JP2020084079A - Manufacturing method of rubber-like polymer - Google Patents
Manufacturing method of rubber-like polymer Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 26
- 239000004816 latex Substances 0.000 claims abstract description 19
- 229920000126 latex Polymers 0.000 claims abstract description 19
- 239000003960 organic solvent Substances 0.000 claims abstract description 19
- 230000002776 aggregation Effects 0.000 claims abstract description 12
- 238000004220 aggregation Methods 0.000 claims abstract description 11
- 230000004931 aggregating effect Effects 0.000 claims description 24
- 229920001971 elastomer Polymers 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 24
- 239000007788 liquid Substances 0.000 description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 239000011259 mixed solution Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000009776 industrial production Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000002245 particle Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 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
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- DEQJGXKCNIZPIF-UHFFFAOYSA-N C(CCCCCCC(C)C)C=C(C(=O)O)C.C(C(=C)C)(=O)OCC(CC(CC(C)C)C)C Chemical compound C(CCCCCCC(C)C)C=C(C(=O)O)C.C(C(=C)C)(=O)OCC(CC(CC(C)C)C)C DEQJGXKCNIZPIF-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 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
- 239000011163 secondary particle Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、ゴム状重合体の製造方法に関するものである。 The present invention relates to a method for producing a rubber-like polymer.
ゴム状重合体を合成して得られたラテックスから、ゴム状重合体を回収するために凝集させることがある。その凝集方法としては、特許文献１の段落００４８に記載のように、無機金属塩や、貧溶媒などの凝集剤を添加する方法が知られている。 From the latex obtained by synthesizing the rubber-like polymer, the rubber-like polymer may be aggregated in order to recover it. As the aggregating method, as described in paragraph 0048 of Patent Document 1, a method of adding an aggregating agent such as an inorganic metal salt or a poor solvent is known.
しかしながら、ゴム状重合体の粒子径が小さい場合、無機金属塩の添加では凝集が不十分な場合がある。 However, when the rubber-like polymer has a small particle size, the addition of the inorganic metal salt may cause insufficient aggregation.
また、工業的にゴム状重合体を製造する場合、一般的には、重合反応を行った後、凝集槽において凝集を行い、凝集槽の下部に設けられた排出口から凝集した重合体の回収を行う。 Further, in the case of industrially producing a rubber-like polymer, generally, after performing a polymerization reaction, the flocculation tank is subjected to flocculation, and the flocculated polymer is recovered from an outlet provided at the bottom of the flocculation tank. I do.
しかしながら、貧溶媒を添加する方法では、ゴム状重合体が塊状に凝固して流動性を失い、凝集槽の排出口から排出できないという問題が生じることがあった。 However, in the method of adding the poor solvent, there is a problem that the rubber-like polymer solidifies into a lump and loses fluidity, so that it cannot be discharged from the discharge port of the coagulation tank.
本発明は、以上の点に鑑み、工業的に製造する際の作業性に優れたゴム状重合体の製造方法を提供することを目的とする。 In view of the above points, an object of the present invention is to provide a method for producing a rubber-like polymer having excellent workability in industrial production.
本発明に係るゴム状重合体の製造方法は、ゴム状重合体を含有するラテックスに、無機金属塩を含む水溶液を添加し、ゴム状重合体を凝集させる第一凝集工程と、ｓｐ値が１１〜１５である有機溶媒を添加し、ゴム状重合体を凝集させる第二凝集工程とを有するものとする。 The method for producing a rubber-like polymer according to the present invention comprises a first aggregating step of aggregating a rubber-like polymer by adding an aqueous solution containing an inorganic metal salt to a latex containing a rubber-like polymer, and an sp value of 11 A second aggregating step of aggregating the rubber-like polymer by adding an organic solvent of 15 to 15.
上記ゴム状重合体は、乳化重合により合成されたものとすることができる。 The rubbery polymer may be one synthesized by emulsion polymerization.
上記無機金属塩は３価の無機金属イオンを有するものとすることができる。 The inorganic metal salt can have a trivalent inorganic metal ion.
本発明のゴム状重合体の製造方法によれば、工業的に製造する際の作業性が大きく向上する。 According to the method for producing a rubber-like polymer of the present invention, workability in industrial production is greatly improved.
以下、本発明の実施に関連する事項について詳細に説明する。 Hereinafter, matters related to the implementation of the present invention will be described in detail.
本実施形態に係るゴム状重合体の製造方法は、ゴム状重合体を含有するラテックスに、無機金属塩を含む水溶液を添加し、ゴム状重合体を凝集させる第一凝集工程と、ｓｐ値が１１〜１５である有機溶媒を添加し、ゴム状重合体を凝集させる第二凝集工程とを有するものとする。 The method for producing a rubber-like polymer according to the present embodiment includes a first aggregation step of adding an aqueous solution containing an inorganic metal salt to a latex containing a rubber-like polymer and aggregating the rubber-like polymer, and the sp value is The second aggregating step of aggregating the rubber-like polymer by adding the organic solvent of 11 to 15 is performed.
無機金属塩としては、特に限定されないが、水酸化ナトリウム、硫酸ナトリウム、硫酸カルシウム、硫酸マグネシウム、硫酸アンモニウム、硫酸アルミニウム、塩化ナトリウム、塩化カルシウム、塩化マグネシウムなどの金属塩が挙げられ、これらを２種以上併用するものであってもよい。これらの無機金属塩の中でも３価の無機金属イオンを有する無機金属塩であることが好ましい。 The inorganic metal salt is not particularly limited, and examples thereof include metal salts such as sodium hydroxide, sodium sulfate, calcium sulfate, magnesium sulfate, ammonium sulfate, aluminum sulfate, sodium chloride, calcium chloride, and magnesium chloride. You may use together. Among these inorganic metal salts, an inorganic metal salt having a trivalent inorganic metal ion is preferable.
無機金属塩を含む水溶液の濃度は、特に限定されないが、０．１〜３０質量％であることが好ましく、１〜１０質量％であることがより好ましい。 The concentration of the aqueous solution containing the inorganic metal salt is not particularly limited, but is preferably 0.1 to 30% by mass, and more preferably 1 to 10% by mass.
無機金属塩の配合量としては、特に限定されないが、ゴム状重合体１００質量部に対して、３〜１０質量部であることが好ましく、３〜７質量部であることがより好ましい。 The compounding amount of the inorganic metal salt is not particularly limited, but is preferably 3 to 10 parts by mass, and more preferably 3 to 7 parts by mass with respect to 100 parts by mass of the rubber-like polymer.
無機金属塩の添加速度は、特に限定されないが、ゴム状重合体１００質量部に対して、０．１〜１００質量部／ｍｉｎであることが好ましく、１〜５０質量部／ｍｉｎであることがより好ましい。 The addition rate of the inorganic metal salt is not particularly limited, but is preferably 0.1 to 100 parts by mass/min, and is 1 to 50 parts by mass/min, relative to 100 parts by mass of the rubber-like polymer. More preferable.
ｓｐ値が１１〜１５である有機溶媒としては、例えば、メタノール（ｓｐ値：１４．５）、イソプロピルアルコール（ｓｐ値：１１．５）、アセトニトリル（ｓｐ値：１１．９）、エタノール（ｓｐ値：１２．７）、ジメチルホルムアミド（ｓｐ値：１２．０）、ジメチルスルホキシド（ｓｐ値：１２．０）、エチレングリコール（ｓｐ値：１４．２）などが挙げられる。ｓｐ値が上記範囲内である場合、スラリー状のゴム状重合体が得られやすい。 Examples of the organic solvent having an sp value of 11 to 15 include methanol (sp value: 14.5), isopropyl alcohol (sp value: 11.5), acetonitrile (sp value: 11.9), ethanol (sp value: :12.7), dimethylformamide (sp value: 12.0), dimethyl sulfoxide (sp value: 12.0), ethylene glycol (sp value: 14.2) and the like. When the sp value is within the above range, a slurry-like rubbery polymer is easily obtained.
ここで本明細書において、ｓｐ値（溶解パラメータ）とは、例えば、向井淳二、金城徳幸著「技術者のための実学高分子」（講談社、１９８１年１０月１日発行）の７１〜７７頁に記載のＦｅｄｏｒｓの式により算出される２５℃における値δ［（ｃａｌ／ｃｍ３）１／２］であり、１（ｃａｌ／ｃｍ３）１／２＝２．０５（ＭＪ／ｍ３）１／２であり、そのため、ＳＰ値が１０（ｃａｌ／ｃｍ３）１／２以下とは２０．５（ＭＪ／ｍ３）１／２以下であることを意味する。
Ｆｅｄｏｒｓの式：
ＳＰ値（δ）＝（Ｅｖ／ｖ）１／２＝（ΣΔｅｉ／ΣΔｖｉ）１／２
Ｅｖ：蒸発エネルギー
ｖ：モル体積
Δｅｉ：各成分の原子又は原子団の蒸発エネルギー
Δｖｉ：各原子又は原子団のモル体積
In the present specification, the sp value (dissolution parameter) refers to, for example, Junji Mukai and Tokuyuki Kaneshiro, "Practical Polymers for Engineers" (Kodansha, October 1, 1981), pages 71 to 77. The value δ [(cal/cm 3 ) 1/2 ] at 25° C. calculated by the Fedors equation described in 1 ), and 1 (cal/cm 3 ) 1/2 =2.05 (MJ/m 3 ) 1 / 2, therefore, SP value and 10 (cal / cm 3) 1/2 or less means that is 20.5 (MJ / m 3) 1/2 or less.
Fedors formula:
SP value (δ)=(Ev/v) 1/2 =(ΣΔei/ΣΔvi) 1/2
Ev: evaporation energy v: molar volume Δei: evaporation energy of atoms or atomic groups of each component Δvi: molar volume of each atom or atomic group
上記の式の計算に使用する各原子又は原子団の蒸発エネルギー、モル体積は、Ｆ． Ｆｅｄｏｒｓ， Ｐｏｌｙｍ． Ｅｎｇ． Ｓｃｉ．， １４， １４７ 〈１９７４〉を参照することができる。 The evaporation energy and the molar volume of each atom or atomic group used for the calculation of the above formula are F. Fedors, Polym. Eng. Sci. , 14, 147 <1974>.
上記有機溶媒の配合量としては、特に限定されないが、ラテックス、無機金属塩を含有する水溶液、及び有機溶媒の混合液の液体成分中、１０〜６０質量％であることが好ましく、１５〜５０質量％であることがより好ましい。１０質量％以上である場合、ゴム状重合体の凝集が起こりやすく、６０質量％以下である場合、スラリー状のゴム状重合体が得られやすい。 The blending amount of the organic solvent is not particularly limited, but is preferably 10 to 60 mass% in the liquid component of the mixed solution of the latex, the aqueous solution containing the inorganic metal salt, and the organic solvent, and preferably 15 to 50 mass. % Is more preferable. When it is 10% by mass or more, aggregation of the rubber-like polymer easily occurs, and when it is 60% by mass or less, a slurry-like rubber-like polymer is easily obtained.
上記有機溶媒の添加速度は、特に限定されないが、ラテックスと、無機金属塩を含有する水溶液との混合液の液体成分１００質量部に対して、０．１〜１００質量部／ｍｉｎであることが好ましく、１〜５０質量部／ｍｉｎであることがより好ましい。 The addition rate of the organic solvent is not particularly limited, but may be 0.1 to 100 parts by mass/min with respect to 100 parts by mass of the liquid component of the mixed liquid of the latex and the aqueous solution containing the inorganic metal salt. It is more preferably 1 to 50 parts by mass/min.
本実施形態のように、ゴム状重合体を含有するラテックス中に、無機金属塩を含む水溶液を添加した場合、ゴム状重合体が凝集によって塊状とはならず、二次粒子や三次粒子のゴム状重合体が分散したスラリー状態を維持することができる。そのメカニズムは定かではないが、ゴム状重合体の表面の電荷が無機金属イオンによって相殺されることで、ゴム状重合体と有機溶媒との相溶性が高まり、ゴム状重合体が緩やかに凝集するためと考えられる。本実施形態の製造方法によれば、工業的に製造する際に得られるゴム状重合体クラムは流動性を有するため、凝集槽の排出口から容易にゴム状重合体を回収することができる。ここで、本明細書において「凝集」とは、コロイド粒子が集まってより大きな粒子になる現象をいう。 As in the present embodiment, in a latex containing a rubber-like polymer, when an aqueous solution containing an inorganic metal salt is added, the rubber-like polymer does not become agglomerate due to aggregation, and the rubber of the secondary particles or the tertiary particles is used. It is possible to maintain the slurry state in which the polymer is dispersed. Although the mechanism is not clear, the surface charge of the rubber-like polymer is offset by the inorganic metal ion, so that the compatibility between the rubber-like polymer and the organic solvent is increased, and the rubber-like polymer is slowly aggregated. It is thought to be because. According to the production method of the present embodiment, since the rubber-like polymer crumb obtained during industrial production has fluidity, the rubber-like polymer can be easily recovered from the discharge port of the coagulation tank. As used herein, the term “aggregation” refers to a phenomenon in which colloidal particles are aggregated into larger particles.
ゴム状重合体の重合方法としては、特に限定されず、例えば、乳化重合法、溶液重合法懸濁重合法が挙げられ、この中でも乳化重合法であることが好ましい。 The method for polymerizing the rubber-like polymer is not particularly limited, and examples thereof include an emulsion polymerization method, a solution polymerization method, and a suspension polymerization method. Among them, the emulsion polymerization method is preferable.
本実施形態の凝集工程において使用する攪拌機は、特に限定されず、例えば、撹拌翼形状としては三方後退翼、パドル型、アンカー型、タービン翼、マックスブレンド翼などの一般的な撹拌翼の攪拌機を用いることができる。 The stirrer used in the aggregating step of the present embodiment is not particularly limited, for example, as the stirring blade shape, a three-way backward blade, paddle type, anchor type, turbine blade, a mixer of a general stirring blade such as Maxblend blade. Can be used.
本実施形態の凝集工程における上記攪拌機の回転数は、特に限定されず、使用する攪拌機の撹拌翼形状によっても異なるが、例えば、三方後退翼を用いた場合、６０〜５００ｒｐｍであってもよく、１００〜４００ｒｐｍであってもよい。 The rotation speed of the stirrer in the aggregating step of the present embodiment is not particularly limited, and varies depending on the shape of the stirring blade of the stirrer used, for example, when using a three-way retraction blade, it may be 60 to 500 rpm, It may be 100 to 400 rpm.
以下、本発明の実施例を示すが、本発明はこれらの実施例に限定されるものではない。
［合成例］
３０００ｇのメタクリル酸２，４，６−トリメチルヘプチル（メタクリル酸イソデシル）、７８．８ｇのエチレングリコールジメタクリレート、３８２．２ｇのドデシル硫酸ナトリウム、６３００ｇの水および７００ｇのエタノールを混合し、１時間撹拌させることによりモノマーを乳化させ、３５．８ｇの過硫酸カリウムを添加した後、撹拌しながら１時間の窒素バブリングを実施し、溶液を７０℃で８時間保持することにより、ゴム状重合体の微粒子が分散したラテックスが得られた。
Examples of the present invention will be shown below, but the present invention is not limited to these examples.
[Synthesis example]
3000 g of 2,4,6-trimethylheptyl methacrylate (isodecyl methacrylate), 78.8 g of ethylene glycol dimethacrylate, 382.2 g of sodium dodecyl sulfate, 6300 g of water and 700 g of ethanol are mixed and stirred for 1 hour. Then, the monomer was emulsified, 35.8 g of potassium persulfate was added, nitrogen bubbling was carried out for 1 hour with stirring, and the solution was kept at 70° C. for 8 hours, whereby fine particles of the rubber-like polymer were obtained. A dispersed latex was obtained.
得られたラテックスを撹拌させながら、凝集液を添加することにより凝集を実施した。 Aggregation was performed by adding an aggregating liquid while stirring the obtained latex.
撹拌は、凝集槽内での撹拌翼による機械撹拌方式で、撹拌翼形状としては三方後退翼にて実施した。 The stirring was carried out by a mechanical stirring method using stirring blades in the aggregating tank, and the stirring blade shape was a three-way retreating blade.
得られたゴム状重合体の凝集状態を目視にて確認した。凝集したゴム状重合体がスラリー状に分散しているものは工業的な製造において優れた作業性を有していると評価し、十分な凝集が得られないものや、ゴム状重合体が凝固して塊状になったものは工業的な製造に不適として評価した。 The aggregation state of the obtained rubber-like polymer was visually confirmed. Those in which the agglomerated rubber-like polymer is dispersed in a slurry state are evaluated as having excellent workability in industrial production, and those in which sufficient agglomeration cannot be obtained or the rubber-like polymer coagulates. The resulting lumps were evaluated as unsuitable for industrial production.
［比較例１］
得られたエマルションを３００ｒｐｍで攪拌させながら、メタノールを１０５００ｇ添加することによりゴム状重合体Ａを凝集させた。ゴム状重合体Ａは、塊状の固体として凝固析出した。有機溶媒の配合量は、ラテックスと凝集液との混合液の液体成分中、６０質量％であった。
[Comparative Example 1]
While stirring the obtained emulsion at 300 rpm, 10500 g of methanol was added to aggregate the rubber-like polymer A. The rubbery polymer A was solidified and precipitated as a lumpy solid. The blending amount of the organic solvent was 60% by mass in the liquid component of the mixed liquid of the latex and the aggregating liquid.
［実施例１］
比較例１で用いたメタノールの代わりに、３ｗｔ％の硫酸アルミニウム水溶液を５２５０ｇ添加して重合体を緩凝集させた後、イソプロピルアルコール（ＩＰＡ）を５２５０ｇ添加した以外は比較例１と同様の手法によりゴム状重合体１を凝集させた。ゴム状重合体１は、溶液中に分散したスラリー状として析出した。無機金属塩の配合量は、ゴム状重合体１００質量部に対して５質量部であり、有機溶媒の配合量は、ラテックスと凝集液との混合液の液体成分中、３０質量％であった。
[Example 1]
Instead of the methanol used in Comparative Example 1, 5250 g of a 3 wt% aluminum sulfate aqueous solution was added to slowly agglomerate the polymer, and then 5250 g of isopropyl alcohol (IPA) was added. The rubber-like polymer 1 was aggregated. The rubbery polymer 1 was deposited as a slurry dispersed in the solution. The content of the inorganic metal salt was 5 parts by mass with respect to 100 parts by mass of the rubber-like polymer, and the content of the organic solvent was 30 mass% in the liquid component of the mixed solution of the latex and the aggregating liquid. ..
［実施例２］
実施例１で用いたイソプロピルアルコールの代わりにアセトニトリルを５２５０ｇ用いた以外は実施例１と同様の手法にてゴム状重合体２を凝集させた。ゴム状重合体２は、溶液中に分散したスラリー状として析出した。無機金属塩の配合量は、ゴム状重合体１００質量部に対して５質量部であり、有機溶媒の配合量は、ラテックスと凝集液との混合液の液体成分中、３０質量％であった。
[Example 2]
The rubbery polymer 2 was aggregated in the same manner as in Example 1 except that 5250 g of acetonitrile was used instead of the isopropyl alcohol used in Example 1. The rubbery polymer 2 was deposited as a slurry dispersed in the solution. The content of the inorganic metal salt was 5 parts by mass with respect to 100 parts by mass of the rubber-like polymer, and the content of the organic solvent was 30 mass% in the liquid component of the mixed solution of the latex and the aggregating liquid. ..
［実施例３］
実施例１で用いたイソプロピルアルコールの代わりにエタノールを５２５０ｇ用いた以外は実施例１と同様の手法にてゴム状重合体３を凝集させた。ゴム状重合体３は、溶液中に分散したスラリー状として析出した。無機金属塩の配合量は、ゴム状重合体１００質量部に対して５質量部であり、有機溶媒の配合量は、ラテックスと凝集液との混合液の液体成分中、３０質量％であった。
[Example 3]
The rubbery polymer 3 was aggregated in the same manner as in Example 1 except that 5250 g of ethanol was used instead of the isopropyl alcohol used in Example 1. The rubber-like polymer 3 was deposited as a slurry dispersed in the solution. The content of the inorganic metal salt was 5 parts by mass with respect to 100 parts by mass of the rubber-like polymer, and the content of the organic solvent was 30 mass% in the liquid component of the mixed solution of the latex and the aggregating liquid. ..
［実施例４］
実施例１で用いたイソプロピルアルコールの代わりにメタノールを５２５０ｇ用いた以外は実施例１と同様の手法にてゴム状重合体４を凝集させた。ゴム状重合体４は、溶液中に分散したスラリー状として析出した。無機金属塩の配合量は、ゴム状重合体１００質量部に対して５質量部であり、有機溶媒の配合量は、ラテックスと凝集液との混合液の液体成分中、３０質量％であった。
[Example 4]
The rubbery polymer 4 was aggregated in the same manner as in Example 1 except that 5250 g of methanol was used instead of the isopropyl alcohol used in Example 1. The rubbery polymer 4 was deposited as a slurry dispersed in the solution. The content of the inorganic metal salt was 5 parts by mass with respect to 100 parts by mass of the rubber-like polymer, and the content of the organic solvent was 30 mass% in the liquid component of the mixed solution of the latex and the aggregating liquid. ..
［比較例２］
実施例１で用いたイソプロピルアルコールの代わりにメチルエチルケトン（ＭＥＫ）を５２５０ｇ用いた以外は実施例１と同様の手法にてゴム状重合体５を凝集させた。ゴム状重合体５は、塊状の固体として凝固析出した。無機金属塩の配合量は、ゴム状重合体１００質量部に対して５質量部であり、有機溶媒の配合量は、ラテックスと凝集液との混合液の液体成分中、３０質量％であった。
[Comparative example 2]
The rubbery polymer 5 was aggregated in the same manner as in Example 1 except that 5250 g of methyl ethyl ketone (MEK) was used instead of the isopropyl alcohol used in Example 1. The rubber-like polymer 5 was solidified and precipitated as a lumpy solid. The content of the inorganic metal salt was 5 parts by mass with respect to 100 parts by mass of the rubber-like polymer, and the content of the organic solvent was 30 mass% in the liquid component of the mixed solution of the latex and the aggregating liquid. ..
［比較例３］
実施例１で用いたイソプロピルアルコールの代わりにテトラヒドロフラン（ＴＨＦ）を５２５０ｇ用いた以外は実施例１と同様の手法にてゴム状重合体６を凝集させた。ゴム状重合体６は、塊状の固体として凝固析出した。無機金属塩の配合量は、ゴム状重合体１００質量部に対して５質量部であり、有機溶媒の配合量は、ラテックスと凝集液との混合液の液体成分中、３０質量％であった。
[Comparative Example 3]
The rubber-like polymer 6 was aggregated in the same manner as in Example 1 except that 5250 g of tetrahydrofuran (THF) was used instead of the isopropyl alcohol used in Example 1. The rubber-like polymer 6 was solidified and precipitated as a lumpy solid. The content of the inorganic metal salt was 5 parts by mass with respect to 100 parts by mass of the rubber-like polymer, and the content of the organic solvent was 30 mass% in the liquid component of the mixed solution of the latex and the aggregating liquid. ..
［実施例５］
実施例４で用いた硫酸アルミニウムの代わりに塩化ナトリウム水溶液を５２５０ｇ用いた以外は実施例４と同様の手法にてゴム状重合体７を凝集させた。ゴム状重合体７は、溶液中に分散したスラリー状として析出した。無機金属塩の配合量は、ゴム状重合体１００質量部に対して５質量部であり、有機溶媒の配合量は、ラテックスと凝集液との混合液の液体成分中、３０質量％であった。
[Example 5]
The rubber-like polymer 7 was aggregated in the same manner as in Example 4 except that 5250 g of an aqueous sodium chloride solution was used instead of the aluminum sulfate used in Example 4. The rubber-like polymer 7 was deposited as a slurry dispersed in the solution. The content of the inorganic metal salt was 5 parts by mass with respect to 100 parts by mass of the rubber-like polymer, and the content of the organic solvent was 30 mass% in the liquid component of the mixed solution of the latex and the aggregating liquid. ..
［実施例６］
実施例４で用いた硫酸アルミニウムの代わりに塩化カルシウム水溶液を５２５０ｇ用いた以外は実施例４と同様の手法にてゴム状重合体８を凝集させた。ゴム状重合体８は、溶液中に分散したスラリー状として析出された。無機金属塩の配合量は、ゴム状重合体１００質量部に対して５質量部であり、有機溶媒の配合量は、ラテックスと凝集液との混合液の液体成分中、３０質量％であった。
[Example 6]
The rubber-like polymer 8 was aggregated in the same manner as in Example 4 except that 5250 g of an aqueous calcium chloride solution was used instead of the aluminum sulfate used in Example 4. The rubbery polymer 8 was deposited as a slurry dispersed in the solution. The content of the inorganic metal salt was 5 parts by mass with respect to 100 parts by mass of the rubber-like polymer, and the content of the organic solvent was 30 mass% in the liquid component of the mixed solution of the latex and the aggregating liquid. ..
結果は、表１に示す通りであり、実施例１〜６では、いずれも流動性を保ったスラリー状態のゴム状重合体が得られ、工業的な製造において優れた作業性が得られることがわかった。 The results are shown in Table 1, and in Examples 1 to 6, rubbery polymers in a slurry state in which fluidity was maintained were obtained, and excellent workability in industrial production was obtained. all right.
比較例１は凝集剤としてメタノールを単独で用いた例であり、ゴム状重合体が塊状になり、工業的な製造には不適であった。 Comparative Example 1 is an example in which methanol was used alone as the coagulant, and the rubber-like polymer became lumpy, which was not suitable for industrial production.
比較例２，３は凝集剤として使用した有機溶媒のｓｐ値が所定範囲外である例であり、いずれもゴム状重合体が塊状になり、工業的な製造には不適であった。 Comparative Examples 2 and 3 are examples in which the sp value of the organic solvent used as the aggregating agent was outside the predetermined range, and in both cases, the rubber-like polymer became lumpy and was not suitable for industrial production.
本発明のゴム状重合体の製造方法は、各種用途に用いられるゴム状重合体を工業的に製造する際に好適に用いることができる。 The method for producing a rubber-like polymer of the present invention can be suitably used when industrially producing a rubber-like polymer used for various purposes.
Claims (3)
無機金属塩を含む水溶液を添加し、ゴム状重合体を凝集させる第一凝集工程と、
ｓｐ値が１１〜１５である有機溶媒を添加し、ゴム状重合体を凝集させる第二凝集工程とを有する、ゴム状重合体の製造方法。 To the latex containing the rubbery polymer,
An aqueous solution containing an inorganic metal salt is added, and a first aggregation step of aggregating the rubber-like polymer,
A second aggregation step of adding an organic solvent having an sp value of 11 to 15 to agglomerate the rubber-like polymer, and producing a rubber-like polymer.
The method for producing a rubber-like polymer according to claim 1 or 2, wherein the inorganic metal salt has a trivalent inorganic metal ion.
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| JPS60124627A (en) * | 1983-12-12 | 1985-07-03 | Mitsubishi Rayon Co Ltd | Production of thermoplastic resin powder |
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|---|---|---|---|---|
| JPS60124627A (en) * | 1983-12-12 | 1985-07-03 | Mitsubishi Rayon Co Ltd | Production of thermoplastic resin powder |
| JPH0625321A (en) * | 1992-03-31 | 1994-02-01 | Nippon Zeon Co Ltd | Production of vinyl chloride resin for processing into paste |
| JPH0873520A (en) * | 1994-08-31 | 1996-03-19 | Kanegafuchi Chem Ind Co Ltd | Production of coagulated particle from polymer latex |
| JP2002363372A (en) * | 2001-06-11 | 2002-12-18 | Kanegafuchi Chem Ind Co Ltd | Polymer composition |
| JP2006104320A (en) * | 2004-10-05 | 2006-04-20 | Kaneka Corp | Method for producing polymer particle |
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