH0539308A (en) | 1991-08-07 | 1991-08-07 | Polymerization method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3197895A JPH0539308A (en) | 1991-08-07 | 1991-08-07 | Polymerization method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0539308A true JPH0539308A (en) | 1993-02-19 |
Family
ID=16382078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3197895A Pending JPH0539308A (en) | 1991-08-07 | 1991-08-07 | Polymerization method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0539308A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10844343B2 (en) * | 2015-01-21 | 2020-11-24 | Hugo Vogelsang Maschinenbau Gmbh | Device for the electrical disintegration of cell structures, and installation and use of the device for producing feed intermediates and feed products |
-
1991
- 1991-08-07 JP JP3197895A patent/JPH0539308A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10844343B2 (en) * | 2015-01-21 | 2020-11-24 | Hugo Vogelsang Maschinenbau Gmbh | Device for the electrical disintegration of cell structures, and installation and use of the device for producing feed intermediates and feed products |
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