JPH0224304A - Manufacture of vinyl chloride resin - Google Patents
Manufacture of vinyl chloride resinInfo
- Publication number
- JPH0224304A JPH0224304A JP17429988A JP17429988A JPH0224304A JP H0224304 A JPH0224304 A JP H0224304A JP 17429988 A JP17429988 A JP 17429988A JP 17429988 A JP17429988 A JP 17429988A JP H0224304 A JPH0224304 A JP H0224304A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- polymerization
- chloride resin
- saponification
- degree
- 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
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229920005989 resin Polymers 0.000 title claims abstract description 34
- 239000011347 resin Substances 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 238000007127 saponification reaction Methods 0.000 claims abstract description 12
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 9
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 8
- 239000012736 aqueous medium Substances 0.000 claims abstract description 7
- 239000011541 reaction mixture Substances 0.000 claims abstract description 6
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- 150000008301 phosphite esters Chemical class 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 abstract description 10
- 238000000465 moulding Methods 0.000 abstract description 4
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 9
- 239000002002 slurry Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 5
- -1 phosphorous ester Chemical class 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241000156978 Erebia Species 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- MOABYHZDQQELLG-UHFFFAOYSA-N OP(O)OP(O)O.C(CCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCC Chemical compound OP(O)OP(O)O.C(CCCCCCCCCCCC)C(O)(C(CO)(CO)CO)CCCCCCCCCCCCC MOABYHZDQQELLG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical group CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000006084 composite stabilizer Substances 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- 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
- 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
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- RTANHMOFHGSZQO-UHFFFAOYSA-N 4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)C#N RTANHMOFHGSZQO-UHFFFAOYSA-N 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910004860 CaZn Inorganic materials 0.000 description 1
- 229920005682 EO-PO block copolymer Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 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 1
- 239000005639 Lauric acid Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- QAEPIAHUOVJOOM-UHFFFAOYSA-N OP(O)OP(O)O.C(CCCCCCCC)C1=C(C=CC=C1)C(O)(C(CO)(CO)CO)C1=C(C=CC=C1)CCCCCCCCC Chemical compound OP(O)OP(O)O.C(CCCCCCCC)C1=C(C=CC=C1)C(O)(C(CO)(CO)CO)C1=C(C=CC=C1)CCCCCCCCC QAEPIAHUOVJOOM-UHFFFAOYSA-N 0.000 description 1
- LZNWGSIDNAGRAJ-UHFFFAOYSA-N P(O)(O)OC(C(C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)(C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)(CCCCCCCCCCCCC)C1=CC=CC=C1 Chemical compound P(O)(O)OC(C(C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)(C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)C(OP(O)O)(CCCCCCCCCCCCC)C1=CC=CC=C1)(CCCCCCCCCCCCC)C1=CC=CC=C1 LZNWGSIDNAGRAJ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- BSVQJWUUZCXSOL-UHFFFAOYSA-N cyclohexylsulfonyl ethaneperoxoate Chemical compound CC(=O)OOS(=O)(=O)C1CCCCC1 BSVQJWUUZCXSOL-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ZFTFAPZRGNKQPU-UHFFFAOYSA-N dicarbonic acid Chemical compound OC(=O)OC(O)=O ZFTFAPZRGNKQPU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 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
- UPWGQKDVAURUGE-UHFFFAOYSA-N glycerine monooleate Natural products CCCCCCCCC=CCCCCCCCC(=O)OC(CO)CO UPWGQKDVAURUGE-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 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 description 1
- 239000007788 liquid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 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
- 239000002994 raw material Substances 0.000 description 1
- 230000009291 secondary effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、塩化ビニル系樹脂の製造方法に関し、特に、
成形加工後の透明性に優れた塩化ビニル系樹脂に関する
。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing vinyl chloride resin, and in particular,
This invention relates to a vinyl chloride resin with excellent transparency after molding.
〔従来の技術］
従来、塩化ビニル系樹脂の製造時に低けん化度の部分け
ん化ポリビニルアルコールを添加して重合することによ
り、得られる塩化ビニル系樹脂の加工性、ポロシティ−
１脱モノマー性等が改良されることが知られている。ま
た、部分けん化ポリビニルアルコールを使用して重合を
行うと、得られる塩化ビニル系樹脂中に水酸基が導入さ
れるため、塩化ビニル系樹脂に安定剤としてＢａ−Ｚｎ
系、Ｃａ−Ｚｎ系等の無毒性安定剤を配合することによ
り、塩化ビニル系樹脂の熱安定性を向上させることがで
きるという副次的効果も得られることも知られている。[Prior Art] Conventionally, during the production of vinyl chloride resin, partially saponified polyvinyl alcohol with a low degree of saponification is added and polymerized to improve the processability and porosity of the resulting vinyl chloride resin.
It is known that demonomer properties and the like are improved. In addition, when polymerization is performed using partially saponified polyvinyl alcohol, hydroxyl groups are introduced into the resulting vinyl chloride resin, so Ba-Zn is used as a stabilizer in the vinyl chloride resin.
It is also known that the secondary effect of improving the thermal stability of vinyl chloride resins can be obtained by blending non-toxic stabilizers such as those based on polyvinyl chloride or Ca-Zn.
しかし、上記のようにして得られる塩化ビニル系樹脂は
、シート、フィルム等に成形加工されると、透明性が低
下するという欠点があった。However, the vinyl chloride resin obtained as described above has a drawback in that its transparency decreases when it is molded into sheets, films, etc.
そこで、本発明の目的は、成形加工品の透明性に優れた
塩化ビニル系樹脂の製造方法を提供することにある。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a method for producing a vinyl chloride resin that provides a molded product with excellent transparency.
本発明は、上記課題を解決するために、塩化ビニル又は
塩化ビニルを含むビニル系単量体を、低けん化度の部分
けん化ポリビニルアルコールの存在下、水性媒体中で懸
濁重合する塩化ビニル系樹脂の製造方法であって、重合
開始前、重合中及び重合終了後の少なくとも１つの段階
で反応混合物に及び／又は反応混合物から分離後の生成
塩化ビニル系樹脂に、多価アルコールの亜リン酸エステ
ルを添加することを特徴とする塩化ビニル系樹脂の製造
方法を提供するものである。In order to solve the above problems, the present invention provides a vinyl chloride resin in which vinyl chloride or a vinyl monomer containing vinyl chloride is suspension-polymerized in an aqueous medium in the presence of partially saponified polyvinyl alcohol with a low degree of saponification. A method for producing a phosphite ester of a polyhydric alcohol, wherein a phosphorous ester of a polyhydric alcohol is added to the reaction mixture at least one stage before the start of polymerization, during the polymerization, and after the end of the polymerization, and/or to the resulting vinyl chloride resin after separation from the reaction mixture. The present invention provides a method for producing a vinyl chloride resin, which is characterized by adding.
本発明の方法において用いられる多価アルコールの亜リ
ン酸エステルとしては、例えば、テトラフェニルテトラ
（トリデシル）ペンタエリスリトールテトラホスファイ
ト、ビス（トリデシル）ペンタエリスリトールジホスフ
ァイト、ビス（ノニルフェニル）ペンタエリスリトール
ジホスファイト、ジステアリルペンタエリスリトールジ
ホスファイト、水添ビスフェノールＡ−ペンタエリスリ
トールホスファイトポリマー等が挙げられ、これらの中
でも分子量５５０以上、リンの含有率６重量％以上のも
のが好ましい。これらは１種単独でも２種以上でも用い
ることができる。Examples of the polyhydric alcohol phosphite used in the method of the present invention include tetraphenyltetra(tridecyl)pentaerythritol tetraphosphite, bis(tridecyl)pentaerythritol diphosphite, and bis(nonylphenyl)pentaerythritol diphosphite. Examples include phosphite, distearyl pentaerythritol diphosphite, hydrogenated bisphenol A-pentaerythritol phosphite polymer, and among these, those with a molecular weight of 550 or more and a phosphorus content of 6% by weight or more are preferred. These can be used alone or in combination of two or more.
本発明の方法において、上記多価アルコールの亜リン酸
エステルの添加量は、得られる塩化ビニル系樹脂に対し
、通常、０．００５〜０．３重量％となる量が好ましい
。多価アルコールの亜リン酸エステルの添加量が少な過
ぎると得られる塩化ビニル系樹脂の透明性が改良されず
、また一定量を超えると透明性がそれ以上改良されない
ので多過ぎると経済的でない。In the method of the present invention, the amount of the polyhydric alcohol phosphite added is generally preferably 0.005 to 0.3% by weight based on the vinyl chloride resin obtained. If the amount of phosphite of polyhydric alcohol added is too small, the transparency of the resulting vinyl chloride resin will not be improved, and if it exceeds a certain amount, the transparency will not be improved any further, so if it is too large, it is not economical.
この多価アルコールの亜リン酸エステルの添加は、重合
開始前又は重合中に重合系に、重合終了後のスラリー中
に、あるいはスラリーから分離後の生成塩化ビニル系樹
脂に、すなわち脱水後のケーキ中、乾燥後又は成形直前
の樹脂中などの段階で行うことができ、これらのうち少
なくとも１つの段階で添加されればよく、また添加を複
数の段階に分けて行ってもよい。添加は、いずれの方法
によっても行うことができ、例えば、水又は溶媒に溶解
した溶液として、分散液として、あるいは粉体又は液状
のまま、重合系、スラリー又は重合体に添加してもよい
。This polyhydric alcohol phosphite is added to the polymerization system before or during polymerization, to the slurry after polymerization, or to the vinyl chloride resin produced after separation from the slurry, that is, to the cake after dehydration. It can be added at a stage such as inside the resin, after drying, or just before molding, and it suffices if it is added at at least one of these stages, or the addition may be carried out in multiple stages. The addition can be carried out by any method, for example, it may be added to the polymerization system, slurry or polymer as a solution in water or a solvent, as a dispersion, or as a powder or liquid.
本発明の方法において重合に供される原料は、塩化ビニ
ル又は塩化ビニルを含むビニル系単量体である。塩化ビ
ニルを含むビニル系単量体は、塩化ビニルと、塩化ビニ
ルと共重合可能な単量体との混合物である。この塩化ビ
ニルと共重合可能な単量体としては、例えば、酢酸ビニ
ル、プロピオン酸ビニル等のビニルエステル；アクリル
酸メチル、アクリル酸エチル等のアクリル酸エステル又
はメタアクリル酸メチル、メタアクリル酸エチル等のメ
タアクリル酸エステル；エチレン、プロピレン等のオレ
フィン；無水マレイン酸；アクリロニトリル；スチレン
；塩化ビニリデンその他が挙げられる。これらの単量体
は、１種単独または２種以上を用いてもよい。塩化ビニ
ルを含むビニル系単量体は、通常、５０重量％以上の塩
化ビニルを含むものであるが、特に限定されない。The raw material subjected to polymerization in the method of the present invention is vinyl chloride or a vinyl monomer containing vinyl chloride. A vinyl monomer containing vinyl chloride is a mixture of vinyl chloride and a monomer copolymerizable with vinyl chloride. Examples of monomers copolymerizable with vinyl chloride include vinyl esters such as vinyl acetate and vinyl propionate; acrylic esters such as methyl acrylate and ethyl acrylate; methyl methacrylate and ethyl methacrylate; methacrylic acid esters; olefins such as ethylene and propylene; maleic anhydride; acrylonitrile; styrene; vinylidene chloride and others. These monomers may be used alone or in combination of two or more. The vinyl monomer containing vinyl chloride usually contains 50% by weight or more of vinyl chloride, but is not particularly limited.
本発明の方法において使用される低けん化度の部分けん
化ポリビニルアルコールは、けん化度２０〜７５モル％
のものである。けん化度が高すぎると得られる塩化ビニ
ル系樹脂の加工性が悪くなり、けん化度が低すぎると重
合時における水性媒体中の塩化ビニルの分散性が悪くな
る。またこの部分けん化ポリビニルアルコールの重合度
は、通常、好ましくは１５０〜７５０である。The partially saponified polyvinyl alcohol with a low saponification degree used in the method of the present invention has a saponification degree of 20 to 75 mol%.
belongs to. If the degree of saponification is too high, the processability of the resulting vinyl chloride resin will be poor, and if the degree of saponification is too low, the dispersibility of vinyl chloride in the aqueous medium during polymerization will be poor. Further, the degree of polymerization of this partially saponified polyvinyl alcohol is usually preferably 150 to 750.
また、本発明の方法においては、上記部分けん化ポリビ
ニルアルコールとともに、水性媒体中での懸濁重合に際
して通常使用されている分散助剤を使用してもよい。こ
の分散助剤としては、例えば、メチルセルロース、ヒド
ロキシエチルセルロース、ヒドロキシプロピルセルロー
ス、ヒドロキシプロピルメチルセルロース等の水溶性セ
ルロースエーテル；アクリル酸重合体；ゼラチン等の水
溶性ポリマー；上記低けん化度の部分けん化ポリビニル
アルコール以外の部分けん化ポリビニルアルコール；ソ
ルビタンモノラウレート、ソルビタントリオレート、グ
リセリントリステアレート、エチレンオキシドープロピ
レンオキシドブロック共重合体等の油溶性乳化剤；ポリ
オキシエチレンソルビタンモノラウレート、ポリオキシ
エチレングリセリンオレート、ラウリン酸ナトリウム等
の水溶性乳化剤などが挙げられる。これらは１種単独で
も２種以上でも用いることができる。Further, in the method of the present invention, a dispersion aid commonly used in suspension polymerization in an aqueous medium may be used in addition to the partially saponified polyvinyl alcohol. Examples of the dispersion aid include water-soluble cellulose ethers such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and hydroxypropyl methyl cellulose; acrylic acid polymers; water-soluble polymers such as gelatin; Partially saponified polyvinyl alcohol; Oil-soluble emulsifiers such as sorbitan monolaurate, sorbitan triolate, glycerin tristearate, ethylene oxide propylene oxide block copolymer; polyoxyethylene sorbitan monolaurate, polyoxyethylene glycerin oleate, lauric acid Examples include water-soluble emulsifiers such as sodium. These can be used alone or in combination of two or more.
本発明の方法において用いられる重合開始剤は、特に制
限されず、従来、塩化ビニル系重合体の製造に使用され
ているものでよく、例えばジイソプロピルパーオキシジ
カーボネート、ジー２−エチルへキシルパーオキシジカ
ーボネート、ジェトキシエチルパーオキシジカーボネー
ト等のパーカーボネート化合物；む−ブチルパーオキシ
ネオデカネート、α−クミルパーオキシネオデカネート
等のパーエステル化合物；アセチルシクロヘキシルスル
ホニルパーオキシド、２，４．１−トリメチルペンチル
−２−パーオキシフェノキシアセテート等の過酸化物：
アゾビス−２，４−ジメチルバレロニトリル、アゾビス
（４−メトキシ−２，４ジメチルバレロニトリル）等の
アブ化合物；過硫酸カリウム、過硫酸アンモニウム、過
酸化水素等が挙げられる。これらは１種単独でも２種以
上でも用いることができる。The polymerization initiator used in the method of the present invention is not particularly limited, and may be those conventionally used in the production of vinyl chloride polymers, such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxy Percarbonate compounds such as dicarbonate and jetoxyethyl peroxydicarbonate; Perester compounds such as m-butylperoxyneodecanate and α-cumylperoxyneodecanate; Acetylcyclohexylsulfonyl peroxide, 2,4.1 -Peroxides such as trimethylpentyl-2-peroxyphenoxyacetate:
Abu compounds such as azobis-2,4-dimethylvaleronitrile and azobis(4-methoxy-2,4dimethylvaleronitrile); potassium persulfate, ammonium persulfate, hydrogen peroxide, and the like. These can be used alone or in combination of two or more.
本発明の方法において、塩化ビニル又は塩化ビニルを含
むビニル系単量体の重合に際しての他の条件、例えば重
合器への水性媒体、単量体、分散助剤、重合開始剤等の
仕込み方法、重合温度、重合圧力等の重合条件は、従来
の塩化ビニル系重合体の製造方法と同様でよく、特に制
限されない。In the method of the present invention, other conditions during polymerization of vinyl chloride or a vinyl monomer containing vinyl chloride, such as the method of charging an aqueous medium, monomer, dispersion aid, polymerization initiator, etc. to the polymerization vessel, Polymerization conditions such as polymerization temperature and polymerization pressure may be the same as in conventional methods for producing vinyl chloride polymers, and are not particularly limited.
本発明の方法においては、さらに必要に応じて塩化ビニ
ル系重合体の製造に通常、使用される重合調整剤、連鎖
移動剤、ｐｌ＋調整剤、ゲル化改良剤、帯電防止剤、ス
ケール防止剤等を使用することもできる。In the method of the present invention, if necessary, a polymerization regulator, a chain transfer agent, a PL+ regulator, a gelling improver, an antistatic agent, an anti-scaling agent, etc., which are usually used in the production of vinyl chloride polymers, etc. You can also use
以下、本発明を実施例及び比較例により具体的に説明す
るが、本発明はこれに限定されるものではない。EXAMPLES Hereinafter, the present invention will be specifically explained using Examples and Comparative Examples, but the present invention is not limited thereto.
実施例１〜４
各実施例において、内容積２０００１の攪拌器及び加熱
用ジャケットを備えたステンレス製重合器に、脱イオン
水９００ｇ、けん化度４８．２モル％の部分けん化ポリ
ビニルアルコール（重合度３００） １８０ｇ、分散助
剤としてけん化度８０．２モル％の部分けん化ポリビニ
ルアルコール（重合度２６００）４２０ｇ 、及び表１
に示す重合開始剤３６０ｇを仕込み、重合器内の圧力が
５０ｍｍＨｇになるまで脱気した後、塩化ビニル６００
ｋｇを仕込んだ。攪拌しながら加熱用ジャケットに熱水
を通して重合器内温を５２°Ｃに昇温し、この温度を保
持して重合反応を進行させた。重合器内の圧力が６．０
ｋｇ／ｃｆｆｌ・Ｇに低下した後、未反応単量体を除
去し、重合体スラリーを得た。この重合体スラリーに表
１に示す多価アルコールの亜リン酸エステル９６０ｇを
加え、重合器から取り出した。Examples 1 to 4 In each example, 900 g of deionized water and partially saponified polyvinyl alcohol with a saponification degree of 48.2 mol% (a polymerization degree of 300 ) 180 g, 420 g of partially saponified polyvinyl alcohol (degree of polymerization 2600) with a saponification degree of 80.2 mol% as a dispersion aid, and Table 1
After charging 360 g of the polymerization initiator shown in , and degassing until the pressure inside the polymerization vessel became 50 mmHg, 600 g of vinyl chloride was added.
I loaded kg. While stirring, hot water was passed through the heating jacket to raise the internal temperature of the polymerization vessel to 52°C, and this temperature was maintained to allow the polymerization reaction to proceed. The pressure inside the polymerization vessel is 6.0
After the concentration was reduced to kg/cffl·G, unreacted monomers were removed to obtain a polymer slurry. 960 g of phosphite ester of polyhydric alcohol shown in Table 1 was added to this polymer slurry, and the slurry was taken out from the polymerization vessel.
取り出した重合体スラリーを脱水、乾燥して塩化ビニル
樹脂を得た。The polymer slurry taken out was dehydrated and dried to obtain a vinyl chloride resin.
得られた塩化ビニル樹脂１００重量部に、ＤＯＰ４５重
量部、エポキシ化大豆油５重量部、Ｂａ −Ｚｎ系の複
合安定剤であるＡ Ｃ−１８６及びＲｕｐ−１０（共に
アデカアーガス社製）をそれぞれ１重量部加えた後、テ
ストロールを用いて、１５０°Ｃで５分間混練し、厚さ
０．５ｍｍのシートに成形した。To 100 parts by weight of the obtained vinyl chloride resin, 45 parts by weight of DOP, 5 parts by weight of epoxidized soybean oil, and Ba-Zn composite stabilizers A C-186 and Rup-10 (both manufactured by Adeka Argus) were added. After adding 1 part by weight, the mixture was kneaded for 5 minutes at 150°C using a test roll and formed into a sheet with a thickness of 0.5 mm.
このシートを１９０’Ｃの温度のギヤーオーブン中に入
れ、完全に黒化するまでの時間を測定し、熱安定性の指
標とした。This sheet was placed in a gear oven at a temperature of 190'C, and the time until it completely blackened was measured, which was used as an index of thermal stability.
さらに厚さ０．５ ｔｒｒｍのシートを１８５°Ｃで６
分間プレスして厚さ５ ｍｍの透明な試験片を作製し、
この試験片の光線透過率及び曇価をヘイズメーター（日
本重色工業社製）を用いて測定した。Furthermore, a sheet with a thickness of 0.5 trrm was heated at 185°C for 6
A transparent test piece with a thickness of 5 mm was prepared by pressing for a minute.
The light transmittance and haze value of this test piece were measured using a haze meter (manufactured by Nihon Heavy Industries Co., Ltd.).
結果を表１に示す。The results are shown in Table 1.
比較例１〜２
比較例１及び２において、多価アルコールの亜リン酸エ
ステルを添加しない以外は、それぞれ実施例１及び２と
同様にして塩化ビニル樹脂を製造し、熱安定性、光線透
過率及び曇価を測定した。Comparative Examples 1 and 2 In Comparative Examples 1 and 2, vinyl chloride resins were produced in the same manner as in Examples 1 and 2, respectively, except that phosphite of polyhydric alcohol was not added, and the thermal stability and light transmittance were and haze value were measured.
結果を表１に示す。The results are shown in Table 1.
実施例５
多価アルコールの亜リン酸エステルを添加しない以外は
、実施例１と同様に重合し、生成した重合体スラリーを
脱水・乾燥して塩化ビニル樹脂を得た。Example 5 Polymerization was carried out in the same manner as in Example 1 except that phosphite of polyhydric alcohol was not added, and the resulting polymer slurry was dehydrated and dried to obtain a vinyl chloride resin.
得られた塩化ビニル樹脂１００重量部に、ビス（トリデ
シル）ペンタエリスリトールジホスファイト０．１重量
部、ＤＯＰ４５重量部、エポキシ化大豆油５重量部、Ｂ
ａ−Ｚｎ系の複合安定剤であるＡＣ１８６及びＲｕｐ−
１０（共にアデカアーガス社製）をそれぞれ１重量部添
加し、実施例１と同様にして熱安定性、光線透過率及び
曇価を測定した。結果を下記に示す。To 100 parts by weight of the obtained vinyl chloride resin, 0.1 part by weight of bis(tridecyl)pentaerythritol diphosphite, 45 parts by weight of DOP, 5 parts by weight of epoxidized soybean oil, B
AC186 and Rup- which are a-Zn based composite stabilizers
10 (both manufactured by Adeka Argus) were added thereto, and the thermal stability, light transmittance, and haze value were measured in the same manner as in Example 1. The results are shown below.
光線透過率： ７６．５％
曇価： １２．７％
熱安定性： １１０ ｍｉｎ
〔発明の効果］
本発明の方法によれば、成形加工後の透明性に優れた塩
化ビニル系樹脂を得ることができる。この塩化ビニル系
樹脂は、シート、フィルム等の成形材料として有用であ
る。しかも、得られる塩化ビニル系樹脂は、加工性、ポ
ロシティ−及び脱モノマー性も良好であり、さらに、Ｂ
ａ−Ｚｎ系、ＣａＺｎ系等の無毒性安定剤を配合した場
合には、これらの安定剤による塩化ビニル系樹脂の熱安
定性の向上効果も得られる。Light transmittance: 76.5% Haze value: 12.7% Thermal stability: 110 min [Effects of the Invention] According to the method of the present invention, a vinyl chloride resin with excellent transparency after molding can be obtained. I can do it. This vinyl chloride resin is useful as a molding material for sheets, films, and the like. In addition, the obtained vinyl chloride resin has good processability, porosity, and demonomerization properties, and also has B
When a non-toxic stabilizer such as a-Zn type or CaZn type is blended, the effect of improving the thermal stability of the vinyl chloride resin can also be obtained by these stabilizers.
Claims (1)
けん化度の部分けん化ポリビニルアルコールの存在下、
水性媒体中で懸濁重合する塩化ビニル系樹脂の製造方法
であって、重合開始前、重合中及び重合終了後の少なく
とも１つの段階で反応混合物に及び／又は反応混合物か
ら分離後の生成塩化ビニル系樹脂に、多価アルコールの
亜リン酸エステル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。Vinyl chloride or a vinyl monomer containing vinyl chloride in the presence of partially saponified polyvinyl alcohol with a low degree of saponification,
A method for producing a vinyl chloride resin by suspension polymerization in an aqueous medium, wherein the produced vinyl chloride is added to the reaction mixture and/or after separation from the reaction mixture in at least one stage before the start of the polymerization, during the polymerization, and after the end of the polymerization. A method for producing a vinyl chloride resin, which comprises adding a phosphite ester of a polyhydric alcohol to the resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17429988A JPH0224304A (en) | 1988-07-13 | 1988-07-13 | Manufacture of vinyl chloride resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17429988A JPH0224304A (en) | 1988-07-13 | 1988-07-13 | Manufacture of vinyl chloride resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0224304A true JPH0224304A (en) | 1990-01-26 |
Family
ID=15976239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17429988A Pending JPH0224304A (en) | 1988-07-13 | 1988-07-13 | Manufacture of vinyl chloride resin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0224304A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011040575A1 (en) | 2009-09-30 | 2011-04-07 | 株式会社日本触媒 | Polyacrylic acid salt-based water absorbent resin and method for producing same |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5250983A (en) * | 1975-10-21 | 1977-04-23 | Adeka Argus Chem Co Ltd | Stabilized organic material composition |
| JPS5333343A (en) * | 1976-09-09 | 1978-03-29 | Mitsubishi Electric Corp | Input monitoring digital protective relay |
| JPS5337678A (en) * | 1976-07-06 | 1978-04-06 | Hoechst Ag | Production and use of novel organic phosphites |
| JPS61165397A (en) * | 1984-12-24 | 1986-07-26 | チバ‐ガイギ‐アクチエンゲゼルシヤフト | Pentaerythritoldiphosphites, manufacture and use as stabilizer |
| JPS62297361A (en) * | 1986-06-18 | 1987-12-24 | Adeka Argus Chem Co Ltd | Stabilized synthetic resin composition |
-
1988
- 1988-07-13 JP JP17429988A patent/JPH0224304A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5250983A (en) * | 1975-10-21 | 1977-04-23 | Adeka Argus Chem Co Ltd | Stabilized organic material composition |
| JPS5337678A (en) * | 1976-07-06 | 1978-04-06 | Hoechst Ag | Production and use of novel organic phosphites |
| JPS5333343A (en) * | 1976-09-09 | 1978-03-29 | Mitsubishi Electric Corp | Input monitoring digital protective relay |
| JPS61165397A (en) * | 1984-12-24 | 1986-07-26 | チバ‐ガイギ‐アクチエンゲゼルシヤフト | Pentaerythritoldiphosphites, manufacture and use as stabilizer |
| JPS62297361A (en) * | 1986-06-18 | 1987-12-24 | Adeka Argus Chem Co Ltd | Stabilized synthetic resin composition |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011040575A1 (en) | 2009-09-30 | 2011-04-07 | 株式会社日本触媒 | Polyacrylic acid salt-based water absorbent resin and method for producing same |
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