JP2019025447A - Defoaming agent for vinyl chloride resin slurry and method for producing vinyl chloride resin - Google Patents
Defoaming agent for vinyl chloride resin slurry and method for producing vinyl chloride resin Download PDFInfo
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- vinyl chloride
- chloride resin
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- polyether compound
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- 229920005989 resin Polymers 0.000 title claims abstract description 67
- 239000011347 resin Substances 0.000 title claims abstract description 67
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000002002 slurry Substances 0.000 title claims abstract description 47
- 239000002518 antifoaming agent Substances 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 229920000570 polyether Polymers 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000005342 ion exchange Methods 0.000 claims abstract description 8
- -1 oxypropylene group Chemical group 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 125000006353 oxyethylene group Chemical group 0.000 claims abstract description 3
- 230000002209 hydrophobic effect Effects 0.000 claims description 41
- 150000004706 metal oxides Chemical class 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 229910044991 metal oxide Inorganic materials 0.000 claims description 23
- 239000013530 defoamer Substances 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 229920002554 vinyl polymer Polymers 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 21
- PKVWFEIPUHJVGV-UHFFFAOYSA-N butan-1-ol;oxirane Chemical compound C1CO1.CCCCO PKVWFEIPUHJVGV-UHFFFAOYSA-N 0.000 description 13
- 229910002012 Aerosil® Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 230000003254 anti-foaming effect Effects 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229910021485 fumed silica Inorganic materials 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000012488 sample solution Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000008235 industrial water Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000012085 test solution Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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
- 229920004482 WACKER® Polymers 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001983 poloxamer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 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
- 229920006310 Asahi-Kasei Polymers 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- NEXSMEBSBIABKL-UHFFFAOYSA-N hexamethyldisilane Chemical compound C[Si](C)(C)[Si](C)(C)C NEXSMEBSBIABKL-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- DWAWYEUJUWLESO-UHFFFAOYSA-N trichloromethylsilane Chemical compound [SiH3]C(Cl)(Cl)Cl DWAWYEUJUWLESO-UHFFFAOYSA-N 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Degasification And Air Bubble Elimination (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、塩化ビニル系樹脂スラリー用消泡剤及びこれを用いる塩化ビニル系樹脂の製造方法に関する。 The present invention relates to an antifoaming agent for a vinyl chloride resin slurry and a method for producing a vinyl chloride resin using the same.
懸濁重合法による塩化ビニル系樹脂の製造方法の重合工程や重合後の残留モノマー回収（脱モノマー）工程において、泡が生じるために生産性が低下したり、泡によって得られる塩化ビニル系樹脂の物性が低下することがある。これを抑制するために、各工程に消泡剤を使用することが提案されており、例えば、消泡剤と特定の部分ケン化ポリビニルアルコールとを用いる製造方法（特許文献１）や塩化ビニル系樹脂水性液に、エチレンオキサイドとプロピレンオキサイドのブロック共重合体を添加し、ストリッピングを行う製造方法（特許文献２）が知られている。 In the polymerization step of the vinyl chloride resin production method by suspension polymerization and the residual monomer recovery (demonomer) step after polymerization, foaming occurs, resulting in a decrease in productivity, or the vinyl chloride resin obtained by the foam. Physical properties may deteriorate. In order to suppress this, it has been proposed to use an antifoaming agent in each step. For example, a production method using a defoaming agent and a specific partially saponified polyvinyl alcohol (Patent Document 1) or a vinyl chloride type A production method (Patent Document 2) is known in which a block copolymer of ethylene oxide and propylene oxide is added to an aqueous resin liquid and stripping is performed.
従来の消泡剤を塩化ビニル系樹脂の製造に適用すると、消泡性が不十分であり、生産性や得られる塩化ビニル系樹脂の物性に問題がある。
本発明の目的は、塩化ビニル系樹脂の製造工程（すなわち、塩化ビニル系樹脂スラリーが存在する工程）において、優れた消泡性を有する消泡剤を提供することである。
When a conventional antifoaming agent is applied to the production of a vinyl chloride resin, the antifoaming property is insufficient, and there is a problem in the productivity and physical properties of the resulting vinyl chloride resin.
An object of the present invention is to provide an antifoaming agent having excellent antifoaming properties in a vinyl chloride resin production process (that is, a process in which a vinyl chloride resin slurry is present).
本発明の塩化ビニル系樹脂スラリー用消泡剤の特徴は、一般式（１）で表されるポリエーテル化合物（Ａ）を含有することを要旨とする。 The feature of the antifoaming agent for vinyl chloride resin slurry of the present invention is that it contains the polyether compound (A) represented by the general formula (1).
Ｒ１Ｏ-（ＥＯ）ｎ（ＰＯ）ｍ-Ｈ （１）
R 1 O— (EO) n (PO) m —H (1)
Ｒ１は炭素数４〜１２のアルキル基、ＥＯはオキシエチレン基、ＰＯはオキシプロピレン基、ｎは３〜３０の整数、ｍは１０〜９０の整数である。 R 1 is an alkyl group having 4 to 12 carbon atoms, EO is an oxyethylene group, PO is an oxypropylene group, n is an integer of 3 to 30, and m is an integer of 10 to 90.
本発明の塩化ビニル系樹脂の製造方法の特徴は、上記の塩化ビニル系樹脂スラリー用消泡剤の存在下で単量体を重合させて塩化ビニル系樹脂スラリーを得る重合工程を含むこと、または、上記の塩化ビニル系樹脂スラリー用消泡剤の存在下で塩化ビニル系樹脂スラリーから残留モノマーを回収及び／又は除去する脱モノマー工程を含むことを要旨とする。 A feature of the method for producing a vinyl chloride resin of the present invention includes a polymerization step of polymerizing a monomer in the presence of the antifoaming agent for vinyl chloride resin slurry to obtain a vinyl chloride resin slurry, or The gist of the present invention is to include a demonomer step of recovering and / or removing residual monomer from the vinyl chloride resin slurry in the presence of the above-mentioned defoamer for vinyl chloride resin slurry.
本発明の塩化ビニル系樹脂スラリー用消泡剤は、塩化ビニル系樹脂スラリーに対して（すなわち、塩化ビニル系樹脂の製造において）優れた消泡性を発揮する。 The defoamer for vinyl chloride resin slurry of the present invention exhibits excellent defoaming properties with respect to the vinyl chloride resin slurry (that is, in the production of vinyl chloride resin).
本発明の塩化ビニル系樹脂の製造方法は、上記の塩化ビニル系樹脂スラリー用消泡剤を用いるので生産性に優れ、得られる塩化ビニル系樹脂の物性が優れる。 The method for producing a vinyl chloride resin of the present invention uses the above-mentioned antifoaming agent for vinyl chloride resin slurry, so that the productivity is excellent and the physical properties of the resulting vinyl chloride resin are excellent.
炭素数４〜１２のアルキル基（Ｒ１）としては、ブチル、ヘキシル、２−エチルヘキシル、デシル、イソデシル及びドデシル等が挙げられる。これらのうち、ブチル、２−エチルヘキシル及びデシルが好ましく、さらに好ましくはブチルである。 Examples of the alkyl group having 4 to 12 carbon atoms (R 1 ) include butyl, hexyl, 2-ethylhexyl, decyl, isodecyl and dodecyl. Of these, butyl, 2-ethylhexyl and decyl are preferable, and butyl is more preferable.
一般式（１）におけるｍのｎに対する比率（ｍ／ｎ）は、消泡性の観点から、０．８〜１０が好ましく、さらに好ましくは０．９〜９．５、特に好ましくは１〜９、最も好ましくは１．１〜８である。 In the general formula (1), the ratio of m to n (m / n) is preferably 0.8 to 10, more preferably 0.9 to 9.5, and particularly preferably 1 to 9 from the viewpoint of defoaming properties. Most preferably, it is 1.1-8.
一般式（１）におけるｍ及びｎの和（ｍ＋ｎ）は、消泡性の観点から、２０〜１５０が好ましく、さらに好ましくは２２〜１２０、特に好ましくは２４〜１００，最も好ましくは２５〜８５である。 In the general formula (1), the sum of m and n (m + n) is preferably 20 to 150, more preferably 22 to 120, particularly preferably 24 to 100, and most preferably 25 to 85, from the viewpoint of defoaming properties. is there.
ポリエーテル化合物（Ａ）の１重量％イオン交換水溶液での曇点（℃）は、１０〜４０が好ましく、さらに好ましくは１１〜３７、特に好ましくは１２〜３５、最も好ましくは１３〜３０である。この範囲であると、消泡性がさらに良好となる。 10-40 are preferable, as for the cloud point (degreeC) in the 1 weight% ion-exchange aqueous solution of a polyether compound (A), More preferably, it is 11-37, Most preferably, it is 12-35, Most preferably, it is 13-30. . Within this range, the antifoaming property is further improved.
１重量％イオン交換水溶液での曇点は、親水性の尺度となる物性値の一つであり、曇点が高いほど親水性が大きいことを意味し、以下のようにして測定される値である。 The cloud point in a 1% by weight ion exchange aqueous solution is one of the physical property values as a measure of hydrophilicity. The higher the cloud point, the greater the hydrophilicity, and the value measured as follows. is there.
イオン交換水９９ｇ及び試料１ｇを均一溶解させ（溶解しない場合溶解するまで冷却する）、この試料溶液約５ｃｃをガラス製の試験管に採り、温度計を試料溶液に入れて攪拌しながら、昇温させて試料溶液を白濁させた後、攪拌しながら、ゆっくり冷却して試料溶液が完全に透明となる温度を読みとり、これを曇点とする。 Dissolve 99 g of ion-exchanged water and 1 g of sample uniformly (cool until dissolved if not dissolved), take about 5 cc of this sample solution in a glass test tube, put the thermometer into the sample solution, and raise the temperature while stirring. After the sample solution is clouded, the sample solution is slowly cooled with stirring to read the temperature at which the sample solution becomes completely transparent.
ポリエーテル化合物（Ａ）の好ましい例としては、ブタノールのエチレンオキシド（２０モル）プロピレンオキシド（６５モル）ブロック付加体、ブタノールのエチレンオキシド（１８モル）プロピレンオキシド（５５モル）ブロック付加体、ブタノールのエチレンオキシド（２０モル）プロピレンオキシド（２５モル）ブロック付加体、ブタノールのエチレンオキシド（５モル）プロピレンオキシド（３０モル）ブロック付加体、ブタノールのエチレンオキシド（２５モル）プロピレンオキシド（２８モル）ブロック付加体、ブタノールのエチレンオキシド（５モル）プロピレンオキシド（４０モル）ブロック付加体、デカノールのエチレンオキシド（１１モル）プロピレンオキシド（１４モル）ブロック付加体及び２−エチルヘキサノールのエチレンオキシド（２０モル）プロピレンオキシド（２５モル）ブロック付加体等が挙げられる。 Preferred examples of the polyether compound (A) include butanol ethylene oxide (20 mol) propylene oxide (65 mol) block adduct, butanol ethylene oxide (18 mol) propylene oxide (55 mol) block adduct, butanol ethylene oxide ( 20 mol) propylene oxide (25 mol) block adduct, butanol ethylene oxide (5 mol) propylene oxide (30 mol) block adduct, butanol ethylene oxide (25 mol) propylene oxide (28 mol) block adduct, butanol ethylene oxide (5 mol) propylene oxide (40 mol) block adduct, ethylene oxide of decanol (11 mol) propylene oxide (14 mol) block adduct and 2-ethylhexanol Of ethylene oxide (20 moles) of propylene oxide (25 moles) block adduct, and the like.
本発明の塩化ビニル系樹脂スラリー用消泡剤は、消泡性の観点から、疎水性金属酸化物（Ｂ）を含有することが好ましい。
疎水性金属酸化物（Ｂ）としては、疎水性シリカ、疎水性アルミナ及び疎水性チタンが含まれ、疎水性ヒュームドシリカ、疎水性ヒュームドアルミナ、疎水性ヒュームドチタン、疎水性沈降シリカ及び疎水性ゲルシリカ等が使用できる。これらのうち、消泡性、コスト及び消泡剤の安定性の観点から、疎水性シリカが好ましい。
The defoamer for vinyl chloride resin slurry of the present invention preferably contains a hydrophobic metal oxide (B) from the viewpoint of defoaming properties.
Hydrophobic metal oxides (B) include hydrophobic silica, hydrophobic alumina and hydrophobic titanium, hydrophobic fumed silica, hydrophobic fumed alumina, hydrophobic fumed titanium, hydrophobic precipitated silica and hydrophobic Can be used. Among these, hydrophobic silica is preferable from the viewpoint of antifoaming property, cost, and stability of the antifoaming agent.
疎水性金属酸化物（Ｂ）は、市場から入手して使用することもできるし、親水性金属酸化物を公知の方法（特開２０１４−２１４２８６号等）で疎水化して得られる疎水性金属酸化物を使用することもできる。 The hydrophobic metal oxide (B) can be obtained from the market and used, or the hydrophobic metal oxide obtained by hydrophobizing the hydrophilic metal oxide by a known method (Japanese Patent Laid-Open No. 2014-214286, etc.) Things can also be used.
親水性金属酸化物としては、シリカ、アルミナ、酸化チタン、酸化亜鉛及び酸化鉄が含まれる。 Examples of the hydrophilic metal oxide include silica, alumina, titanium oxide, zinc oxide and iron oxide.
親水性粉体の疎水化に用いる疎水化剤としては特に制限は無いが、シリコーン系疎水化剤（シリコーンオイル、ヘキサメチルジシラン、ヘキサメチルジシラザン、ジクロロジメチルシラン、クロロトリメチルシラン、トリクロロメチルシラン、ジアルキルジクロロシラン、ジアルキルジアルコキシシラン及びシリコーン樹脂等）が挙げられる。 The hydrophobizing agent used for hydrophobizing the hydrophilic powder is not particularly limited, but silicone hydrophobizing agents (silicone oil, hexamethyldisilane, hexamethyldisilazane, dichlorodimethylsilane, chlorotrimethylsilane, trichloromethylsilane, And dialkyldichlorosilane, dialkyldialkoxysilane, and silicone resin).
親水性粉体を疎水化する疎水化方法として特に制限は無いが、疎水化剤と親水性粉体とを直接添加混合する方法（乾式法）及び疎水性溶媒中で疎水化剤と親水性粉体とを混合する方法（湿式法）等が挙げられる。疎水化時の温度や反応触媒は用いる疎水化剤に応じて、適切な条件にすればよい。 There is no particular limitation on the hydrophobizing method for hydrophobizing the hydrophilic powder, but the method of directly adding and mixing the hydrophobizing agent and the hydrophilic powder (dry method) and the hydrophobizing agent and the hydrophilic powder in the hydrophobic solvent The method (wet method) etc. which mix a body are mentioned. The temperature at the time of hydrophobization and the reaction catalyst may be set to appropriate conditions according to the hydrophobizing agent used.
疎水性ヒュームドシリカとして市場から入手できる商品としては、ＡＥＲＯＳＩＬシリーズ（Ｒ９７２、Ｒ９７４、ＲＸ２００、ＲＸ３００、ＲＹ２００、Ｒ２０２及びＲ８０５等、日本アエロジル株式会社、「ＡＥＲＯＳＩＬ」はエボニック デグサ ゲーエムベーハーの登録商標である。以下、同様である。）；ＲＥＯＬＯＳＩＬシリーズ（ＭＴ−１０、ＤＭ−１０及びＤＭ−２０Ｓ等、株式会社トクヤマ、「ＲＥＯＬＯＳＩＬ」は同社の登録商標である。以下、同様である。）；ＨＤＫシリーズ（ＨＤＫＨ１５及びＨＤＫＨ１８等、旭化成ワッカーシリコーン株式会社、「ＨＤＫ」はＷａｃｋｅｒ Ｃｈｅｍｉｅ ＡＧの登録商標である。以下、同様である。）；並びにＣＡＢ−Ｏ−ＳＩＬシリーズ（ＴＳ−７２０、ＴＳ−６２２及びＴＳ−３８２等、キャボットカーボン社、「ＣＡＢ−Ｏ−ＳＩＬ」はキヤボツト コ−パレイシヤンの登録商標である。以下、同様である。）等が挙げられる。 As products that can be obtained from the market as hydrophobic fumed silica, AEROSIL series (R972, R974, RX200, RX300, RY200, R202, and R805, etc., Nippon Aerosil Co., Ltd., “AEROSIL” is a registered trademark of Evonik Degussa GM Becher. The same shall apply hereinafter.); REOLOSIL series (MT-10, DM-10, DM-20S, etc., Tokuyama Corporation, “REOLOSIL” is a registered trademark of the same company. The same shall apply hereinafter); HDK series ( HDKH15 and HDKH18, etc. Asahi Kasei Wacker Silicone Co., Ltd. “HDK” is a registered trademark of Wacker Chemie AG. The same shall apply hereinafter.); And CAB-O-SIL series (TS-720, TS-622 and T -382 etc., Cabot Carbon Co., "CAB-O-SIL" is Kiyabotsuto co -.. Is a registered trademark of Pareishiyan the same applies hereinafter), and the like.
疎水性ヒュームドアルミナとして市場から入手できる商品としては、ＡＥＲＯＸＩＤＥシリーズ（ＡｌｕＣ８０５等、日本アエロジル株式会社、「ＡＥＲＯＸＩＤＥ」はエボニック デグサ ゲーエムベーハーの登録商標である。以下、同様である。）が挙げられる。 Examples of products that can be obtained from the market as hydrophobic fumed alumina include the AEROXIDE series (AluC805, etc., Nippon Aerosil Co., Ltd., “AEROXIDE” is a registered trademark of Evonik DGSAME BAH. The same applies hereinafter).
疎水性ヒュームドチタンとして市場から入手できる商品としては、ＡＥＲＯＸＩＤＥシリーズ（Ｔ８０５及びＮＫＴ９０等）が挙げられる。 AEROXIDE series (T805, NKT90, etc.) is mentioned as a product which can be obtained from the market as hydrophobic fumed titanium.
疎水性沈降シリカとして市場から入手できる商品としては、Ｎｉｐｓｉｌ ＳＳ−１０、ＳＳ−４０、ＳＳ−５０及びＳＳ−１００（東ソー・シリカ株式会社、「Ｎｉｐｓｉｌ」は東ソー・シリカ株式会社 の登録商標である。）及びＳＩＰＥＲＮＡＴ Ｄ１０、Ｄ１３及びＤ１７（デグサジャパン株式会社、「ＳＩＰＥＲＮＡＴ」はエボニック デグサ ゲーエムベーハーの登録商標である。 ）等が挙げられる。 Commercially available products as hydrophobic precipitated silica include Nipsil SS-10, SS-40, SS-50 and SS-100 (Tosoh Silica Co., Ltd., “Nipsil” is a registered trademark of Tosoh Silica Co., Ltd. ) And SIPERNAT D10, D13, and D17 (Degussa Japan Co., Ltd., “SIPRNAT” is a registered trademark of Evonik Degussa M. Becher.).
疎水性ゲルシリカとして市場から入手できる商品としては、サイロホービック１００及び２００（富士シリシア化学株式会社、「サイロホービック」は富士シリシア化学株式会社の登録商標である。）等が挙げられる。 Examples of commercially available products as hydrophobic gel silica include Silo Hovic 100 and 200 (Fuji Silysia Chemical Co., Ltd., “Silo Hovic” is a registered trademark of Fuji Silysia Chemical Co., Ltd.).
疎水性金属酸化物（Ｂ）のメタノール湿潤性（Ｍ値）は、３５〜７５が好ましく、さらに好ましくは３６〜７０、特に好ましくは３８〜６７、最も好ましくは４０〜６５である。この範囲であると、消泡性及び消泡剤の分離安定性がさらに良好となる。 The methanol wettability (M value) of the hydrophobic metal oxide (B) is preferably 35 to 75, more preferably 36 to 70, particularly preferably 38 to 67, and most preferably 40 to 65. Within this range, antifoaming properties and separation stability of the antifoaming agent are further improved.
Ｍ値は、疎水化の度合いを表す指標であり、濃度の相違するいくつかの水／メタノール混合溶液のうち、メタノール濃度が最も小さい均一分散液の容量％を意味し、以下のようにして測定される値である。この値が高い程、疎水性が高いといえる。 The M value is an index representing the degree of hydrophobicity, and means the volume% of a uniform dispersion having the smallest methanol concentration among several water / methanol mixed solutions having different concentrations, and is measured as follows. Is the value to be It can be said that the higher this value, the higher the hydrophobicity.
＜メタノール湿潤性（Ｍ値）の測定方法＞
メタノール濃度を５容量％の間隔で変化させた水／メタノール混合溶液を調製し、これを容積１０ｍｌの試験管に５ｍｌ入れる。次いで測定試料０．２ｇを入れ、試験管にふたをして、２０回上下転倒してから１〜２分間静置した後、試験管内を観察して、凝集物がなく、測定試料の全部が湿潤して均一分散した分散液のうち、メタノール濃度が最も小さい分散液のメタノールの濃度（容量％）をＭ値とする｛Ｍ値の単位（容量％）は記載しないことが通例である。｝。
<Measuring method of methanol wettability (M value)>
A mixed water / methanol solution is prepared in which the methanol concentration is changed at intervals of 5% by volume, and this is placed in a test tube having a volume of 10 ml. Next, 0.2 g of the measurement sample is put, the test tube is capped, and the sample is turned upside down 20 times, and then left to stand for 1 to 2 minutes. Of the dispersions wet and uniformly dispersed, the concentration (volume%) of methanol in the dispersion having the smallest methanol concentration is taken as the M value. Usually, the unit (volume%) of the M value is not described. }.
疎水性金属酸化物（Ｂ）の含有量（重量％）は、ポリエーテル化合物（Ａ）の重量に基づいて、０．１〜１０が好ましく、さらに好ましくは０．２〜８、特に好ましくは０．３〜７、最も好ましくは０．５〜５である。これらの範囲であると、消泡性及び取り扱い性がさらに良好となる。 The content (% by weight) of the hydrophobic metal oxide (B) is preferably 0.1 to 10, more preferably 0.2 to 8, particularly preferably 0, based on the weight of the polyether compound (A). .3-7, most preferably 0.5-5. Within these ranges, the defoaming property and handleability are further improved.
本発明の塩化ビニル系樹脂スラリー用消泡剤は、さらに水（Ｃ）を含むことができる。水を含有させることにより、引火危険性を低減させ取扱上の安全性を高める効果がある。また、消泡剤の低温流動性の向上効果がある。水としては、蒸留水、イオン交換水、水道水、工業用水、井戸水、湧き水及び河川水等が使用できる。これらのうち、水道水、工業用水、イオン交換水及び蒸留水が好ましく、さらに好ましくはイオン交換水及び蒸留水である。 The defoamer for vinyl chloride resin slurry of the present invention may further contain water (C). By containing water, there is an effect of reducing the danger of ignition and enhancing the safety in handling. In addition, there is an effect of improving the low temperature fluidity of the antifoaming agent. As water, distilled water, ion exchange water, tap water, industrial water, well water, spring water, river water, and the like can be used. Among these, tap water, industrial water, ion exchange water and distilled water are preferable, and ion exchange water and distilled water are more preferable.
水（Ｃ）を含有する場合、水（Ｃ）の含有量（重量％）は、ポリエーテル化合物（Ａ）の重量に基づいて、０．１〜５０が好ましく、さらに好ましくは０．３〜２０、特に好ましくは０．５〜１５、最も好ましくは１〜１０である。 When water (C) is contained, the content (% by weight) of water (C) is preferably 0.1 to 50, more preferably 0.3 to 20 based on the weight of the polyether compound (A). Particularly preferably, it is 0.5 to 15, most preferably 1 to 10.
本発明の塩化ビニル系樹脂スラリー用消泡剤は、塩化ビニル系樹脂スラリーに対して効果的であり、塩化ビニル系樹脂の製造工程（塩化ビニル系樹脂スラリーを得る重合工程や、塩化ビニル系樹脂スラリーから残留モノマーを回収及び／又は除去する脱モノマー工程）において優れた消泡性を発揮する。 The defoamer for vinyl chloride resin slurry of the present invention is effective for vinyl chloride resin slurry, and is a process for producing vinyl chloride resin (polymerization process for obtaining vinyl chloride resin slurry, vinyl chloride resin Excellent defoaming property is exhibited in a demonomer process for recovering and / or removing residual monomer from the slurry.
本発明の塩化ビニル系樹脂スラリー用消泡剤は、いずれのタイミングで添加してもよく、添加に際しては消泡剤を適当な希釈溶媒（たとえば水）で希釈してもよい。 The antifoaming agent for the vinyl chloride resin slurry of the present invention may be added at any timing, and the antifoaming agent may be diluted with an appropriate diluent solvent (for example, water).
塩化ビニル系樹脂としては、塩化ビニル及び塩化ビニルと共重合可能なモノマーの重合物であり、塩化ビニルと共重合可能なモノマーとしては、塩化ビニリデン、酢酸ビニル、（メタ）アクリル酸エステル、エチレン、プロピレン、アルキルビニルエーテル、無水マレイン酸、アクリロニトリル及びスチレンが含まれる。 The vinyl chloride resin is a polymer of vinyl chloride and a monomer copolymerizable with vinyl chloride, and the monomer copolymerizable with vinyl chloride includes vinylidene chloride, vinyl acetate, (meth) acrylic acid ester, ethylene, Propylene, alkyl vinyl ether, maleic anhydride, acrylonitrile and styrene are included.
（メタ）アクリル酸エステルとしては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ヒドロキシエチルが含まれる。 (Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, and hydroxyethyl (meth) acrylate.
消泡剤の含有量は発泡状態に応じて適宜決定できるが、塩化ビニル系樹脂の重量に基づいて、０．００１〜０．１重量％程度である。 The content of the antifoaming agent can be appropriately determined according to the foamed state, but is about 0.001 to 0.1% by weight based on the weight of the vinyl chloride resin.
塩化ビニル系樹脂スラリーの濃度、樹脂粒子径、重合工程の条件、脱モノマー工程の条件等の詳細については、通常の条件、範囲がそのまま適用できる。 For details such as the concentration of the vinyl chloride resin slurry, the resin particle diameter, the conditions of the polymerization process, the conditions of the demonomer process, etc., the usual conditions and ranges can be applied as they are.
以下、特記しない限り「部」は重量部を、「％」は重量％をそれぞれ意味し、また、「曇点」は１重量％イオン交換水溶液での曇点（℃）を意味する。 Hereinafter, unless otherwise specified, “parts” means parts by weight, “%” means percent by weight, and “cloud point” means the cloud point (° C.) in a 1% by weight ion exchange aqueous solution.
ポリエーテル化合物（Ａ）として、以下のポリエーテル化合物（ａ１）〜（ａ７）を使用した。
ポリエーテル化合物（ａ１）：ブタノールのエチレンオキシド（２０モル）プロピレンオキシド（６５モル）ブロック付加体、曇点１４℃、和（ｍ＋ｎ）＝８５、比率（ｍ／ｎ）＝３．３
ポリエーテル化合物（ａ２）：ブタノールのエチレンオキシド（１８モル）プロピレンオキシド（５５モル）ブロック付加体、曇点１５℃、和（ｍ＋ｎ）＝７３、比率（ｍ／ｎ）＝３．１
ポリエーテル化合物（ａ３）：ブタノールのエチレンオキシド（２０モル）プロピレンオキシド（２５モル）ブロック付加体、曇点２３℃、和（ｍ＋ｎ）＝４５、比率（ｍ／ｎ）＝１．３
ポリエーテル化合物（ａ４）：ブタノールのエチレンオキシド（５モル）プロピレンオキシド（３０モル）ブロック付加体、曇点１６℃、和（ｍ＋ｎ）＝３５、比率（ｍ／ｎ）＝６．０
ポリエーテル化合物（ａ５）：ブタノールのエチレンオキシド（２５モル）プロピレンオキシド（２８モル）ブロック付加体、曇点３０℃、和（ｍ＋ｎ）＝５３、比率（ｍ／ｎ）＝１．１
ポリエーテル化合物（ａ６）：ブタノールのエチレンオキシド（５モル）プロピレンオキシド（４０モル）ブロック付加体、曇点１３℃、和（ｍ＋ｎ）＝４５、比率（ｍ／ｎ）＝８．０
ポリエーテル化合物（ａ７）：デカノールのエチレンオキシド（１１モル）プロピレンオキシド（１４モル）ブロック付加体、曇点２３℃、和（ｍ＋ｎ）＝２５、比率（ｍ／ｎ）＝１．３
The following polyether compounds (a1) to (a7) were used as the polyether compound (A).
Polyether compound (a1): Butanol ethylene oxide (20 mol) propylene oxide (65 mol) block adduct, cloud point 14 ° C., sum (m + n) = 85, ratio (m / n) = 3.3
Polyether compound (a2): Butanol ethylene oxide (18 mol) propylene oxide (55 mol) block adduct, cloud point 15 ° C., sum (m + n) = 73, ratio (m / n) = 3.1
Polyether compound (a3): Butanol ethylene oxide (20 mol) propylene oxide (25 mol) block adduct, cloud point 23 ° C., sum (m + n) = 45, ratio (m / n) = 1.3
Polyether compound (a4): Butanol ethylene oxide (5 mol) propylene oxide (30 mol) block adduct, cloud point 16 ° C., sum (m + n) = 35, ratio (m / n) = 6.0
Polyether compound (a5): Butanol ethylene oxide (25 mol) propylene oxide (28 mol) block adduct, cloud point 30 ° C., sum (m + n) = 53, ratio (m / n) = 1.1
Polyether compound (a6): Butanol ethylene oxide (5 mol) propylene oxide (40 mol) block adduct, cloud point 13 ° C., sum (m + n) = 45, ratio (m / n) = 8.0
Polyether compound (a7): decanol ethylene oxide (11 mol) propylene oxide (14 mol) block adduct, cloud point 23 ° C., sum (m + n) = 25, ratio (m / n) = 1.3
疎水性金属酸化物（Ｂ）として、以下の疎水性金属酸化物（ｂ１）〜（ｂ４）を使用した。
疎水性金属酸化物（ｂ１）：ＡＥＲＯＳＩＬ Ｒ９７４、疎水性ヒュームドシリカ、Ｍ値４０、日本アエロジル株式会社
疎水性金属酸化物（ｂ２）：ＡＥＲＯＳＩＬ ＲＸ２００、疎水性ヒュームドシリカ、Ｍ値６０、日本アエロジル株式会社
疎水性金属酸化物（ｂ３）：ＡＥＲＯＳＩＬ Ｒ９７２、疎水性ヒュームドシリカ、Ｍ値４５ 、日本アエロジル株式会社
疎水性金属酸化物（ｂ４）：ＮｉｐｓｉｌＳＳ−１５、疎水性沈降シリカ、Ｍ値６０、東ソー・シリカ株式会社
疎水性金属酸化物（ｂ５）：ＳＩＰＥＲＮＡＴＤ１０、疎水性沈降シリカ、Ｍ値６５、デグサジャパン株式会社
The following hydrophobic metal oxides (b1) to (b4) were used as the hydrophobic metal oxide (B).
Hydrophobic metal oxide (b1): AEROSIL R974, hydrophobic fumed silica, M value 40, Nippon Aerosil Co., Ltd. Hydrophobic metal oxide (b2): AEROSIL RX200, hydrophobic fumed silica, M value 60, Nippon Aerosil Hydrophobic metal oxide (b3): AEROSIL R972, hydrophobic fumed silica, M value 45, Nippon Aerosil Co., Ltd. Hydrophobic metal oxide (b4): Nipsil SS-15, hydrophobic precipitated silica, M value 60, Tosoh Silica Co., Ltd. Hydrophobic metal oxide (b5): SIPERNATD10, hydrophobic precipitated silica, M value 65, Degussa Japan Co., Ltd.
＜実施例１＞
攪拌の可能な容器内で、ポリエーテル化合物（ａ１）１０００部及び疎水性金属酸化物（ｂ１）３０部を３０分間攪拌混合して均一にした後、水（ｃ１）｛工業用水｝５０部を加えてさらに３０分間攪拌混合して、本発明の塩化ビニル系樹脂スラリー用消泡剤（１）を得た。
<Example 1>
In a stirrable container, 1000 parts of the polyether compound (a1) and 30 parts of the hydrophobic metal oxide (b1) are stirred and mixed for 30 minutes, and then 50 parts of water (c1) {industrial water} are added. In addition, the mixture was further stirred and mixed for 30 minutes to obtain the defoamer (1) for vinyl chloride resin slurry of the present invention.
＜実施例２＞
攪拌の可能な容器内で、ポリエーテル化合物（ａ２）１０００部及び疎水性金属酸化物（ｂ２）１０部を３０分間攪拌混合して均一にした後、水（ｃ１）５０部を加えてさらに３０分間攪拌混合して、本発明の塩化ビニル系樹脂スラリー用消泡剤（２）を得た。
<Example 2>
In a stirrable container, 1000 parts of the polyether compound (a2) and 10 parts of the hydrophobic metal oxide (b2) were stirred and mixed for 30 minutes, and then 50 parts of water (c1) was added to further 30 parts. By stirring and mixing for a minute, the defoamer (2) for vinyl chloride resin slurry of the present invention was obtained.
＜実施例３＞
攪拌の可能な容器内で、ポリエーテル化合物（ａ３）１０００部及び疎水性金属酸化物（ｂ３）５０部を３０分間攪拌混合して均一にした後、水（ｃ１）１０部を加えてさらに３０分間攪拌混合して、本発明の塩化ビニル系樹脂スラリー用消泡剤（３）を得た。
<Example 3>
In a stirrable container, 1000 parts of the polyether compound (a3) and 50 parts of the hydrophobic metal oxide (b3) were stirred and mixed for 30 minutes, and then 10 parts of water (c1) was added and further 30 By stirring and mixing for a minute, an antifoaming agent (3) for vinyl chloride resin slurry of the present invention was obtained.
＜実施例４＞
ポリエーテル化合物（ａ４）を本発明の塩化ビニル系樹脂スラリー用消泡剤（４）とした。
<Example 4>
The polyether compound (a4) was used as the defoamer (4) for vinyl chloride resin slurry of the present invention.
＜実施例５＞
攪拌の可能な容器内で、ポリエーテル化合物（ａ５）１０００部及び疎水性金属酸化物（ｂ４）５部を３０分間攪拌混合して均一にした後、水（ｃ１）５０部を加えてさらに３０分間攪拌混合して、本発明の塩化ビニル系樹脂スラリー用消泡剤（５）を得た。
<Example 5>
In a stirrable container, 1000 parts of the polyether compound (a5) and 5 parts of the hydrophobic metal oxide (b4) were stirred and mixed for 30 minutes to be uniform, and then 50 parts of water (c1) was added to further 30 parts. By stirring and mixing for a minute, an antifoaming agent (5) for vinyl chloride resin slurry of the present invention was obtained.
＜実施例６＞
攪拌の可能な容器内で、ポリエーテル化合物（ａ６）１０００部及び疎水性金属酸化物（ｂ１）３０部を３０分間攪拌混合して均一にした後、水（ｃ１）５０部を加えてさらに３０分間攪拌混合して、本発明の塩化ビニル系樹脂スラリー用消泡剤（６）を得た。
<Example 6>
In a stirrable container, 1000 parts of the polyether compound (a6) and 30 parts of the hydrophobic metal oxide (b1) were stirred and mixed for 30 minutes, and then 50 parts of water (c1) was added to further 30 parts. By stirring and mixing for a minute, an antifoaming agent (6) for vinyl chloride resin slurry of the present invention was obtained.
＜実施例７＞
攪拌の可能な容器内で、ポリエーテル化合物（ａ７）１０００部及び疎水性金属酸化物（ｂ５）１０部を３０分間攪拌混合して均一にした後、水（ｃ１）１００部を加えてさらに３０分間攪拌混合して、本発明の塩化ビニル系樹脂スラリー用消泡剤（７）を得た。
<Example 7>
In a stirrable container, 1000 parts of the polyether compound (a7) and 10 parts of the hydrophobic metal oxide (b5) are stirred and mixed for 30 minutes to be uniform, and then 100 parts of water (c1) is added to further 30 parts. By stirring and mixing for a minute, the defoamer (7) for vinyl chloride resin slurry of the present invention was obtained.
＜比較例１＞
ブタノールのプロピレンオキシド（４０モル）付加体（曇点７℃）を比較用の消泡剤（Ｈ１）とした。
<Comparative Example 1>
A propylene oxide (40 mol) adduct of butanol (cloud point 7 ° C.) was used as a defoaming agent (H1) for comparison.
＜比較例２＞
ブタノールのエチレンオキシド（１１モル）プロピレンオキシド（７モル）付加体（曇点５２℃）を比較用の消泡剤（Ｈ２）とした。
<Comparative example 2>
Butanol ethylene oxide (11 mol) propylene oxide (7 mol) adduct (cloud point 52 ° C.) was used as a defoaming agent (H2) for comparison.
＜比較例３＞
エチレンオキシド（１０モル）プロピレンオキシド（３０モル）ブロック付加体（プルロニック型、曇点３０℃）を比較用の消泡剤（Ｈ３）とした。
<Comparative Example 3>
An ethylene oxide (10 mol) propylene oxide (30 mol) block adduct (pluronic type, cloud point 30 ° C.) was used as a comparative antifoaming agent (H3).
＜比較例４＞
エチレンオキシド（２３モル）プロピレンオキシド（３５モル）ブロック付加体（プルロニック型、曇点５９℃）を比較用の消泡剤（Ｈ４）とした。
<Comparative example 4>
An ethylene oxide (23 mol) propylene oxide (35 mol) block adduct (pluronic type, cloud point 59 ° C.) was used as a comparative antifoaming agent (H4).
＜比較例５＞
ジメチルポリシロキサンからなるシリコーン系消泡剤を比較用の消泡剤（Ｈ５）とした。
<Comparative Example 5>
A silicone antifoaming agent made of dimethylpolysiloxane was used as a comparative antifoaming agent (H5).
消泡剤（１）〜（７）及び（Ｈ１）〜（Ｈ５）を用いて、以下のようにして消泡性を評価し、評価結果を表１に示した。 Using the antifoaming agents (1) to (7) and (H1) to (H5), the antifoaming property was evaluated as follows, and the evaluation results are shown in Table 1.
＜消泡性の評価＞
１．試験用スラリーの調製
水６００部及び塩化ビニル樹脂粒子（カネビニールＳ−１００８、株式会社カネカ、「カネビニール」は同社の登録商標である。）４００部を均一混合して試験用スラリーを得た。
<Evaluation of antifoaming properties>
1. Preparation of test slurry 600 parts of water and 400 parts of vinyl chloride resin particles (Kane Vinyl S-1008, Kaneka Corporation, "Kane Vinyl" is a registered trademark of the company) were uniformly mixed to obtain a test slurry. .
２．消泡試験液の調製
試験用スラリー１０００部を６０℃まで加熱し、消泡剤を０．１２部を加えて混合し、消泡試験液を得た。
消泡剤を加えないこと以外、上記と同様にして、消泡試験液(ブランク)も調製した。
2. Preparation of antifoam test liquid 1000 parts of the test slurry was heated to 60 ° C., and 0.12 part of the antifoaming agent was added and mixed to obtain an antifoam test liquid.
An antifoam test solution (blank) was also prepared in the same manner as above except that no antifoam was added.
３．消泡性試験
１００ｍＬのガラス製メスシリンダー（以下、発泡管と称する。）を６０℃に温度調節しながら、この発泡管に、６０℃に温度調節した消泡試験液４０ｇを入れ、デフューザーストーンを発泡管の底部まで挿入し３００ｍｌ／分で窒素ガスをバブリングすることによって消泡試験液を泡立てながら、変化する泡及び発泡液の容量を試験開始１５秒後、１分後及び１０分後に読み取った。数値の小さい方が消泡性が高いことを意味し好ましい。
3. Defoaming property test While adjusting the temperature of a 100 mL glass graduated cylinder (hereinafter referred to as a foamed tube) to 60 ° C, put 40 g of the defoaming test solution temperature-adjusted to 60 ° C into this foamed tube. While foaming the defoaming test solution by bubbling nitrogen gas at 300 ml / min by inserting it to the bottom of the foaming tube, the changing foam and the volume of the foaming solution were read 15 seconds later, 1 minute later and 10 minutes later. . A smaller value means that the defoaming property is higher, which is preferable.
本発明の塩化ビニル系樹脂スラリー用消泡剤は、比較用の消泡剤に比べて、優れた消泡性を発揮した。したがって、本発明の塩化ビニル系樹脂スラリー用消泡剤を用いると、塩化ビニル系樹脂の製造方法において生産性に優れ、得られる塩化ビニル系樹脂の物性が優れると予想される。 The antifoaming agent for the vinyl chloride resin slurry of the present invention exhibited excellent antifoaming properties as compared with a comparative antifoaming agent. Therefore, when the antifoaming agent for vinyl chloride resin slurry of the present invention is used, it is expected that the vinyl chloride resin production method is excellent in productivity and the resulting vinyl chloride resin is excellent in physical properties.
本発明の消泡剤は、塩化ビニル系樹脂スラリー用消泡剤として好適であり、塩化ビニル系樹脂スラリーを得る重合工程、塩化ビニル系樹脂スラリーから残留モノマーを回収及び／又は除去する脱モノマー工程を含む塩化ビニル系樹脂の製造方法に最適である。 The antifoaming agent of the present invention is suitable as an antifoaming agent for vinyl chloride resin slurry, a polymerization step for obtaining a vinyl chloride resin slurry, and a demonomer step for recovering and / or removing residual monomers from the vinyl chloride resin slurry. It is most suitable for the production method of vinyl chloride resin containing
Claims (9)
Ｒ１Ｏ-（ＥＯ）ｎ（ＰＯ）ｍ-Ｈ （１）
Ｒ１は炭素数４〜１２のアルキル基、ＥＯはオキシエチレン基、ＰＯはオキシプロピレン基、ｎは３〜３０の整数、ｍは１０〜９０の整数である。 An antifoaming agent for vinyl chloride resin slurry, comprising a polyether compound (A) represented by the general formula (1).
R 1 O— (EO) n (PO) m —H (1)
R 1 is an alkyl group having 4 to 12 carbon atoms, EO is an oxyethylene group, PO is an oxypropylene group, n is an integer of 3 to 30, and m is an integer of 10 to 90.
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| JP2021023891A (en) * | 2019-08-06 | 2021-02-22 | サンノプコ株式会社 | Defoaming agent and vinyl chloride resin manufacturing method |
| CN113993911A (en) * | 2019-06-19 | 2022-01-28 | 信越化学工业株式会社 | Process for producing vinyl chloride polymer |
| CN114008085A (en) * | 2019-06-19 | 2022-02-01 | 信越化学工业株式会社 | Process for producing vinyl chloride polymer |
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| CN114008085B (en) * | 2019-06-19 | 2023-12-22 | 信越化学工业株式会社 | Process for producing vinyl chloride polymer |
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| JP6993710B2 (en) | 2019-08-06 | 2022-01-14 | サンノプコ株式会社 | Manufacturing method of defoamer and vinyl chloride resin |
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