JPH04145104A - Production of polymer powder - Google Patents
Production of polymer powderInfo
- Publication number
- JPH04145104A JPH04145104A JP26791590A JP26791590A JPH04145104A JP H04145104 A JPH04145104 A JP H04145104A JP 26791590 A JP26791590 A JP 26791590A JP 26791590 A JP26791590 A JP 26791590A JP H04145104 A JPH04145104 A JP H04145104A
- Authority
- JP
- Japan
- Prior art keywords
- salting
- polymer
- emulsion
- rubber
- styrene
- 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
- 229920000642 polymer Polymers 0.000 title claims abstract description 66
- 239000000843 powder Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 238000005185 salting out Methods 0.000 claims abstract description 51
- 239000000839 emulsion Substances 0.000 claims abstract description 36
- -1 acetylene alcohol Chemical compound 0.000 claims abstract description 24
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002002 slurry Substances 0.000 abstract description 23
- 238000003756 stirring Methods 0.000 abstract description 15
- 229920001971 elastomer Polymers 0.000 abstract description 14
- 239000005060 rubber Substances 0.000 abstract description 14
- 239000003795 chemical substances by application Substances 0.000 abstract description 11
- 229920001577 copolymer Polymers 0.000 abstract description 11
- 238000005187 foaming Methods 0.000 abstract description 10
- 239000004094 surface-active agent Substances 0.000 abstract description 6
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 abstract description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 abstract description 3
- 229920002379 silicone rubber Polymers 0.000 abstract description 2
- 239000004945 silicone rubber Substances 0.000 abstract description 2
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 abstract 1
- NUYADIDKTLPDGG-UHFFFAOYSA-N 3,6-dimethyloct-4-yne-3,6-diol Chemical compound CCC(C)(O)C#CC(C)(O)CC NUYADIDKTLPDGG-UHFFFAOYSA-N 0.000 abstract 1
- 229920001897 terpolymer Polymers 0.000 abstract 1
- 238000000034 method Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000002245 particle Substances 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000011362 coarse particle Substances 0.000 description 7
- 238000010981 drying operation Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 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 5
- 239000010802 sludge Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229920006243 acrylic copolymer Polymers 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 description 4
- 229920001038 ethylene copolymer Polymers 0.000 description 4
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003254 anti-foaming effect Effects 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- WRPYDXWBHXAKPT-UHFFFAOYSA-N (2-ethenylphenyl) acetate Chemical compound CC(=O)OC1=CC=CC=C1C=C WRPYDXWBHXAKPT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-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
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001291 polyvinyl halide Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VXYADVIJALMOEQ-UHFFFAOYSA-K tris(lactato)aluminium Chemical compound CC(O)C(=O)O[Al](OC(=O)C(C)O)OC(=O)C(C)O VXYADVIJALMOEQ-UHFFFAOYSA-K 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）発明の目的
［産業上の利用分野］
本発明は、重合体の乳化分散液であるエマルジョンから
塩析により重合体を析出させ重合体粉末を得る際に、特
定の薬剤を使用する重合体粉末の製造方法に関するもの
であり、エマルジョンにより高分子を製造している化学
業界、高分子を利用している電機、機械、自動車等の幅
広い業界に利用できるものである。Detailed Description of the Invention (a) Purpose of the Invention [Industrial Field of Application] The present invention provides the following methods: It relates to a method for producing polymer powder using specific chemicals, and can be used in a wide range of industries such as the chemical industry, which manufactures polymers using emulsions, and the electrical, mechanical, and automobile industries that use polymers. be.
特に、本発明により得られる重合体粉末は、塩析剤或い
は界面活性剤等の含育量が少ないため、該重合体粉末を
そのまま、或いは応力緩和剤等として他の樹脂に配合し
て使用する場合、すなわちエンジニアリングプラスチッ
ク基材、接着剤或いは塗料基材の製造に用いる時に、電
気特性或いは耐湿性を低下させることなく、材料に靭性
、耐衝撃性を付与することか可能であるため、これらの
材料を使用する幅広い業界において賞用され得るもので
ある。In particular, since the polymer powder obtained by the present invention has a low content of salting-out agents or surfactants, the polymer powder may be used as it is or mixed with other resins as a stress relaxation agent. When used in the production of engineering plastic base materials, adhesives, or paint base materials, it is possible to impart toughness and impact resistance to the material without reducing electrical properties or moisture resistance. It can be used in a wide range of industries that use the material.
［従来の技術］
重合体エマルシヨンより重合体粉末を製造する方法とし
て、該エマルジョンを塩析し重合体のスラリーを得て、
これを洗浄・脱水し、最後に乾燥する方法が知られてい
る。[Prior Art] As a method for producing a polymer powder from a polymer emulsion, the emulsion is salted out to obtain a polymer slurry,
A method is known in which this is washed, dehydrated, and finally dried.
この塩析工程においては、高撹拌の条件を採用しなけれ
ばならない場合が多いが、この様な高撹拌条件下では、
エマルジョンに発泡現象が生じ、均一な撹拌か困難とな
ることが多い。このため塩析時には、発泡現象を抑える
ために、低温で塩析を行ったり又は高温度に於て多量の
メタノール或いはシリコーン等の消泡剤を投入して塩析
を行っている。In this salting-out process, it is often necessary to use high-stirring conditions, but under such high-stirring conditions,
Foaming phenomenon occurs in the emulsion, which often makes uniform stirring difficult. For this reason, during salting out, in order to suppress the foaming phenomenon, salting out is carried out at a low temperature or at a high temperature by adding a large amount of antifoaming agent such as methanol or silicone.
［本発明が解決しようとする課題］
しかしながら、上記メタノール或いはシリコーン等の消
泡剤は、加温してゆくと消泡効果か激減したり、洗浄等
の後処理によりスラリーから除去することが困難である
という問題を有している。[Problems to be Solved by the Present Invention] However, the antifoaming effect of the above-mentioned antifoaming agents such as methanol or silicone decreases drastically when heated, and it is difficult to remove them from the slurry by post-processing such as washing. The problem is that
本発明者は、エマルジョンから塩析により重合体粉末を
製造する際に、高温度及び高撹拌下の塩析に於ても発泡
現象を起こさず、重合体スラリーの純水による洗浄が容
易で、さらに、最終的に得られる製品中に塩析剤等の不
純物が少ない微粒子状の重合体粉末の製造方法を見い出
すため鋭意検討を行ったのである。The present inventor has discovered that when producing a polymer powder from an emulsion by salting out, no foaming phenomenon occurs even during salting out at high temperature and with high stirring, and the polymer slurry can be easily washed with pure water. Furthermore, intensive research was conducted to find a method for producing fine particulate polymer powder with fewer impurities such as salting-out agents in the final product.
（ロ）発明の構成
［課題を解決するための手段］
本発明者は、上記課題の解決には、アセチレンアルコー
ルの存在下に塩析を行うことが有効であることを見出し
本発明を完成した。(B) Structure of the Invention [Means for Solving the Problems] The present inventor has discovered that salting out in the presence of acetylene alcohol is effective in solving the above problems, and has completed the present invention. .
すなわち、本発明は重合体エマルジョンの塩析をアセチ
レンアルコールの存在下に行うことを特徴とする重合体
粉末の製造方法に関するものであ本発明の製造方法によ
れば、高温度及び高撹拌下でのエマルジョンの塩析か可
能となり、析出したスラリー状重合体の純水による洗浄
が容易である為重合体の回収率が高く、且つ最終的に得
られた重合体粉末を微粒子状で極めて不純分の少ないも
のとすることが出来る。That is, the present invention relates to a method for producing a polymer powder, characterized in that salting out of a polymer emulsion is carried out in the presence of acetylene alcohol. The emulsion can be salted out, and the precipitated slurry polymer can be easily washed with pure water, resulting in a high polymer recovery rate. It can be made smaller.
Ｏ重合体エマルジョン
本発明に使用し得る重合体エマルジョンは、従来知られ
た熱可塑性重合体或いは熱硬化性重合体がアニオン、カ
チオン或いはノニオンの界面活性剤でエマルジョンとさ
れたものである。O Polymer Emulsion The polymer emulsion that can be used in the present invention is one in which a conventionally known thermoplastic polymer or thermosetting polymer is made into an emulsion with an anionic, cationic or nonionic surfactant.
熱可塑性重合体としては、例えば、ポリオレフィン、ポ
リジエン、ポリハロゲン化ビニル、ポリスチレン、不飽
和脂肪酸或いはこれらのエステル等の重合体、脂肪酸ビ
ニル或いは不飽和ニトリル等の重合体、又はこれらを構
成単位とする共重合体が挙げられる。又、熱硬化性樹脂
としては、尿素樹脂、エポキシ樹脂、反応性ポリエステ
ル樹脂、メラミン樹脂、フェノール樹脂、ポリアリル樹
脂、アルキド樹脂、或いはこれらの重合体の骨格を育し
、加熱による架橋性を有するグリンジル基、水酸基、カ
ルボキシル基、アミノ基或いはアリル基を結合する重合
体、又はこれらを構成単位とする共重合体が挙げられる
。Examples of thermoplastic polymers include polyolefins, polydienes, polyvinyl halides, polystyrene, unsaturated fatty acids or esters thereof, polymers such as fatty acid vinyls or unsaturated nitriles, or polymers containing these as constituent units. Examples include copolymers. In addition, as thermosetting resins, urea resins, epoxy resins, reactive polyester resins, melamine resins, phenol resins, polyallyl resins, alkyd resins, or Grindyl, which grows the skeleton of these polymers and has crosslinking properties by heating, can be used. Examples include polymers bonding groups, hydroxyl groups, carboxyl groups, amino groups, or allyl groups, or copolymers having these as constituent units.
本発明は、とりわけアクリルゴム、アクリロニドルーブ
タジェンゴム、スチレン−ブタジェンゴム、スチレン−
イソプレンゴム、スチレン−プロピレン−ジエン三次元
共重合ゴム、シリコーンゴム或いはスチレン−酢ビゴム
等のゴムエマルジョンから、塩析で重合体粉末を得るの
に適している方法である。The invention particularly relates to acrylic rubber, acrylonidol-butadiene rubber, styrene-butadiene rubber, styrene-butadiene rubber,
This method is suitable for obtaining a polymer powder by salting out from a rubber emulsion such as isoprene rubber, styrene-propylene-diene three-dimensional copolymer rubber, silicone rubber, or styrene-acetate rubber.
それらの中でも、これらの重合体エマルジョン、特には
ゴムエマルジョン存在下にガラス転移点が５０〜２００
℃の重合体を形成する単量体を重合させることにより得
られる、上記重合体を芯に持ち、外壁にガラス転移温度
の高い重合体を有する、いわゆるコアーシェル型の重合
体エマルジョンから、塩析で重合体粉末を得るのに、本
発明方法は適している。Among them, in the presence of these polymer emulsions, especially rubber emulsions, the glass transition temperature is 50 to 200.
From a so-called core-shell type polymer emulsion, which has the above-mentioned polymer in the core and a polymer with a high glass transition temperature on the outer wall, which is obtained by polymerizing monomers that form a polymer at The process according to the invention is suitable for obtaining polymer powders.
なお、上記コアーシェル型重合体におけるシェル部の重
合体としては、アクリロニトリル或いはメタアクリロニ
トリル、又はアクリルオキシ基、メタアクリルオキシ基
或いはビニルオキシを存するアルコキンシラン等を共重
合体構成成分とする重合体が用いられる。In addition, as the polymer of the shell part in the above-mentioned core-shell type polymer, a polymer having a copolymer component such as acrylonitrile, methacrylonitrile, or an alkoxysilane containing an acryloxy group, a methacryloxy group, or a vinyloxy group is used. It will be done.
本発明方法に適用される重合体エマルジョンにおける重
合体粒子の粒径は０．０５〜３０μであることが好まし
い。０．０５μより細かい場合は、塩析時に増粘し易く
、他方３０μを越える場合は最終製品としての重合体が
粗粒子状となり易く、各々好ましくない。The particle size of the polymer particles in the polymer emulsion applied to the method of the present invention is preferably 0.05 to 30 microns. If it is finer than 0.05μ, the viscosity tends to increase during salting out, while if it exceeds 30μ, the final product tends to be coarse particles, which are both undesirable.
又、これらの重合体エマルジョンには、無機質ゾルを混
合して使用することが出来、重合体の特性向上のために
好ましい方法である。該混合液を塩析して得られる、無
機質ゾル由来の無機質を表面に担持する重合体粉末は、
樹脂に配合する場合、樹脂への分散が容易で、且つ該樹
脂に靭性、耐衝撃性、内部応力緩和性を付与することか
可能となる。Furthermore, an inorganic sol can be mixed with these polymer emulsions, which is a preferred method for improving the properties of the polymer. A polymer powder carrying an inorganic substance derived from an inorganic sol on the surface obtained by salting out the mixed liquid is
When blended into a resin, it is easy to disperse into the resin, and it is possible to impart toughness, impact resistance, and internal stress relaxation properties to the resin.
無機質ゾルとは無機質の超微粒子を分散せしめたコロイ
ド溶液のことであり、無機質としてはソリ力、アルミナ
、酸化チタン或いは酸化鉄等を挙げることができる。An inorganic sol is a colloidal solution in which ultrafine inorganic particles are dispersed, and examples of the inorganic material include warp, alumina, titanium oxide, and iron oxide.
○アセチレンアルコール
本発明の重合体粉末製造における塩析工程で使用するア
セチレンアルコールは、分子内にアセチレン結合を持つ
アルコールを言い、一般的には、アセチレンとケトン又
はアルデヒドの付加反応により合成される化合物である
。○Acetylene alcohol Acetylene alcohol used in the salting out process in the production of polymer powder of the present invention refers to an alcohol having an acetylene bond in the molecule, and is generally a compound synthesized by an addition reaction between acetylene and a ketone or aldehyde. It is.
本発明に使用できるアセチレンアルコールとしては種々
挙げることが出来るが、市販されていて、入手し易い２
． ４． ７． ９−テトラメチル−５−デシン−４，
７−ジオール及びこれの酸化エチレン付加体、３，６−
シメチルー４−才クチン−３゜６−ジオール、並びに３
，５−ジメチル−１−ヘキシン−３−オール等を好まし
いものとして挙げることができる。There are various acetylene alcohols that can be used in the present invention, but two are commercially available and easily available.
．． 4. 7. 9-tetramethyl-5-decyne-4,
7-diol and its ethylene oxide adduct, 3,6-
Cymethyl-4-cutin-3゜6-diol, and 3
, 5-dimethyl-1-hexyn-3-ol and the like are preferred.
これらのアセチレンアルコールは、水系塗料に添加する
場合には、濡れ性、分散性或は消泡性を高めることか出
来、又オルガノゾル中に添加する場合には、該オルガノ
ゾルの粘度を低下させる機能を有することか知られてい
るが、塩析工程中に添加して使用することにより、塩析
工程を優れたものとするということは、本発明者が始め
て見出したことである。When added to water-based paints, these acetylene alcohols can improve wettability, dispersibility, or antifoaming properties, and when added to organosols, they have the function of reducing the viscosity of the organosol. However, the present inventors have discovered for the first time that the salting-out process can be improved by adding it to the salting-out process.
すなわち、重合体粉末製造の塩析工程においてアセチレ
ンアルコールを使用するとき、高温及び高撹拌下におい
ても、発泡現象が見られず、塩析か効率良く、且つ濾過
或いは重力沈降により得られるスラリーの洗浄が容易で
あること、さらには、アセチレンアルコールは、洗浄過
程に於て純水による洗浄除去が容易であり、さらに乾燥
過程で揮散し易いため、最終製品の重合体粉末中の残存
量は極めて少ないことを本発明者は見出したのである。That is, when acetylene alcohol is used in the salting-out process of polymer powder production, no foaming phenomenon is observed even under high temperature and high stirring, and the salting-out process is efficient, and the slurry obtained by filtration or gravity sedimentation can be washed. In addition, acetylene alcohol can be easily removed by washing with pure water during the washing process, and it also evaporates easily during the drying process, so the amount remaining in the final product polymer powder is extremely small. This is what the inventors have discovered.
アセチレンアルコールの使用方法としては、塩析時に、
重合体のエマルジョン中にアセチレンアルコールを溶解
或いは分散させる方法、塩析剤を溶解或いは分散する水
中にアセチレンアルコールを溶解或いは分散させる方法
、及び両者を併用して使用する方法を挙げることかでき
る。How to use acetylene alcohol is during salting out.
Examples include a method of dissolving or dispersing acetylene alcohol in a polymer emulsion, a method of dissolving or dispersing acetylene alcohol in water in which a salting-out agent is dissolved or dispersed, and a method of using both in combination.
アセチレンアルコールの好ましい使用量は、エマルジョ
ン中に存在する重合体１００重量部に対して０．０１−
１．０重量部である。０．０１重量部を満たさない場合
は、高温及び高撹拌時の塩析工程に於て発泡現象が見ら
れ、他方１．０重量部を越えて使用しても上記の本発明
の効果は同程度に得られるが、コスト的に不利な場合が
多い。The preferred amount of acetylene alcohol used is 0.01- parts by weight per 100 parts by weight of polymer present in the emulsion.
It is 1.0 part by weight. If the amount is less than 0.01 part by weight, foaming phenomenon will be observed in the salting out process at high temperature and high stirring; on the other hand, even if it is used in excess of 1.0 part by weight, the above-mentioned effects of the present invention will not be the same. However, it is often disadvantageous in terms of cost.
Ｏ塩析方法
本発明の重合体粉末製造における塩析方法としては、一
般的な公知の方法で良く、例えばアセチレンアルコール
を重合体のエマルジョン中、又は塩析剤が存在する洛中
、又は両者に添加して、塩析浴中に重合体のエマルジョ
ンを高撹拌下で連続的に添加するという方法であり、該
方法により重合体がスラリーとして析出される。Salting-out method The salting-out method for producing the polymer powder of the present invention may be a general known method, such as adding acetylene alcohol to the emulsion of the polymer, to the liquid containing the salting-out agent, or to both. In this method, an emulsion of a polymer is continuously added to a salting-out bath under high stirring, and the polymer is precipitated as a slurry.
この際、塩析剤としては、公知のもののいずれもが使用
できるが、酸類或いは多価金属塩が好ましく、特に硫酸
アルミニウム、乳酸アルミニウム或いは酢酸カルシウム
か好ましい。これらの好ましい使用量は、エマルジョン
中の重合体１． Ｏ０重量部に対して０．２〜１０重量
部である。０．２重量部を満たさない場合は重合体は塩
析され難く、他方１０重量部を越える場合は、不純物と
して最終製品に残存し易いために各々好ましくない。In this case, any known salting-out agent can be used, but acids or polyvalent metal salts are preferred, and aluminum sulfate, aluminum lactate, or calcium acetate are particularly preferred. Preferred amounts of these are 1. The amount is 0.2 to 10 parts by weight relative to O0 parts by weight. If the amount is less than 0.2 parts by weight, the polymer is difficult to be salted out, while if it exceeds 10 parts by weight, it tends to remain as impurities in the final product, which is not preferable.
塩析工程の効率に大きく影響を及ぼすため、塩析工程に
おける温度は慎重に検討して決める必要があるが、本発
明方法においては、一般的には５０〜９０°Ｃで行うの
か好ましい。５０″Ｃを満たさない場合は、塩析工程中
にスラッジが浮上し易く、他方９０°Ｃを越える場合は
粗粒子状重合体のスラリーを生成し易く各々好ましくな
い。The temperature in the salting-out step must be carefully considered and determined because it greatly affects the efficiency of the salting-out step, but in the method of the present invention, it is generally preferable to carry out the temperature at 50 to 90°C. If the temperature is less than 50"C, sludge tends to float during the salting-out step, while if it exceeds 90"C, a slurry of coarse particles is likely to be produced, which are both undesirable.
Ｏスラリーの洗浄法及び乾燥法
上記塩析法により得られた重合体のスラリーは、常法に
より重力沈降法で濃縮するか又は濾過した後、純水を加
える操作を繰り返すことにより洗浄する。Method for washing and drying O slurry The polymer slurry obtained by the above-mentioned salting-out method is concentrated by gravity sedimentation or filtered in a conventional manner, and then washed by repeating the operation of adding pure water.
又、該洗浄工程に入る前に、スラリーに酸を添加して混
合すれば、電気絶縁性を不良にするアルカリ金属イオン
或いはアルカリ土類金属イオン類を除去することか出来
、好ましいことである。Furthermore, it is preferable to add and mix an acid to the slurry before entering the cleaning step, since it is possible to remove alkali metal ions or alkaline earth metal ions that cause poor electrical insulation.
このようにして得られたスラリーは、ケーキ状に脱水し
て棚段乾燥機に通すか、又は該スラリーをノズル式又は
遠心式のスプレー乾燥機に通して霧状に分散させながら
乾燥することにより、微粉末状の重合体として得られる
。この際、乾燥温度を高めることは、沸点が低いアセチ
レンアルコール化合物を揮散し易くするため好ましい手
段である。The slurry thus obtained can be dehydrated into a cake shape and passed through a tray dryer, or the slurry can be dried by passing it through a nozzle type or centrifugal spray dryer and being dispersed in a mist. , obtained as a finely powdered polymer. In this case, increasing the drying temperature is a preferable means because it facilitates volatilization of the acetylene alcohol compound having a low boiling point.
以上の方法により、粒径１００μ以下、３０μ以下、さ
らにはｌＯμ以下の不純分が少ない重合体粉末が極めて
効率的に得られるのである。By the above method, a polymer powder with a particle size of 100 μm or less, 30 μm or less, and even 10 μm or less and containing few impurities can be obtained extremely efficiently.
［作用］
本発明の重合体粉末製造における塩析工程で、アセチレ
ンアルコールを使用することにより塩析時の発泡を防ぐ
ことができる理由は明らかではないか、アセチレンアル
コールの特異な界面活性効果による消泡効果が、常温に
おいても、高温においても発揮されるためと思われる。[Function] It is not clear why foaming can be prevented by using acetylene alcohol in the salting-out process in the production of polymer powder of the present invention, or it may be due to the unique surfactant effect of acetylene alcohol. This is thought to be because the foaming effect is exhibited both at room temperature and at high temperature.
また、塩析により得られる重合体のスラリーは、泡を含
まず水中で分散し易いものであるため、該スラリーに吸
着している塩析剤や界面活性剤の除去が容易になり、真
空濾過或いは遠心分離等の操作も容易になる。In addition, since the polymer slurry obtained by salting out does not contain bubbles and is easily dispersed in water, it is easy to remove the salting out agent and surfactant adsorbed to the slurry. Alternatively, operations such as centrifugation become easier.
従って、本発明の製造方法によれば、塩析か効率よく行
え、塩析で得られるスラリー状重合体の洗浄が容易であ
り、最終的に得られる重合体粉末を微粒子状で塩析剤或
いは界面活性剤等の不純分の少ないものとすることがで
きるのである。Therefore, according to the production method of the present invention, salting out can be carried out efficiently, the slurry polymer obtained by salting out can be easily washed, and the finally obtained polymer powder can be treated with a salting out agent or a salting out agent in the form of fine particles. This allows it to contain less impurities such as surfactants.
［実施例］ 以下実施例に基づいて、本発明を更に詳細に説明する。[Example] The present invention will be described in more detail below based on Examples.
実施例！。Example! .
［ブタジェン共重合体の調製］
２１ステンレス製オートクレーブに純水７００ｃｃ、レ
ベノールＷＺ（ポリオキシエチレンアルキルフェニルエ
ーテル硫酸ナトリウムの２６％水溶液：花王■製）５３
．８ｇｒ、過硫酸カリウム７ｇｒ、第三級ドデシルメル
カプタン１．４ ｇｒ、２−ヒドロキシエチルアクリレ
ート７ ｇｒ、アクリロニトリル１４０ｇｒ及びブタジ
ェン５５３ｇｒを仕込み、プロペラ型撹拌機で撹拌（３
５０ｒｐｍ）Ｌ、なから５０℃で！５時間乳化重合を行
った。[Preparation of butadiene copolymer] 21 In a stainless steel autoclave, add 700 cc of pure water and Lebenol WZ (26% aqueous solution of sodium polyoxyethylene alkyl phenyl ether sulfate: manufactured by Kao ■) 53
．． 8 gr, potassium persulfate 7 gr, tertiary dodecyl mercaptan 1.4 gr, 2-hydroxyethyl acrylate 7 gr, acrylonitrile 140 gr and butadiene 553 gr were charged and stirred with a propeller type stirrer (3 gr).
50rpm) L, at 50℃! Emulsion polymerization was carried out for 5 hours.
その結果、粒子径０．２〜０．４μ、固形分４５重量％
のブタジェン共重合体エマルジョンを得た。As a result, the particle size was 0.2 to 0.4μ, and the solid content was 45% by weight.
A butadiene copolymer emulsion was obtained.
［塩析操作］
塩析剤としてＡ１．（Ｓｏ、）、・＋４Ｈ！Ｏを４．５
ｇｒ、アセチレンアルコールとして２． ４． ７．
９−テトラメチル−５−デシン−４，７−ジオールを０
．４５ ｇｒ及び純水１５００ｃｃを３１ビーカーに仕
込み、プロペラ型撹拌機で撹拌（６００ｒｌｌａ＋）し
ながら上記のブタジェン共重合体エマルジョン５００ｇ
ｒを１０分間かけて連続的に添加した。[Salting out operation] A1. (So,), +4H! O to 4.5
gr, as acetylene alcohol2. 4. 7.
9-tetramethyl-5-decyne-4,7-diol 0
．． Pour 45 gr and 1500 cc of pure water into a 31 beaker, and add 500 g of the above butadiene copolymer emulsion while stirring with a propeller type stirrer (600 rlla+).
r was added continuously over 10 minutes.
さらに、６０℃に昇温し、１時間撹拌を続けたところ、
気液界面にスラッジを浮上させることなく、粗粒子のな
いスラリーが得られた。Furthermore, when the temperature was raised to 60°C and stirring was continued for 1 hour,
A slurry free of coarse particles was obtained without floating sludge on the gas-liquid interface.
［洗浄及び乾燥操作］
上記の得られたスラリーをブフナー濾過器に通してケー
キを得、それを純水１５１で再度スラリーとなし、同様
に濾過を行って水分３０重量％を含有するケーキを得た
。[Washing and drying operation] The slurry obtained above was passed through a Buchner filter to obtain a cake, which was again made into a slurry with 151 pure water and filtered in the same manner to obtain a cake containing 30% by weight of water. Ta.
該ケーキを５０°ＣでｌＯ分間棚段式乾燥器で乾燥して
平均粒径５０〜１００μの粉末状ゴム２１０ｇｒを得た
。該粉末ゴムはナトリウム６０ｐｐｍ及びアルミニウム
３０ｐｐｍ含有していた。The cake was dried in a tray dryer at 50 DEG C. for 10 minutes to obtain 210 gr of powdered rubber with an average particle size of 50 to 100 microns. The powdered rubber contained 60 ppm sodium and 30 ppm aluminum.
比較例！。Comparative example! .
［塩析操作］
実施例１に於て、使用したブタジェン共重合体エマルジ
ョンに対して、実施例１の塩析操作の中でアセチレンア
ルコールを使用せず、その代わりにメタノール２２５ｇ
ｒを投入して、他の条件は実施例１と同様にして行った
ところ、６０°Ｃに昇温した時点で発泡現象が起こり、
多量のスラッジか気液界面に浮上し、同時に気液界面に
スラリーか一部凝集した。[Salting-out operation] In Example 1, for the butadiene copolymer emulsion used, acetylene alcohol was not used in the salting-out operation of Example 1, and 225 g of methanol was used instead.
When the other conditions were the same as in Example 1, a foaming phenomenon occurred when the temperature was raised to 60°C.
A large amount of sludge floated to the gas-liquid interface, and at the same time some of the slurry coagulated at the gas-liquid interface.
し洗浄及び乾燥操作］
洗浄及び乾燥操作を実施例１と同様に行ったか、得られ
たゴムは＋７０ｇｒであり、平均粒径が２００〜３００
μの粗粒子であった。また、該粗粒子状ゴムはナトリウ
ム量１５００ｐｐｍ及びアルミニウム量５００ ｐｐｍ
含有していた。Washing and drying operation] Washing and drying operations were performed in the same manner as in Example 1, and the obtained rubber had a weight of +70 gr and an average particle size of 200 to 300.
It was a coarse particle of μ. Further, the coarse particle rubber has a sodium content of 1500 ppm and an aluminum content of 500 ppm.
It contained.
実施例２
［アクリル共重合体エマルジョンの調製］２Ａ４つロフ
ラスコに純水１０００ｃｃ、 レベノールＷＺ１９．
２ｇｒ、過硫酸カリウム０．２５ ｇｒ、アリルメタア
クリレート１． Ｏｇｒ及びｎ−ブチルアクリレ−ｈ５
００ｇｒを仕込み、プロペラ型撹拌翼で撹拌（３５０ｒ
ｐｍ）Ｌながら、フラスコの空間部分に窒素をＯ，ｌ
ｌ ／ｍｉｎて流し、７０°Ｃで３時間乳化重合を行っ
た。Example 2 [Preparation of acrylic copolymer emulsion] 1000 cc of pure water and Levenol WZ19.
2 gr, potassium persulfate 0.25 gr, allyl methacrylate 1. Ogr and n-butyl acrylate-h5
00gr and stirred with a propeller type stirring blade (350r
Pour nitrogen into the space of the flask at 0,1 pm)
The emulsion polymerization was carried out at 70°C for 3 hours at a flow rate of 1/min.
更に、レベノールＷＺ ｌ ９．２ ｇｒ、過硫酸カリ
ウム１． Ｏｇｒ、スチレンｌ ４０ ｇｒ、アクリロ
ニトリル６０ｇ「及びγ−メタアクリロキシプロピルト
リメトキシシラン５ｇｒを仕込み、更に７０℃で４時間
乳化重合を続けた。Additionally, 9.2 gr of Lebenol WZ l, 1.2 gr of potassium persulfate. Ogr, 40 gr of styrene, 60 g of acrylonitrile, and 5 gr of γ-methacryloxypropyltrimethoxysilane were charged, and emulsion polymerization was further continued at 70°C for 4 hours.
その結果、粒子径０．１〜０．２μ、固形分４０重量％
のアクリル共重合体エマルジョンを得た。As a result, the particle size was 0.1 to 0.2μ, and the solid content was 40% by weight.
An acrylic copolymer emulsion was obtained.
［有機重合体エマルジョンと無機質ゾルとの混合］上記
で得られたアクリル共重合体エマルジョン４００ｇｒと
スノーテックスＵＰ（長さ３０〜５０ｍμ及びアスペク
ト比３〜５の円柱状粒子を含む轍水珪酸含存量２０重量
％のンリカゾル：日産化学工業■製）２００ｇｒをＩｆ
ビーカーに仕込み、プロペラ型撹拌翼で３０分間撹拌（
２００ｒｌ）ｍ）混合した。[Mixing of organic polymer emulsion and inorganic sol] 400g of the acrylic copolymer emulsion obtained above and Snowtex UP (containing cylindrical particles with a length of 30 to 50 mμ and an aspect ratio of 3 to 5) If 20% by weight of Nrikasol (manufactured by Nissan Chemical Industries, Ltd.) 200g
Pour into a beaker and stir for 30 minutes with a propeller-type stirring blade (
200 rl) m) mixed.
［塩析操作］
上記で得られた育機重合体エツルノヨンとシリカゾルと
の混合エマルジョン６００ｇｒに対して、アセチレンア
ルコールとしてサーフィノール４４０ （２，４，７，
９−テトラメチル−５−デシン−４７−ジオールの酸化
エチレン付加体１日信化学工業■製）１．Ｏｇｒを使用
した以外は実施例１の［塩析操作コと同様の条件で塩析
を行ったところ、気液界面にスラッジを浮上させること
なく、粗粒子かないスラリーか得られた。[Salting out operation] Surfynol 440 (2,4,7,
Ethylene oxide adduct of 9-tetramethyl-5-decyne-47-diol (manufactured by Nissin Chemical Industry ■) 1. When salting out was carried out under the same conditions as in Example 1 except that Ogr was used, a slurry free of coarse particles was obtained without floating sludge on the gas-liquid interface.
［洗浄及び乾燥操作］
洗浄及び乾燥操作を実施例１と同様に行ったところ、平
均粒径１０〜３０μの複合嬰の重合体粉末１９０ｇｒを
得た。該重合体粉末はアクリル共重合体８０重量％、ソ
リ力成分２０重量％、ナトリウム４０ｐｐｍ及びアルミ
ニウムｌＯｐｐｍを含有していた。[Washing and Drying Operations] Washing and drying operations were carried out in the same manner as in Example 1 to obtain 190 gr of composite polymer powder with an average particle size of 10 to 30 μm. The polymer powder contained 80% by weight of acrylic copolymer, 20% by weight of warp component, 40 ppm of sodium, and 1 Oppm of aluminum.
実施例３
［エチレン共重合体エマルジョンの調製コ２１ステンレ
ス製オートクレーブに純水７００ｃｃ、ゴーセノールＧ
Ｍ−１４（ケン化度８６モル％、平均重合度１４００の
部分ケン化ＰＶＡ ；日本合成化学工業■製）＋４ｇｒ
、過硫酸カリウム１４ｇｒ、レベノールＷＺ８ｇｒ、ア
クリル酸１４ｇｒ、酢酸ビニル２７０ｇｒ及びエチレン
４１６ｇｒを仕込み、プロペラ型撹拌翼で撹拌（４００
ｒｐｍ ） Ｌなから５０°Ｃで２０時間乳化重合を行
った。Example 3 [Preparation of ethylene copolymer emulsion 21 700 cc of pure water and Gohsenol G were placed in a stainless steel autoclave.
M-14 (partially saponified PVA with a degree of saponification of 86 mol% and an average degree of polymerization of 1400; manufactured by Nippon Gosei Kagaku Kogyo ■) + 4 gr
, 14 gr of potassium persulfate, 8 gr of Lebenol WZ, 14 gr of acrylic acid, 270 gr of vinyl acetate, and 416 gr of ethylene, and stirred with a propeller type stirring blade (400 gr).
rpm) Emulsion polymerization was carried out at 50°C for 20 hours.
その結果、粒子径０．３〜０．６μ、固形分４０重量％
のエチレン共重合エマルジョンを得た。As a result, the particle size was 0.3 to 0.6μ, and the solid content was 40% by weight.
An ethylene copolymer emulsion was obtained.
［有機重合体エマルジョンと無機質ゾルとの混合］上記
で得たエチレン共重合エマルジョン４００ｇ「とスノー
テックスＵＰ２００ｇｒを実施例２と同様に混合した。[Mixing of organic polymer emulsion and inorganic sol] 400 g of the ethylene copolymer emulsion obtained above and 200 gr of Snowtex UP were mixed in the same manner as in Example 2.
［塩析操作］
上記で得られた有機重合体エマルジョンとシリカゾルと
の混合エマルジョン６００ｇｒに対して、アセチレンア
ルコールとして３，６−シメチルー４−オクチン−３，
６−ジオールＯ，ｌ ６ ｇｒを使用した以外は実施例
１の［塩析操作］と同様の条件て塩析を行ったところ、
気液界面にスラッジを浮上させることなく、粗粒子か燦
いスラリーか得られた。[Salting out operation] To 600g of the mixed emulsion of the organic polymer emulsion and silica sol obtained above, 3,6-dimethyl-4-octyne-3,
Salting out was carried out under the same conditions as [salting out operation] in Example 1 except that 6-diol O,l 6 gr was used.
Coarse particles or bright slurry were obtained without sludge floating on the air-liquid interface.
［洗浄及び乾燥操作］
洗浄及び乾燥操作を実施例Ｉと同様に行ったところ、平
均粒径ｌＯ〜３０μの複合型の重合体粉末を得た。該重
合体粉末はエチレン共重合体８０重量％、シリカ成分２
０重量％、ナトリウムｌＯｐｐｍ及びアルミニウムＩＯ
ｐｐｍ含育していた。[Washing and Drying Operations] Washing and drying operations were carried out in the same manner as in Example I to obtain a composite polymer powder with an average particle size of 10 to 30 μm. The polymer powder contains 80% by weight of ethylene copolymer and 2% of silica component.
0% by weight, sodium lOppm and aluminum IO
It contained ppm.
（ハ）発明の効果
本発明の重合体粉末製造方法によれば、高温度或いは高
攪拌下の塩析においても発泡が起きず、塩析で得られた
スラリーの洗浄か容易であり、商業的に効率よく重合体
粉末を得ることかできる。(c) Effects of the Invention According to the method for producing polymer powder of the present invention, no foaming occurs even during salting out at high temperatures or with high stirring, and the slurry obtained by salting out can be easily washed, making it commercially viable. It is possible to obtain polymer powder efficiently.
又、本発明の製造方法により得られる重合体粉末は、塩
析剤或いは界面活性剤等の含有量力１大幅に低減されて
いるめ、該重合体粉末をそのまま、或いは他の樹脂に配
合して使用する場合、電気絶縁性等を低下させることな
く、靭性や応力緩和性に優れた樹脂となり得るものであ
る。Furthermore, since the polymer powder obtained by the production method of the present invention has a significantly reduced content of salting-out agents, surfactants, etc., the polymer powder can be used as it is or mixed with other resins. When used, it can become a resin with excellent toughness and stress relaxation properties without reducing electrical insulation properties or the like.
Claims (1)
の存在下に行うことを特徴とする重合体粉末の製造方法
。1. A method for producing a polymer powder, which comprises salting out a polymer emulsion in the presence of acetylene alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26791590A JPH04145104A (en) | 1990-10-05 | 1990-10-05 | Production of polymer powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26791590A JPH04145104A (en) | 1990-10-05 | 1990-10-05 | Production of polymer powder |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04145104A true JPH04145104A (en) | 1992-05-19 |
Family
ID=17451391
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26791590A Pending JPH04145104A (en) | 1990-10-05 | 1990-10-05 | Production of polymer powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04145104A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2840617A1 (en) * | 2002-06-10 | 2003-12-12 | Rhodia Chimie Sa | A porous silicone material used for, eg, artificial leather, hydrophobic and breathable fabrics prepared by breaking an aqueous emulsion of polyorganosiloxanes and crosslinking the gel formed by coalescence of the droplets |
| JP2020084080A (en) * | 2018-11-28 | 2020-06-04 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Manufacturing method of rubber-like polymer |
-
1990
- 1990-10-05 JP JP26791590A patent/JPH04145104A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2840617A1 (en) * | 2002-06-10 | 2003-12-12 | Rhodia Chimie Sa | A porous silicone material used for, eg, artificial leather, hydrophobic and breathable fabrics prepared by breaking an aqueous emulsion of polyorganosiloxanes and crosslinking the gel formed by coalescence of the droplets |
| WO2003104312A1 (en) * | 2002-06-10 | 2003-12-18 | Rhodia Chimie | Method for producing porous silicone materials |
| JP2020084080A (en) * | 2018-11-28 | 2020-06-04 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Manufacturing method of rubber-like polymer |
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