JP5941806B2 - Method for producing polymer composition - Google Patents
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- 239000000203 mixture Substances 0.000 title claims description 164
- 229920000642 polymer Polymers 0.000 title claims description 120
- 238000004519 manufacturing process Methods 0.000 title claims description 76
- 229920001577 copolymer Polymers 0.000 claims description 97
- 230000003472 neutralizing effect Effects 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000003795 chemical substances by application Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical group CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 claims description 35
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 26
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 description 42
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000002270 dispersing agent Substances 0.000 description 19
- 230000002776 aggregation Effects 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- 238000004220 aggregation Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 239000000843 powder Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000010954 inorganic particle Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000012860 organic pigment Substances 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- -1 hydroxyethyl group Chemical group 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000003125 aqueous solvent Substances 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001256 steam distillation Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- RGYAVZGBAJFMIZ-UHFFFAOYSA-N 2,3-dimethylhex-2-ene Chemical compound CCCC(C)=C(C)C RGYAVZGBAJFMIZ-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229920005603 alternating copolymer Polymers 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
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 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
- 239000000919 ceramic Substances 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- AVWWPFWBTLONRB-UHFFFAOYSA-N furan-2,5-dione;2-methylprop-1-ene Chemical compound CC(C)=C.CC(C)=C.O=C1OC(=O)C=C1 AVWWPFWBTLONRB-UHFFFAOYSA-N 0.000 description 1
- LSAOZCAKUIANSQ-UHFFFAOYSA-N heptobarbital Chemical compound C=1C=CC=CC=1C1(C)C(=O)NC(=O)NC1=O LSAOZCAKUIANSQ-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- NIWMEUWZZDPUEQ-UHFFFAOYSA-M sodium;azane;hydroxide Chemical compound N.[OH-].[Na+] NIWMEUWZZDPUEQ-UHFFFAOYSA-M 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、重合体組成物の製造方法に関する。 The present invention relates to a method for producing a polymer composition.
ジイソブチレンと無水マレイン酸との共重合体を中和して得られる重合体組成物は、水系分散剤、すなわち無機粒子、有機顔料などの粉体用の水系媒体中における分散剤として有用であり、幅広く使用されている。前記重合体組成物は、一般的に以下の方法によって製造される。すなわち、ジイソブチレンと無水マレイン酸との混合物を有機溶媒中で溶液重合させて共重合体を得た後、有機溶媒を水に置換する溶媒置換を行って、共重合体を沈殿させる。次いで、アルカリ性化合物を添加して共重合体を中和し、重合体組成物を得る。ジイソブチレン−無水マレイン酸の共重合体の中和工程では、重合体組成物の水系分散剤としての性能向上、すなわち、無機粒子、有機顔料などの粉体の分散性向上の観点から、中和剤として通常アルカリ金属水酸化物が使用される。 A polymer composition obtained by neutralizing a copolymer of diisobutylene and maleic anhydride is useful as an aqueous dispersant, that is, a dispersant in an aqueous medium for powders such as inorganic particles and organic pigments. Widely used. The polymer composition is generally produced by the following method. That is, a mixture of diisobutylene and maleic anhydride is solution polymerized in an organic solvent to obtain a copolymer, and then the solvent is replaced by replacing the organic solvent with water to precipitate the copolymer. Next, an alkaline compound is added to neutralize the copolymer to obtain a polymer composition. In the step of neutralizing the copolymer of diisobutylene-maleic anhydride, neutralization is performed from the viewpoint of improving the performance of the polymer composition as an aqueous dispersant, that is, improving the dispersibility of powders such as inorganic particles and organic pigments. Alkali metal hydroxide is usually used as the agent.
特許文献１は、無水マレイン酸、トリメチルペンテン及びジトリメチルペンテンの共重合体並びにその製造方法を開示している。特許文献２は、イソブチレン−無水マレイン酸共重合体の中和物を架橋して得られる吸水性樹脂の製造方法を開示している。 Patent Document 1 discloses a copolymer of maleic anhydride, trimethylpentene and ditrimethylpentene and a method for producing the same. Patent Document 2 discloses a method for producing a water-absorbent resin obtained by crosslinking a neutralized product of isobutylene-maleic anhydride copolymer.
しかしながら、水溶媒中で、ジイソブチレンと無水マレイン酸との共重合体の中和を、アルカリ金属水酸化物を用いて行うと、中和工程の開始直後から前記共重合体の凝集や反応槽への付着が発生し、中和を完了させるために長時間の加熱及び攪拌を要していた。また、中和反応が均一に進行しないため、得られる重合体組成物の分散剤としての性能が低下するという課題があった。特許文献１及び２に開示された方法では、これらの課題は解決されていない。 However, when the copolymer of diisobutylene and maleic anhydride is neutralized using an alkali metal hydroxide in an aqueous solvent, the copolymer agglomeration or reaction tank is started immediately after the start of the neutralization step. Adhesion to the surface occurred, and heating and stirring for a long time were required to complete neutralization. Moreover, since the neutralization reaction does not proceed uniformly, there has been a problem that the performance of the resulting polymer composition as a dispersant deteriorates. These problems are not solved by the methods disclosed in Patent Documents 1 and 2.
本発明は、ジイソブチレンと無水マレイン酸との共重合体を中和して得られる重合体組成物を製造する方法であって、共重合体の中和工程での凝集や反応槽への付着を抑制することによって、中和を完了させるための長時間の加熱および攪拌といった中和工程における負荷を大幅に低減するとともに、得られる重合体組成物の分散剤としての性能を向上できる、重合体組成物の製造方法を提供することを課題とする。 The present invention relates to a method for producing a polymer composition obtained by neutralizing a copolymer of diisobutylene and maleic anhydride, which is agglomerated in a neutralization step of the copolymer and attached to a reaction vessel. A polymer capable of significantly reducing the load in the neutralization step such as long-time heating and stirring for completing the neutralization and improving the performance of the resulting polymer composition as a dispersant. It is an object to provide a method for producing a composition.
本発明は、無水マレイン酸とジイソブチレンとの共重合体と、中和剤とを混合して得られる重合体組成物の製造方法であって、
工程１ 前記共重合体及び水を含有する組成物と、一般式（Ｉ）で表される化合物からなる第１の中和剤とを、混合する工程、
（式中、Ｒ1、Ｒ2及びＲ3は同一又は異なって、水素原子が水酸基で置換されていてもよい炭素数１〜３のアルキル基又は水素原子を示す）
工程２ 工程１で得られた混合物と、アルカリ金属水酸化物からなる第２の中和剤とを、混合する工程、を含む重合体組成物の製造方法に関する。
The present invention is a method for producing a polymer composition obtained by mixing a copolymer of maleic anhydride and diisobutylene and a neutralizing agent,
Process 1 The process of mixing the composition containing the said copolymer and water, and the 1st neutralizing agent which consists of a compound represented by general formula (I),
(In formula, R < 1 >, R < 2 > and R < 3 > are the same or different, and the C1-C3 alkyl group or hydrogen atom in which the hydrogen atom may be substituted by the hydroxyl group is shown.)
Process 2 It is related with the manufacturing method of a polymer composition including the process of mixing the mixture obtained at the process 1, and the 2nd neutralizing agent consisting of an alkali metal hydroxide.
本発明の重合体組成物の製造方法によれば、ジイソブチレンと無水マレイン酸との共重合体を中和して得られる重合体組成物を製造するに際して、共重合体の中和工程での凝集や反応槽への付着を抑制することによって、中和工程の負荷を大幅に低減するとともに、得られる重合体組成物の分散剤としての性能を向上できる。 According to the method for producing a polymer composition of the present invention, when producing a polymer composition obtained by neutralizing a copolymer of diisobutylene and maleic anhydride, By suppressing aggregation and adhesion to the reaction tank, the load of the neutralization step can be greatly reduced, and the performance of the resulting polymer composition as a dispersant can be improved.
本発明は、無水マレイン酸とジイソブチレンとの共重合体と、中和剤とを混合して得られる重合体組成物の製造方法であって、
工程１ 前記共重合体及び水を含有する組成物と、前記一般式（Ｉ）で表される化合物からなる第１の中和剤とを、混合する工程、
工程２ 工程１で得られた混合物と、アルカリ金属水酸化物からなる第２の中和剤とを、混合する工程、を含む重合体組成物の製造方法により、共重合体の中和工程での凝集や反応槽への付着を抑制することによって、中和工程の負荷を大幅に低減するとともに、得られる重合体組成物の分散剤としての性能を向上できるという知見に基づく。
The present invention is a method for producing a polymer composition obtained by mixing a copolymer of maleic anhydride and diisobutylene and a neutralizing agent,
Process 1 The process of mixing the composition containing the said copolymer and water, and the 1st neutralizing agent which consists of a compound represented by the said general formula (I),
Step 2 In the step of neutralizing the copolymer by the method for producing a polymer composition comprising the step of mixing the mixture obtained in Step 1 and the second neutralizing agent comprising an alkali metal hydroxide. It is based on the knowledge that the performance of the resulting polymer composition as a dispersant can be improved while the load of the neutralization process is greatly reduced by suppressing the aggregation of the polymer and the adhesion to the reaction tank.
本発明の効果発現のメカニズムの詳細は不明であるが、以下の様に推定している。本発明における共重合体及び水を含有する組成物と、アルカリ性化合物とを混合すると、まず共重合体の塊状粒子表面で中和反応が起こり、塊状粒子を覆う膜（中和膜）が形成される。この際、前記アルカリ性化合物としてアルカリ金属水酸化物を用いると、高密度で粘性の高い中和膜が形成されるため、塊状粒子表面の中和膜同士が粘着して塊状粒子の凝集が進行する。一方、アルカリ性化合物として一般式（Ｉ）で表される化合物を用いた場合、カチオン基が嵩高いために中和膜は低密度で高水溶性となる。そのため、中和膜が共重合体の塊状粒子の分散剤として作用し、塊状粒子の流動性が向上すると共に中和膜同士の粘着による凝集が抑制される。また、その状態の共重合体と水を含有する組成物にアルカリ金属水酸化物を混合しても、塊状粒子の良好な分散状態が維持されるので、中和工程での共重合体の凝集や反応槽への付着が抑制され、中和工程における負荷が大幅に低減する。更には、中和が均一に進行しやすくなるため、得られる重合体組成物の分散剤としての性能も向上する。但し、これらは推定であって、本発明は、これらメカニズムに限定されない。 The details of the mechanism of the effect of the present invention are not clear, but are estimated as follows. When the composition containing the copolymer and water in the present invention is mixed with an alkaline compound, first, a neutralization reaction occurs on the surface of the copolymer bulk particles, and a film (neutralization film) covering the bulk particles is formed. The At this time, when an alkali metal hydroxide is used as the alkaline compound, a neutralized film having high density and high viscosity is formed. Therefore, the neutralized films on the surface of the massive particles adhere to each other and aggregation of the massive particles proceeds. . On the other hand, when the compound represented by the general formula (I) is used as the alkaline compound, the neutralization film becomes low density and highly water-soluble because the cationic group is bulky. Therefore, the neutralization film acts as a dispersing agent for the bulk particles of the copolymer, and the fluidity of the bulk particles is improved and aggregation due to adhesion between the neutralization films is suppressed. In addition, even when an alkali metal hydroxide is mixed with the composition containing the copolymer and water in that state, a good dispersion state of the massive particles is maintained, so that the copolymer is aggregated in the neutralization step. And the adhesion to the reaction tank is suppressed, and the load in the neutralization process is greatly reduced. Furthermore, since neutralization easily proceeds uniformly, the performance of the resulting polymer composition as a dispersant is also improved. However, these are estimations, and the present invention is not limited to these mechanisms.
すなわち本発明は、一つの態様において、無水マレイン酸とジイソブチレンとの共重合体と、中和剤とを混合して得られる重合体組成物の製造方法であって、
工程１ 前記共重合体及び水を含有する組成物と、前記一般式（Ｉ）で表される化合物からなる第１の中和剤とを、混合する工程、
工程２ 工程１で得られた混合物と、アルカリ金属水酸化物からなる第２の中和剤とを、混合する工程、を有する重合体組成物の製造方法に関する。本発明の重合体組成物の製造方法によれば、共重合体の中和工程での凝集や反応槽への付着を抑制することによって、中和工程における負荷を大幅に低減するとともに、得られる重合体組成物の分散剤としての性能を向上できるという効果が奏されうる。
That is, the present invention, in one embodiment, is a method for producing a polymer composition obtained by mixing a copolymer of maleic anhydride and diisobutylene and a neutralizing agent,
Process 1 The process of mixing the composition containing the said copolymer and water, and the 1st neutralizing agent which consists of a compound represented by the said general formula (I),
Process 2 It is related with the manufacturing method of the polymer composition which has the process of mixing the mixture obtained at the process 1, and the 2nd neutralizing agent consisting of an alkali metal hydroxide. According to the method for producing a polymer composition of the present invention, it is possible to significantly reduce the load in the neutralization step by suppressing aggregation in the neutralization step of the copolymer and adhesion to the reaction tank. The effect that the performance as a dispersing agent of a polymer composition can be improved can be produced.
［共重合体］
ジイソブチレンと無水マレイン酸との共重合体は、例えば特開昭５５−４０７９７記載の公知の方法によって製造することができる。
[Copolymer]
A copolymer of diisobutylene and maleic anhydride can be produced by, for example, a known method described in JP-A-55-40797.
また、前記共重合体の製造は、例えば以下の方法による。すなわち、有機溶媒とモノマーとしてのジイソブチレンとを含有する液を加熱および攪拌しながら、前記液に開始剤及びモノマーとしての無水マレイン酸を添加して重合を行い、共重合体を含有する溶液を得る。更に前記共重合体溶液に含まれる有機溶媒を水系溶媒に置換する溶媒置換を行って共重合体を沈殿させ、共重合体と水とを含有する組成物を得る。製造の容易性の観点、安価に製造できる観点から、重合法は沈殿重合法が好ましい。 The copolymer is produced, for example, by the following method. That is, while heating and stirring a liquid containing an organic solvent and diisobutylene as a monomer, an initiator and maleic anhydride as a monomer are added to the liquid to perform polymerization, and a solution containing a copolymer is obtained. obtain. Furthermore, solvent substitution which substitutes the organic solvent contained in the copolymer solution with an aqueous solvent is performed to precipitate the copolymer, thereby obtaining a composition containing the copolymer and water. The polymerization method is preferably a precipitation polymerization method from the viewpoint of easy production and low cost production.
前記共重合体は、分散性に優れる重合体組成物、すなわち無機粒子、有機顔料などの粉体用の分散剤として使用した際に水系分散剤として性能が高い重合体組成物を製造する観点及び共重合体の製造の容易性の観点から、ジイソブチレンと無水マレイン酸との交互共重合体が好ましい。前記共重合体を構成する、ジイソブチレンに由来する構成単位と無水マレイン酸に由来する構成単位とのモル比（ジイソブチレン由来の構成単位／無水マレイン酸由来の構成単位）は、水溶性及び分散性に優れる重合体組成物を製造する観点並びに共重合体の製造の容易性の観点から、実質的に１／１であることが好ましい。 The copolymer is a polymer composition excellent in dispersibility, that is, a viewpoint of producing a polymer composition having high performance as an aqueous dispersant when used as a dispersant for powders such as inorganic particles and organic pigments, and From the viewpoint of ease of production of the copolymer, an alternating copolymer of diisobutylene and maleic anhydride is preferred. The molar ratio of the structural unit derived from diisobutylene and the structural unit derived from maleic anhydride constituting the copolymer (the structural unit derived from diisobutylene / the structural unit derived from maleic anhydride) is water-soluble and dispersed. From the viewpoint of producing a polymer composition having excellent properties and ease of production of the copolymer, it is preferably substantially 1/1.
前記共重合体の合成を効率良く行う観点から、共重合体を製造する際の仕込み量において、無水マレイン酸に対しジイソブチレンを過剰に用いることが好ましい。また、無水マレイン酸に対する過剰のジイソブチレンが、共重合体の合成における有機溶媒として利用できる観点からも好ましい。無水マレイン酸の仕込み量に対するジイソブチレンの仕込み量のモル比（ジイソブチレン／無水マレイン酸）は、共重合体の合成においてモノマーの反応速度を確保する観点から、１．２以上が好ましく、２以上がより好ましく、２．５以上が更に好ましい。また、前記モル比（ジイソブチレン／無水マレイン酸）は、共重合体を含有する溶液を得た後に、ジイソブチレンの回収を効率よく行う観点から、５以下が好ましく、４以下がより好ましく、３．５以下が更に好ましい。 From the viewpoint of efficiently synthesizing the copolymer, it is preferable to use an excess of diisobutylene with respect to maleic anhydride in the charged amount when producing the copolymer. Further, an excess of diisobutylene with respect to maleic anhydride is also preferable from the viewpoint of being usable as an organic solvent in the synthesis of the copolymer. The molar ratio of the amount of diisobutylene charged relative to the amount of maleic anhydride charged (diisobutylene / maleic anhydride) is preferably 1.2 or more from the viewpoint of securing the reaction rate of the monomer in the synthesis of the copolymer. Is more preferable, and 2.5 or more is still more preferable. The molar ratio (diisobutylene / maleic anhydride) is preferably 5 or less, more preferably 4 or less, from the viewpoint of efficiently recovering diisobutylene after obtaining a solution containing a copolymer. .5 or less is more preferable.
前記共重合体の製造において、本発明の重合体組成物の水系分散剤としての性能及び水溶性を損なわない範囲で、モノマーとしてジイソブチレン以外のオレフィンを加えても良い。前記ジイソブチレン以外のオレフィンとしては、イソブチレン、１−ヘキセン、１−オクテン等が挙げられる。また同様に、モノマーとして、重合性二価カルボン酸及び／又は無水マレイン酸以外の重合性二価カルボン酸の無水物を加えても良い。前記重合性二価カルボン酸としては、マレイン酸、イタコン酸、フマル酸等が挙げられる。 In the production of the copolymer, an olefin other than diisobutylene may be added as a monomer as long as the performance and water solubility of the polymer composition of the present invention are not impaired. Examples of olefins other than diisobutylene include isobutylene, 1-hexene, 1-octene and the like. Similarly, polymerizable divalent carboxylic acid and / or anhydride of polymerizable divalent carboxylic acid other than maleic anhydride may be added as a monomer. Examples of the polymerizable divalent carboxylic acid include maleic acid, itaconic acid, fumaric acid and the like.
前記重合体組成物の水系分散剤としての性能を向上する観点、前記共重合体の製造容易性の観点、及び合成を効率良く行う観点から、共重合体を製造する際の仕込み量において、ジイソブチレンに対する前記ジイソブチレン以外のオレフィンのモル比（ジイソブチレン以外のオレフィン／ジイソブチレン）は、０．１以下が好ましく、０．０５以下がより好ましく、０．０２以下が更に好ましく、実質的に０が更により好ましい。また、同様の観点から、共重合体を製造する際の仕込み量において、前記無水マレイン酸に対する重合性二価カルボン酸及び／又は無水マレイン酸以外の重合性二価カルボン酸の無水物のモル比［（重合性二価カルボン酸及び／又は無水マレイン酸以外の重合性二価カルボン酸の無水物）／無水マレイン酸］は、０．１以下が好ましく、０．０５以下がより好ましく、０．０２以下が更に好ましく、実質的に０が更により好ましい。 From the viewpoint of improving the performance of the polymer composition as an aqueous dispersant, from the viewpoint of ease of production of the copolymer, and from the viewpoint of efficiently performing the synthesis, The molar ratio of olefins other than diisobutylene to isobutylene (olefins other than diisobutylene / diisobutylene) is preferably 0.1 or less, more preferably 0.05 or less, still more preferably 0.02 or less, substantially 0 Is even more preferred. From the same viewpoint, the molar ratio of the polymerizable dicarboxylic acid and / or polymerizable dicarboxylic acid anhydride other than maleic anhydride to maleic anhydride in the amount charged when producing the copolymer [(Polymerizable dicarboxylic acid and / or anhydride of polymerizable dicarboxylic acid other than maleic anhydride) / maleic anhydride] is preferably 0.1 or less, more preferably 0.05 or less, and 02 or less is more preferable, and substantially 0 is even more preferable.
前記共重合体の重量平均分子量は、分散性に優れる重合体組成物を製造する観点から、１００００以上が好ましく、１５０００以上がより好ましく、２００００以上が更に好ましい。また、前記共重合体の重量平均分子量は、同様の観点から、１０００００以下が好ましく、８００００以下がより好ましく、６００００以下が更に好ましく、３００００以下が更により好ましい。共重合体の重量平均分子量の測定方法は実施例記載の通りである。 The weight average molecular weight of the copolymer is preferably 10,000 or more, more preferably 15,000 or more, and still more preferably 20,000 or more from the viewpoint of producing a polymer composition having excellent dispersibility. Further, from the same viewpoint, the copolymer preferably has a weight average molecular weight of 100,000 or less, more preferably 80000 or less, still more preferably 60000 or less, and even more preferably 30000 or less. The method for measuring the weight average molecular weight of the copolymer is as described in the examples.
［工程１］
工程１は、前記共重合体及び水を含有する組成物と、一般式（Ｉ）で表される化合物からなる第１の中和剤とを、混合する工程である。
（式中、Ｒ1、Ｒ2及びＲ3は同一又は異なって、水素原子が水酸基で置換されていてもよい炭素数１〜３のアルキル基又は水素原子を示す）
[Step 1]
Step 1 is a step of mixing the composition containing the copolymer and water with a first neutralizing agent composed of the compound represented by the general formula (I).
(In formula, R < 1 >, R < 2 > and R < 3 > are the same or different, and the C1-C3 alkyl group or hydrogen atom in which the hydrogen atom may be substituted by the hydroxyl group is shown.)
中和工程における凝集を抑制する観点及び分散性に優れる重合体組成物を製造する観点から、一般式（Ｉ）におけるＲ1、Ｒ2及びＲ3は、同一又は異なって、水素原子が水酸基で置換されていてもよい炭素数１〜３のアルキル基又は水素原子である。一般式（Ｉ）で表される化合物としては、アンモニア、メチルアミン、ジメチルアミン、トリメチルアミン、エチルアミン、ジエチルアミン、トリエチルアミン、トリプロピルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、メチルジエタノールアミン、ジメチルエタノールアミン、トリイソプロパノールアミン等が挙げられる。これらは単独で用いても良いし、２種以上を組み合わせて用いても良い。一般式（Ｉ）で表される化合物としては、取扱いの容易性の観点、重合体組成物の製造容易性の観点及び分散性に優れる重合体組成物を製造する観点から、アンモニア、並びにＲ1、Ｒ2及びＲ3のいずれか１つ以上がヒドロキシエチル基若しくはヒドロキシプロピル基である化合物が好ましく、アンモニア、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、メチルジエタノールアミン、ジメチルエタノールアミン及びトリイソプロパノールアミンがより好ましく、アンモニア及びトリエタノールアミンが更に好ましく、アンモニアが更により好ましい。 From the viewpoint of suppressing aggregation in the neutralization step and from the viewpoint of producing a polymer composition excellent in dispersibility, R 1 , R 2 and R 3 in the general formula (I) are the same or different, and the hydrogen atom is a hydroxyl group. An optionally substituted alkyl group having 1 to 3 carbon atoms or a hydrogen atom. Examples of the compound represented by the general formula (I) include ammonia, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, tripropylamine, monoethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, dimethylethanolamine, Examples include triisopropanolamine. These may be used alone or in combination of two or more. As the compound represented by the general formula (I), from the viewpoint of easy handling, from the viewpoint of easy manufacture of the polymer composition and from the viewpoint of manufacturing a polymer composition excellent in dispersibility, ammonia and R 1 , R 2 and R 3 are preferably a compound in which at least one of them is a hydroxyethyl group or a hydroxypropyl group, and ammonia, monoethanolamine, diethanolamine, triethanolamine, methyldiethanolamine, dimethylethanolamine and triisopropanolamine are more preferable. Preferably, ammonia and triethanolamine are more preferred, and ammonia is even more preferred.
工程１における共重合体及び水を含有する組成物に対する前記一般式（Ｉ）で表される化合物の混合量は、中和工程における凝集を抑制する観点及び分散性に優れる重合体組成物を製造する観点から、前記共重合体に含まれる無水マレイン酸由来の構成単位１００ｍｏｌに対し、１ｍｏｌ以上が好ましく、２ｍｏｌ以上がより好ましく、４ｍｏｌ以上が更に好ましく、５ｍｏｌ以上が更により好ましい。また、共重合体及び水を含有する組成物に対する前記一般式（Ｉ）で表される化合物の混合量は、分散性に優れる重合体組成物を製造する観点から、前記共重合体に含まれる無水マレイン酸由来の構成単位１００ｍｏｌに対し、１５ｍｏｌ以下が好ましく、１０ｍｏｌ以下がより好ましく、８ｍｏｌ以下が更に好ましい。 The mixing amount of the compound represented by the general formula (I) with respect to the composition containing the copolymer and water in the step 1 produces a polymer composition excellent in dispersibility from the viewpoint of suppressing aggregation in the neutralization step. In view of the above, 1 mol or more is preferable, 2 mol or more is more preferable, 4 mol or more is further preferable, and 5 mol or more is even more preferable with respect to 100 mol of the structural unit derived from maleic anhydride contained in the copolymer. Moreover, the mixing amount of the compound represented by the general formula (I) with respect to the composition containing the copolymer and water is included in the copolymer from the viewpoint of producing a polymer composition having excellent dispersibility. 15 mol or less is preferable with respect to 100 mol of the structural unit derived from maleic anhydride, 10 mol or less is more preferable, and 8 mol or less is still more preferable.
第１の中和剤は、水に溶解され水溶液の状態で前記組成物と混合されてもよい。一般式（Ｉ）で表される化合物の沸点が１００℃より低い場合、取扱い容易性の観点から、第１の中和剤は水溶液の状態で用いることが好ましい。第１の中和剤を水溶液の状態で用いる場合、前記水溶液における一般式（Ｉ）で表される化合物と水との質量比（一般式（Ｉ）で表される化合物／水）は、重合体組成物の収率向上の観点から、１０／９０以上がより好ましく、２０／８０以上がより好ましい。また、第１の中和剤の取扱い容易性の観点から、４０／６０以下が好ましく、３０／７０以下がより好ましい。 The first neutralizing agent may be dissolved in water and mixed with the composition in the form of an aqueous solution. When the boiling point of the compound represented by the general formula (I) is lower than 100 ° C., the first neutralizing agent is preferably used in the form of an aqueous solution from the viewpoint of easy handling. When the first neutralizing agent is used in the form of an aqueous solution, the mass ratio of the compound represented by the general formula (I) to water in the aqueous solution (compound / water represented by the general formula (I)) is From the viewpoint of improving the yield of the combined composition, 10/90 or more is more preferable, and 20/80 or more is more preferable. Further, from the viewpoint of easy handling of the first neutralizing agent, 40/60 or less is preferable, and 30/70 or less is more preferable.
更に第１の中和剤は、本発明の効果を阻害しない範囲で、一般式（Ｉ）で表される化合物以外の成分を含有してもよい。第１の中和剤は、中和工程での凝集を抑制する観点から、アルカリ金属水酸化物を含まないことが好ましい。第１の中和剤における一般式（Ｉ）で表される化合物の含有量は、中和工程おける凝集を抑制する観点から、９０質量％以上が好ましく、９５質量％以上がより好ましく、実質的に１００質量％が更に好ましく、１００質量％が更により好ましい。 Furthermore, the first neutralizing agent may contain components other than the compound represented by the general formula (I) as long as the effects of the present invention are not impaired. The first neutralizing agent preferably does not contain an alkali metal hydroxide from the viewpoint of suppressing aggregation in the neutralization step. The content of the compound represented by the general formula (I) in the first neutralizing agent is preferably 90% by mass or more, more preferably 95% by mass or more, from the viewpoint of suppressing aggregation in the neutralization step. 100 mass% is further more preferable, and 100 mass% is still more preferable.
工程１における共重合体及び水を含有する組成物と第１の中和剤との混合方法は、特に限定されないが、重合体組成物の製造の容易性の観点から、共重合体及び水を含有する組成物を攪拌しながら第１の中和剤を加える方法が好ましい。また、第１の中和剤は、一度に加えても滴下して加えても良い。第１の中和剤を添加してから第２の中和剤を添加するまでの時間は、中和を均一に進行させる観点及び中和速度向上の観点から、５分以上が好ましく、１０分以上がより好ましい。また、重合体組成物を効率よく製造できる観点から、３０分以下が好ましく、２０分以下がより好ましい。 The mixing method of the copolymer and water-containing composition in Step 1 and the first neutralizing agent is not particularly limited, but from the viewpoint of ease of production of the polymer composition, the copolymer and water are added. The method of adding a 1st neutralizing agent, stirring the composition to contain is preferable. Further, the first neutralizing agent may be added at once or may be added dropwise. The time from the addition of the first neutralizing agent to the addition of the second neutralizing agent is preferably 5 minutes or more from the viewpoint of uniformly promoting the neutralization and improving the neutralization rate. The above is more preferable. Moreover, from a viewpoint which can manufacture a polymer composition efficiently, 30 minutes or less are preferable and 20 minutes or less are more preferable.
工程１における前記共重合体及び水を含有する組成物の温度は、中和を均一に進行させる観点及び中和速度向上の観点から、５０℃以上が好ましく、６０℃以上がより好ましく、７０℃以上が更に好ましい。また、工程１における前記共重合体及び水を含有する組成物の温度は、前記共重合体及び水を含有する組成物の泡立ちを抑制して攪拌性を向上する観点並びに第１の中和剤の揮発及び水の蒸発を抑制する観点から、９０℃以下が好ましく、８５℃以下がより好ましく、８０℃以下が更に好ましい。 The temperature of the composition containing the copolymer and water in step 1 is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and 70 ° C. from the viewpoint of uniformly promoting neutralization and improving the neutralization rate. The above is more preferable. In addition, the temperature of the composition containing the copolymer and water in step 1 is the first neutralizing agent in terms of suppressing the foaming of the composition containing the copolymer and water and improving the stirrability. From the viewpoint of suppressing volatilization of water and evaporation of water, 90 ° C. or lower is preferable, 85 ° C. or lower is more preferable, and 80 ° C. or lower is still more preferable.
工程１における前記共重合体及び水を含有する組成物の固形分は、収率向上の観点から、２０質量％以上が好ましく、２５質量％以上がより好ましく、３０質量％以上が更に好ましい。また、増粘の抑制による攪拌性向上の観点から、５０質量％以下が好ましく、４５質量％以下がより好ましく、４０質量％以下が更に好ましい。 The solid content of the composition containing the copolymer and water in step 1 is preferably 20% by mass or more, more preferably 25% by mass or more, and still more preferably 30% by mass or more from the viewpoint of yield improvement. Moreover, from a viewpoint of the stirrability improvement by suppression of thickening, 50 mass% or less is preferable, 45 mass% or less is more preferable, and 40 mass% or less is still more preferable.
［工程２］
工程２は、工程１で得られた混合物と、アルカリ金属水酸化物からなる第２の中和剤とを、混合する工程である。
[Step 2]
Step 2 is a step of mixing the mixture obtained in Step 1 with a second neutralizing agent made of an alkali metal hydroxide.
アルカリ金属水酸化物としては、水酸化リチウム、水酸化ナトリウム、水酸化カリウム等が挙げられる。これらは単独で用いても良いし、２種以上を組み合わせて用いても良い。アルカリ金属水酸化物としては、分散性に優れる重合体組成物を製造する観点から、水酸化ナトリウム及び水酸化カリウムが好ましく、水酸化ナトリウムがより好ましい。 Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like. These may be used alone or in combination of two or more. As the alkali metal hydroxide, sodium hydroxide and potassium hydroxide are preferable, and sodium hydroxide is more preferable from the viewpoint of producing a polymer composition having excellent dispersibility.
工程２における工程１で得られた混合物に対する前記アルカリ金属水酸化物の混合量は、中和工程における凝集を抑制する観点及び分散性に優れる重合体組成物を製造する観点から、前記共重合体に含まれる無水マレイン酸由来の構成単位１００ｍｏｌに対し、５０ｍｏｌ以上が好ましく、７０ｍｏｌ以上がより好ましく、９０ｍｏｌ以上が更に好ましく、１４０ｍｏｌ以上が更により好ましい。また、工程１で得られた混合物に対する前記アルカリ金属水酸化物の混合量は、同様の観点から、前記共重合体に含まれる無水マレイン酸由来の構成単位１００ｍｏｌに対し、３００ｍｏｌ以下が好ましく、２５０ｍｏｌ以下がより好ましく、２３０ｍｏｌ以下が更に好ましい。 The amount of the alkali metal hydroxide mixed with the mixture obtained in step 1 in step 2 is the copolymer from the viewpoint of suppressing aggregation in the neutralization step and producing a polymer composition excellent in dispersibility. Is preferably 50 mol or more, more preferably 70 mol or more, still more preferably 90 mol or more, and still more preferably 140 mol or more with respect to 100 mol of the structural unit derived from maleic anhydride contained in. In addition, the amount of the alkali metal hydroxide mixed with the mixture obtained in Step 1 is preferably 300 mol or less with respect to 100 mol of the maleic anhydride-derived structural unit contained in the copolymer, from the same viewpoint, The following is more preferable, and 230 mol or less is still more preferable.
工程１における一般式（Ｉ）で表される化合物と、工程２におけるアルカリ金属水酸化物との合計は、中和工程における凝集を抑制する観点及び分散性に優れる重合体組成物を製造する観点から、前記共重合体に含まれる無水マレイン酸由来の構成単位１００ｍｏｌに対し、５０ｍｏｌ以上が好ましく、７０ｍｏｌ以上がより好ましく、１００ｍｏｌ以上が更に好ましく、１３０ｍｏｌ以上が更により好ましく、１５０ｍｏｌ以上が更によりより好ましい。また、工程１における一般式（Ｉ）で表される化合物と、工程２におけるアルカリ金属水酸化物との合計は、中和工程における凝集を抑制する観点、分散性に優れる重合体組成物を製造する観点及び第１の中和剤に由来する臭いを抑制する観点から、３００ｍｏｌ以下が好ましく、２６０ｍｏｌ以下がより好ましく、２３０ｍｏｌ以下が更に好ましく、２００ｍｏｌ以下が更により好ましく、１８０ｍｏｌ以下が更によりより好ましい。 The total of the compound represented by the general formula (I) in Step 1 and the alkali metal hydroxide in Step 2 is a viewpoint of suppressing aggregation in the neutralization process and a viewpoint of producing a polymer composition excellent in dispersibility. From 100 mol of the structural unit derived from maleic anhydride contained in the copolymer, it is preferably 50 mol or more, more preferably 70 mol or more, still more preferably 100 mol or more, still more preferably 130 mol or more, and even more preferably 150 mol or more. preferable. Moreover, the sum total of the compound represented by the general formula (I) in Step 1 and the alkali metal hydroxide in Step 2 produces a polymer composition excellent in dispersibility from the viewpoint of suppressing aggregation in the neutralization step. From the viewpoint of reducing the odor derived from the first neutralizing agent, it is preferably 300 mol or less, more preferably 260 mol or less, further preferably 230 mol or less, even more preferably 200 mol or less, and even more preferably 180 mol or less. .
第２の中和剤は、取扱い容易性の観点から、水に溶解され水溶液の状態で用いることが好ましい。第２の中和剤を水溶液の状態で用いる場合、前記水溶液におけるアルカリ金属水酸化物と水との質量比（アルカリ金属水酸化物／水）は、重合体組成物の収率向上の観点から、１５／８５以上がより好ましく、２５／７５以上がより好ましい。また、第２の中和剤の取扱い容易性の観点から、５０／５０以下が好ましく、更に、アルカリ金属水酸化物が水酸化ナトリウムの場合は、４０／６０以下がより好ましい。 From the viewpoint of easy handling, the second neutralizing agent is preferably dissolved in water and used in the form of an aqueous solution. When the second neutralizing agent is used in the form of an aqueous solution, the mass ratio of the alkali metal hydroxide to water (alkali metal hydroxide / water) in the aqueous solution is from the viewpoint of improving the yield of the polymer composition. 15/85 or more is more preferable, and 25/75 or more is more preferable. Further, from the viewpoint of easy handling of the second neutralizing agent, 50/50 or less is preferable, and when the alkali metal hydroxide is sodium hydroxide, 40/60 or less is more preferable.
更に第２の中和剤は、本発明の効果を阻害しない範囲で、アルカリ金属水酸化物以外の成分を含有してもよい。第２の中和剤におけるアルカリ金属水酸化物の含有量は、重合体組成物を効率よく製造できる観点及び分散性に優れる重合体組成物を製造する観点から、８０質量％以上が好ましく、９０質量％以上がより好ましく、９５質量％が更に好ましく、実質的に１００質量％が更により好ましい。 Furthermore, the second neutralizing agent may contain components other than the alkali metal hydroxide as long as the effects of the present invention are not impaired. The content of the alkali metal hydroxide in the second neutralizing agent is preferably 80% by mass or more from the viewpoint of efficiently producing the polymer composition and from the viewpoint of producing a polymer composition having excellent dispersibility. More preferably, it is more preferably 95% by weight, still more preferably 95% by weight, and still more preferably 100% by weight.
工程２における工程１で得られた混合物と第２の中和剤との混合方法は、特に限定されないが、重合体組成物の製造の容易性の観点から、工程１で得られた混合物を攪拌しながら、第２の中和剤を前記混合物中に加える方法が好ましく、滴下する方法が更に好ましい。第２の中和剤を滴下する時間は、共重合体の凝集や反応槽への付着を抑制する観点から、０．５時間以上が好ましく、１時間以上がより好ましく、１．２時間以上が更に好ましい。また、第２の中和剤を滴下する時間は、重合体組成物を効率よく製造できる観点から、３時間以下が好ましく、２．５時間以下がより好ましく、２時間以下が更に好ましい。 The method for mixing the mixture obtained in step 1 and the second neutralizing agent in step 2 is not particularly limited, but the mixture obtained in step 1 is stirred from the viewpoint of ease of production of the polymer composition. However, a method of adding the second neutralizing agent to the mixture is preferable, and a method of adding dropwise is more preferable. The time for dropping the second neutralizing agent is preferably 0.5 hours or more, more preferably 1 hour or more, and 1.2 hours or more from the viewpoint of suppressing aggregation of the copolymer and adhesion to the reaction tank. Further preferred. The time for dropping the second neutralizing agent is preferably 3 hours or less, more preferably 2.5 hours or less, and even more preferably 2 hours or less, from the viewpoint of efficiently producing the polymer composition.
工程２における工程１で得られた混合物の温度は、中和を均一に進行させる観点及び中和速度向上の観点から、５０℃以上が好ましく、６０℃以上がより好ましく、７０℃以上が更に好ましい。また、工程１で得られた混合物の泡立ちを抑制して攪拌性を向上する観点及び水の蒸発を抑制する観点から、９０℃以下が好ましく、８５℃以下がより好ましく、８０℃以下が更に好ましい。 The temperature of the mixture obtained in step 1 in step 2 is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and even more preferably 70 ° C. or higher, from the viewpoint of uniformly proceeding neutralization and improving the neutralization rate. . Further, from the viewpoint of suppressing foaming of the mixture obtained in step 1 and improving the stirring property and from the viewpoint of suppressing water evaporation, 90 ° C or lower is preferable, 85 ° C or lower is more preferable, and 80 ° C or lower is still more preferable. .
［重合体組成物］
本発明の重合体組成物に含まれる重合体は、ジイソブチレン由来の構成単位とマレイン酸のアルカリ金属塩由来の構成単位とを含む。前記アルカリ金属としては、重合体組成物の水系分散剤としての性能を向上する観点から、ナトリウム及びカリウムが好ましく、ナトリウムがより好ましい。
[Polymer composition]
The polymer contained in the polymer composition of the present invention contains a structural unit derived from diisobutylene and a structural unit derived from an alkali metal salt of maleic acid. As the alkali metal, sodium and potassium are preferable and sodium is more preferable from the viewpoint of improving the performance of the polymer composition as an aqueous dispersant.
本発明の重合体組成物は、前記共重合体に含まれる無水マレイン酸由来の構成単位の一部又は全てが加水分解し、更に加水分解によって生じたカルボキシ基の一部又は全てが塩となった重合体を含有する。また、本発明の重合体組成物は、重合体組成物の製造の容易性の観点及び重合体組成物の取扱い容易性の観点から、前記重合体と水とを含有することが好ましく、前記重合体の水溶液であることがより好ましい。 In the polymer composition of the present invention, a part or all of the structural unit derived from maleic anhydride contained in the copolymer is hydrolyzed, and a part or all of the carboxy group generated by the hydrolysis is converted into a salt. Containing polymers. Further, the polymer composition of the present invention preferably contains the polymer and water from the viewpoint of ease of production of the polymer composition and ease of handling of the polymer composition. A combined aqueous solution is more preferable.
本発明の重合体組成物は、無水マレイン酸とジイソブチレンとの共重合体と、中和剤とを混合する工程を含む製造方法であって、
工程１ 前記共重合体及び水を含有する組成物と、前記一般式（Ｉ）で表される化合物からなる第１の中和剤とを、混合する工程、
工程２ 工程１で得られた混合物と、アルカリ金属水酸化物からなる第２の中和剤とを、混合する工程、を含む製造方法によって製造される。
The polymer composition of the present invention is a production method comprising a step of mixing a copolymer of maleic anhydride and diisobutylene and a neutralizing agent,
Process 1 The process of mixing the composition containing the said copolymer and water, and the 1st neutralizing agent which consists of a compound represented by the said general formula (I),
Process 2 It manufactures by the manufacturing method including the process of mixing the mixture obtained at the process 1, and the 2nd neutralizing agent consisting of an alkali metal hydroxide.
本発明の重合体組成物の製造方法において、更に工程２で得られた組成物に対して濾過処理を行って、不溶物を除去しても良い。前記濾過処理は工程２の後に行われることが好ましい。濾過処理方法としては、フィルタープレス、セラミックフィルター、リキッドフィルター等の処理方法が挙げられる。前記濾過処理において、濾過助剤を併用することも好ましい。濾過助剤としては、珪藻土、ゼオライト、活性炭等が挙げられる。 In the method for producing a polymer composition of the present invention, the composition obtained in step 2 may be further filtered to remove insoluble matters. The filtration treatment is preferably performed after step 2. Examples of the filtering method include processing methods such as a filter press, a ceramic filter, and a liquid filter. In the filtration treatment, it is also preferable to use a filter aid together. Examples of the filter aid include diatomaceous earth, zeolite, activated carbon and the like.
本発明の重合体組成物の固形分は、重合体組成物の耐防腐性向上の観点及び分散性向上の観点から、１０質量％以上が好ましく、１５質量％以上がより好ましく、２０質量％以上が更に好ましい。また、本発明の重合体組成物の固形分は、重合体組成物の増粘を抑制して取扱い性を向上する観点から、４０質量％以下が好ましく、３５質量％以下がより好ましく、３０質量％以下が更に好ましい。 The solid content of the polymer composition of the present invention is preferably 10% by mass or more, more preferably 15% by mass or more, and more preferably 20% by mass or more from the viewpoint of improving antiseptic properties and dispersibility of the polymer composition. Is more preferable. Further, the solid content of the polymer composition of the present invention is preferably 40% by mass or less, more preferably 35% by mass or less, and more preferably 30% by mass from the viewpoint of suppressing the increase in viscosity of the polymer composition and improving handleability. % Or less is more preferable.
本発明の重合体組成物のｐＨは、水溶性向上の観点及び分散性向上の観点から、７．５以上が好ましく、９以上がより好ましく、１０以上が更に好ましく、１１以上が更により好ましい。また、本発明の重合体組成物のｐＨは、分散性向上の観点及び第１の中和剤に由来する臭いを抑制する観点から、１３．８以下が好ましく、１３．５以下がより好ましく、１３以下が更に好ましく、１２．５以下が更により好ましく、１２以下が更によりより好ましい。 The pH of the polymer composition of the present invention is preferably 7.5 or more, more preferably 9 or more, still more preferably 10 or more, and even more preferably 11 or more, from the viewpoint of improving water solubility and improving dispersibility. Further, the pH of the polymer composition of the present invention is preferably 13.8 or less, more preferably 13.5 or less, from the viewpoint of improving dispersibility and suppressing the odor derived from the first neutralizer. 13 or less is more preferable, 12.5 or less is still more preferable, and 12 or less is still more preferable.
本発明の重合体組成物は、無機粒子、有機顔料などの粉体用の水系分散剤として好ましく用いられる。無機粒子としては、酸化チタン、シリカ、アルミナ等が挙げられる。また有機顔料としては、カーボンブラック、フタロシアニンブルー、アントラキノン等が挙げられる。 The polymer composition of the present invention is preferably used as an aqueous dispersant for powders such as inorganic particles and organic pigments. Examples of the inorganic particles include titanium oxide, silica, and alumina. Examples of the organic pigment include carbon black, phthalocyanine blue, and anthraquinone.
本発明の重合体組成物を粉体用の水系分散剤として使用するにあたっては、重合体組成物の使用量は、粉体の分散性向上の観点から、粉体１００質量部に対し、重合体組成物の固形分で０．０５質量部以上が好ましく、０．１質量部以上がより好ましく、０．１５質量部以上が更に好ましい。また、同様の観点から、５質量部以下が好ましく、４質量部以下がより好ましく、３質量部以下が更に好ましい。 In using the polymer composition of the present invention as an aqueous dispersant for powders, the amount of the polymer composition used is from the viewpoint of improving the dispersibility of the powder with respect to 100 parts by mass of the powder. The solid content of the composition is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and still more preferably 0.15 parts by mass or more. Moreover, from the same viewpoint, 5 mass parts or less are preferable, 4 mass parts or less are more preferable, and 3 mass parts or less are still more preferable.
［共重合体の製造例１：共重合体Ａの製造］
攪拌機、温度計、還流冷却管、窒素導入管、滴下ロートを備えたガラス製反応容器内に、ジイソブチレン（丸善石油化学社製） ６２１．８ｇ及びルトナールＡ−５０（ＢＡＳＦ社製、ポリビニルエチルエーテル） ３．１ｇを仕込んだ。反応容器内を窒素雰囲気とし、攪拌を開始した。反応容器内容物を１０５℃まで加熱し、これ以降、重合反応を完結させるまで、反応容器内容物の温度を１０５℃に保った。７０℃に保温した液体の無水マレイン酸（三井化学ポリウレタン社製） １９０．０ｇ、及び開始剤溶液としてジイソブチレン ２３．１ｇに溶解させたパーブチルＯ（日油社製、ｔ−ブチルパーオキシ−２−エチルヘキサノエート） １０．３ｇを、それぞれ別の滴下ロートから反応容器内に４時間かけて滴下した。滴下の終了から２０分後に、ジイソブチレン７．３ｇに溶解させたパーブチルＯ １．２ｇを反応容器内に加え、更に２時間４０分熟成を行って重合反応を完結させ、共重合体Ａを含む溶液を得た。反応容器内にイオン交換水 ８００ｇを加え、共重合体Ａの沈殿を析出させた。次いで、水蒸気蒸留によって、未反応のジイソブチレンの留去を行った。前記水蒸気蒸留は、常圧で反応容器を加熱し、反応容器内容物が１００℃に達し、ジイソブチレンの留出が無くなるまで行った。以上の操作を経て、共重合体Ａと水とを含有する組成物を得た。前記組成物の固形分は３７質量％であった。また、共重合体Ａの重量平均分子量は２５０００であった。
[Copolymer Production Example 1: Production of Copolymer A]
In a glass reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen inlet tube, and dropping funnel, 621.8 g of diisobutylene (manufactured by Maruzen Petrochemical Co., Ltd.) and Rutonal A-50 (manufactured by BASF, polyvinyl ethyl ether) ) 3.1g was charged. The reaction vessel was filled with a nitrogen atmosphere and stirring was started. The reaction vessel contents were heated to 105 ° C., and thereafter, the temperature of the reaction vessel contents was maintained at 105 ° C. until the polymerization reaction was completed. 190.0 g of liquid maleic anhydride (manufactured by Mitsui Chemicals Polyurethanes) kept at 70 ° C. and perbutyl O (manufactured by NOF Corporation, t-butylperoxy-2) dissolved in 23.1 g of diisobutylene as an initiator solution -Ethylhexanoate) 10.3 g was dripped in a reaction container from another dropping funnel over 4 hours. 20 minutes after the completion of the dropwise addition, 1.2 g of perbutyl O dissolved in 7.3 g of diisobutylene is added to the reaction vessel, and further aged for 2 hours and 40 minutes to complete the polymerization reaction, and the copolymer A is contained. A solution was obtained. In the reaction vessel, 800 g of ion-exchanged water was added to precipitate the copolymer A. Subsequently, unreacted diisobutylene was distilled off by steam distillation. The steam distillation was performed until the reaction vessel was heated at normal pressure until the contents of the reaction vessel reached 100 ° C. and diisobutylene was not distilled. Through the above operations, a composition containing copolymer A and water was obtained. The solid content of the composition was 37% by mass. Moreover, the weight average molecular weight of the copolymer A was 25000.
［共重合体の製造例２：共重合体Ｂの製造］
開始剤溶液としてジイソブチレン（丸善石油化学社製） ２３．１ｇに溶解させたパーブチルＯ（日油社製、ｔ−ブチルパーオキシ−２−エチルヘキサノエート） １３．５ｇを用いたこと以外は、前記共重合体Ａの製造例１に従い、共重合体Ｂと水とを含有する組成物を得た。前記組成物の固形分は３７質量％であった。また、共重合体Ｂの重量平均分子量は１２０００であった。
[Copolymer Production Example 2: Production of Copolymer B]
Except for using 13.5 g of perbutyl O (manufactured by NOF Corporation, t-butylperoxy-2-ethylhexanoate) dissolved in 23.1 g of diisobutylene (manufactured by Maruzen Petrochemical Co., Ltd.) as the initiator solution. According to Production Example 1 of Copolymer A, a composition containing Copolymer B and water was obtained. The solid content of the composition was 37% by mass. Further, the weight average molecular weight of the copolymer B was 12,000.
［共重合体の製造例３：共重合体Ｃの製造］
開始剤溶液としてジイソブチレン（丸善石油化学社製） ２３．１ｇに溶解させたパーブチルＯ（日油社製、ｔ−ブチルパーオキシ−２−エチルヘキサノエート） ２．６ｇを用いたこと以外は、前記共重合体Ａの製造例１に従い、共重合体Ｃと水とを含有する組成物を得た。前記組成物の固形分は３７質量％であった。また、共重合体Ｃの重量平均分子量は９７０００であった。
[Copolymer Production Example 3: Production of Copolymer C]
Except for using 2.6 g of dibutylene (manufactured by Maruzen Petrochemical Co., Ltd.) perbutyl O (manufactured by NOF Corporation, t-butylperoxy-2-ethylhexanoate) dissolved in 23.1 g as an initiator solution. According to Production Example 1 of Copolymer A, a composition containing Copolymer C and water was obtained. The solid content of the composition was 37% by mass. Further, the weight average molecular weight of the copolymer C was 97,000.
［重合体組成物の製造例１：重合体組成物Ａ１の製造］
前記共重合体の製造例１記載の方法に従い、共重合体Ａと水とを含有する組成物を得た操作に続いて、以下に示す中和工程を行った。反応容器内容物を７５℃まで冷却し、これ以降、中和反応を完結させるまで、反応容器内の液体の温度を７５℃に保った。工程１として、２５質量％アンモニア水溶液（昭和電工社製） ８．４ｇを反応容器内に加えて１５分間保持した。次に、工程２として、３２質量％水酸化ナトリウム水溶液（南海化学社製） ３８７．４ｇを反応容器内に１．５時間かけて滴下し、中和反応を完結させた。室温まで冷却し、固形分が２５質量％となるようにイオン交換水を加え、３０分間保持してから攪拌を停止し、ジイソブチレンとマレイン酸塩とを構成単位として含む重合体組成物Ａ１を得た。
[Production Example 1 of Polymer Composition: Production of Polymer Composition A1]
In accordance with the method described in Production Example 1 for the copolymer, following the operation for obtaining the composition containing the copolymer A and water, the following neutralization step was performed. The reaction vessel contents were cooled to 75 ° C., and thereafter, the temperature of the liquid in the reaction vessel was kept at 75 ° C. until the neutralization reaction was completed. As Step 1, 8.4 g of a 25% by mass aqueous ammonia solution (manufactured by Showa Denko) was added to the reaction vessel and held for 15 minutes. Next, as step 2, 387.4 g of a 32% by mass aqueous sodium hydroxide solution (manufactured by Nankai Chemical Co., Ltd.) was dropped into the reaction vessel over 1.5 hours to complete the neutralization reaction. Cool to room temperature, add ion-exchanged water so that the solid content is 25% by mass, hold for 30 minutes, and then stop stirring to obtain a polymer composition A1 containing diisobutylene and maleate as structural units. Obtained.
［重合体組成物の製造例２：重合体組成物Ａ５１の製造］
工程１を行わなかったこと以外は、前記重合体組成物の製造例１に従い、重合体組成物Ａ５１を得た。
[Production Example 2 of Polymer Composition: Production of Polymer Composition A51]
A polymer composition A51 was obtained according to Production Example 1 of the polymer composition except that Step 1 was not performed.
［重合体組成物の製造例３：重合体組成物Ａ５２の製造］
工程２における、３２質量％水酸化ナトリウム水溶液 ３８７．４ｇを、２５質量％アンモニア水溶液（昭和電工社製） ２１１．１ｇに代えたこと以外は、前記重合体組成物の製造例２に従い、重合体組成物Ａ５２を得た。
[Production Example 3 of Polymer Composition: Production of Polymer Composition A52]
In accordance with Production Example 2 of the polymer composition, except that 387.4 g of 32 mass% aqueous sodium hydroxide solution in Step 2 was replaced with 211.1 g of 25 mass% aqueous ammonia solution (manufactured by Showa Denko KK). Composition A52 was obtained.
［重合体組成物の製造例４：重合体組成物Ａ５３の製造］
工程２における、３２質量％水酸化ナトリウム水溶液 ３８７．４ｇを、予め調製した２５質量％アンモニア水溶液（昭和電工社製） ８．４ｇと、３２質量％水酸化ナトリウム水溶液（南海化学社製） ３８７．４ｇとを混合した、均一な水酸化ナトリウム−アンモニア混合水溶液に代えたこと以外は、前記重合体組成物の製造例２に従い、重合体組成物Ａ５３を得た。
[Production Example 4 of Polymer Composition: Production of Polymer Composition A53]
8.4 g of a 25% by mass aqueous ammonia solution (manufactured by Showa Denko KK) prepared in advance, 387.4 g of a 32% by mass sodium hydroxide aqueous solution in Step 2, and a 32% by mass sodium hydroxide aqueous solution (manufactured by Nankai Chemical) 387. A polymer composition A53 was obtained according to Production Example 2 of the polymer composition, except that 4 g was mixed with a uniform aqueous sodium hydroxide-ammonia solution.
［重合体組成物の製造例５：重合体組成物Ａ５４の製造］
前記共重合体の製造例１記載の方法に従い、共重合体Ａと水とを含有する組成物を得た操作に続いて、以下に示す中和工程を行った。反応容器内容物を７５℃まで冷却し、これ以降、中和反応を完結させるまで、反応容器内の液体の温度を７５℃に保った。工程１として、３２質量％水酸化ナトリウム水溶液（南海化学社製） ３８７．４ｇを反応容器内に１．５時間かけて滴下した。次に、工程２として、２５質量％アンモニア水溶液（昭和電工社製） ８．４ｇを反応容器内に加えて１５分間保持し、中和反応を完結させた。室温まで冷却し、固形分が２５質量％となるようにイオン交換水を加え、３０分間保持してから攪拌を停止し、重合体組成物Ａ５４を得た。
[Production Example 5 of Polymer Composition: Production of Polymer Composition A54]
In accordance with the method described in Production Example 1 for the copolymer, following the operation for obtaining the composition containing the copolymer A and water, the following neutralization step was performed. The reaction vessel contents were cooled to 75 ° C., and thereafter, the temperature of the liquid in the reaction vessel was kept at 75 ° C. until the neutralization reaction was completed. As step 1, 387.4 g of a 32% by mass aqueous sodium hydroxide solution (manufactured by Nankai Chemical Co., Ltd.) was dropped into the reaction vessel over 1.5 hours. Next, as step 2, 8.4 g of a 25% by mass aqueous ammonia solution (manufactured by Showa Denko) was added to the reaction vessel and held for 15 minutes to complete the neutralization reaction. The mixture was cooled to room temperature, ion-exchanged water was added so that the solid content was 25% by mass, the mixture was held for 30 minutes, and stirring was stopped to obtain a polymer composition A54.
［重合体組成物の製造例６：重合体組成物Ａ２〜Ａ１４の製造］
工程１における２５質量％アンモニア水溶液、及び、工程２における３２質量％水酸化ナトリウム水溶液の量を、表１に記載の量とした以外は、前記重合体組成物の製造例１に従い、重合体組成物Ａ２〜Ａ１４を得た。
[Production Example 6 of Polymer Composition: Production of Polymer Compositions A2 to A14]
The polymer composition according to Production Example 1 of the polymer composition except that the amount of the 25 mass% aqueous ammonia solution in Step 1 and the amount of the 32 mass% sodium hydroxide aqueous solution in Step 2 were the amounts shown in Table 1. The thing A2-A14 was obtained.
［重合体組成物の製造例７：重合体組成物Ａ１５の製造］
工程１における２５質量％アンモニア水溶液 ８．４ｇをトリエタノールアミン（日本触媒社製） １８．４ｇに代えたこと以外は、前記重合体組成物の製造例１に従い、重合体組成物Ａ１５を得た。
[Production Example 7 of Polymer Composition: Production of Polymer Composition A15]
A polymer composition A15 was obtained according to Production Example 1 of the polymer composition, except that 8.4 g of the 25% by mass aqueous ammonia solution in Step 1 was replaced with 18.4 g of triethanolamine (manufactured by Nippon Shokubai Co., Ltd.). .
［重合体組成物の製造例８：重合体組成物Ａ１６の製造］
工程２における３２質量％水酸化ナトリウム水溶液 ３８７．４ｇを４８質量％水酸化カリウム水溶液（ＡＧＣ旭硝子社製） ３６２．２ｇに代えたこと以外は、前記重合体組成物の製造例１に従い、重合体組成物Ａ１６を得た。
[Production Example 8 of Polymer Composition: Production of Polymer Composition A16]
A polymer according to Production Example 1 of the above polymer composition, except that 387.4 g of 32 mass% aqueous sodium hydroxide solution in Step 2 was replaced with 362.2 g of 48 mass% aqueous potassium hydroxide solution (manufactured by AGC Asahi Glass Co., Ltd.). Composition A16 was obtained.
［重合体組成物の製造例９：重合体組成物Ｂ１の製造］
前記共重合体の製造例２記載の方法に従い、共重合体Ｂと水とを含有する組成物を得た操作に続いて、前記重合体組成物の製造例１に示した中和工程を行い、重合体組成物Ｂ１を得た。
[Production Example 9 of Polymer Composition: Production of Polymer Composition B1]
In accordance with the method described in Production Example 2 of the copolymer, following the operation of obtaining the composition containing the copolymer B and water, the neutralization step shown in Production Example 1 of the polymer composition is performed. The polymer composition B1 was obtained.
［重合体組成物の製造例１０：重合体組成物Ｃ１の製造］
前記共重合体の製造例３記載の方法に従い、共重合体Ｃと水とを含有する組成物を得た操作に続いて、前記重合体組成物の製造例１に示した中和工程を行い、重合体組成物Ｃ１を得た。
[Production Example 10 of Polymer Composition: Production of Polymer Composition C1]
In accordance with the method described in Production Example 3 of the copolymer, following the operation of obtaining the composition containing the copolymer C and water, the neutralization step shown in Production Example 1 of the polymer composition is performed. A polymer composition C1 was obtained.
［共重合体の重量平均分子量測定］
共重合体の重量平均分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）により、下記条件で測定した。重量平均分子量は、予め作成した検量線に基づき算出した。検量線の作成には、下記の標準試料を用いた。
測定装置：ＨＬＣ−８１２０ＧＰＣ（東ソー社製）
カラム：ＴＳＫ α−Ｍ ＋ α−Ｍ（いずれも東ソー株式会社製）
カラム温度：４０℃
検出器：ＲＩ
溶離液：Ｈ3ＰＯ4（６０ｍｍｏｌ／Ｌ）及びＬｉＢｒ（５０ｍｍｏｌ／Ｌ）を加えたＮ，Ｎ−ジメチルホルムアミド溶液
流速：１．０ｍＬ／ｍｉｎ
試料濃度：０．１質量％（固形分）
試料注入量：０．１ｍＬ
標準試料：東ソー社製ポリスチレン ５．２６×１０2、１．０２×１０5、８．４２×１０6；西尾工業社製ポリスチレン ４．０×１０3、３．０×１０4、９．０×１０5（数字はそれぞれ分子量）
[Measurement of weight average molecular weight of copolymer]
The weight average molecular weight of the copolymer was measured by GPC (gel permeation chromatography) under the following conditions. The weight average molecular weight was calculated based on a calibration curve prepared in advance. The following standard samples were used for preparing the calibration curve.
Measuring device: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK α-M + α-M (both manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Detector: RI
Eluent: N, N-dimethylformamide solution added with H 3 PO 4 (60 mmol / L) and LiBr (50 mmol / L) Flow rate: 1.0 mL / min
Sample concentration: 0.1% by mass (solid content)
Sample injection volume: 0.1 mL
Standard samples: polystyrene manufactured by Tosoh Corporation 5.26 × 10 2 , 1.02 × 10 5 , 8.42 × 10 6 ; polystyrene manufactured by Nishio Kogyo Co., Ltd. 4.0 × 10 3 , 3.0 × 10 4 , 9.0 × 10 5 (Numbers are each molecular weight)
［固形分の測定］
実施例における、各固形分の測定は以下の方法で行った。質量Ｗ3（ｇ）のシャーレに試料１ｇを採り、前記試料を含んだシャーレ全体の質量を測定し、Ｗ1（ｇ）とした。シャーレ全体を、熱風循環型乾燥機（いすゞ製作所製 Ｈｏｔ Ａｉｒ Ｒａｐｉｄ Ｄｒｙｉｎｇ Ｏｖｅｎ Ｓｏｙｏｋａｚｅ）で１７０℃２時間の条件で乾燥させ、更にデシケータで３０分放冷した後、前記試料の不揮発分を含んだシャーレ全体の質量を測定し、Ｗ2（ｇ）とした。次式より得られた値を固形分とした。
固形分（質量％）＝１００−（Ｗ1−Ｗ2）／（Ｗ1−Ｗ3）×１００
[Measurement of solid content]
In the examples, each solid content was measured by the following method. 1 g of a sample was taken in a petri dish having a mass of W 3 (g), and the mass of the entire petri dish including the sample was measured to obtain W 1 (g). The entire petri dish was dried at 170 ° C. for 2 hours with a hot air circulation dryer (Hot Air Rapid Drying Soyokaze manufactured by Isuzu Seisakusho), allowed to cool for 30 minutes with a desiccator, and then the petri dish containing the non-volatile content of the sample was collected. The total mass was measured and designated as W 2 (g). The value obtained from the following formula was defined as the solid content.
Solid content (mass%) = 100− (W 1 −W 2 ) / (W 1 −W 3 ) × 100
［沈殿物量の測定］
重合体組成物（固形分として２５質量％）１００ｇを１００メッシュワイヤーにて濾過を行い、メッシュ上の残渣を１０５℃、２時間、乾燥機中に入れ、冷却後乾燥させた沈殿物質量（ｇ）を測定した。沈殿物質量が少ないほど、中和工程での凝集を抑制する効果が優れることを示す。
[Measurement of amount of sediment]
100 g of a polymer composition (25% by mass as a solid content) is filtered through a 100 mesh wire, and the residue on the mesh is placed in a dryer at 105 ° C. for 2 hours, cooled and dried (g) ) Was measured. It shows that the effect which suppresses the aggregation in a neutralization process is excellent, so that the amount of precipitation substances is small.
［分散性の測定］
５０ｍＬのガラス製サンプルびん（マルエム社製スクリュー管Ｎｏ．７）に平均粒径０．５μｍの酸化チタン粒子（東邦チタニウム製ＨＴ０５１４） ０．３ｇと、固形分に換算して重合体組成物 ０．６ｍｇとを加え、更にイオン交換水を加えて、酸化チタン粒子、重合体組成物及び水の合計を３０ｇとし、密栓した後、ヤマト科学（株）製の超音波洗浄器ｙａｍａｔｏ１５１０で３０分間超音波処理を行い、１質量％の酸化チタンスラリーを調製した。得られたスラリーを内径１０ｍｍの沈降試験管に移して２５℃にて静置し、酸化チタン粒子の沈降によって生じるスラリー上層の透明層の高さ（ｍｍ）を、静置時間１分、３分、５分、１０分、３０分、６０分及び１２０分で測定した。透明層の高さが小さい程、重合体組成物の分散剤としての性能が優れることを示す。
[Measurement of dispersibility]
Polymer composition in terms of solid content, 0.3 g of titanium oxide particles (HT0514 manufactured by Toho Titanium) having an average particle size of 0.5 μm in a 50 mL glass sample bottle (screw tube No. 7 manufactured by Marum) 6 mg is added, and ion-exchanged water is further added to make the total amount of titanium oxide particles, the polymer composition and water 30 g, and after sealing, ultrasonication is performed for 30 minutes with an ultrasonic cleaner Yamato 1510 manufactured by Yamato Scientific Co., Ltd. The treatment was performed to prepare a 1% by mass titanium oxide slurry. The obtained slurry was transferred to a sedimentation test tube having an inner diameter of 10 mm and allowed to stand at 25 ° C. The height (mm) of the transparent upper layer of the slurry generated by the sedimentation of the titanium oxide particles was set to a standing time of 1 minute, 3 minutes. Measurements were taken at 5 minutes, 10 minutes, 30 minutes, 60 minutes and 120 minutes. It shows that the performance as a dispersing agent of a polymer composition is excellent, so that the height of a transparent layer is small.
重合体組成物の製造例で得られた重合体組成物Ａ１〜Ａ１６、Ｂ１、Ｃ１及びＡ５１〜Ａ５４を用い、実施例１〜１８及び比較例１〜４として、前述の［沈殿物量の測定］及び［分散性試験］を行った。また比較例５として、重合体組成物を用いずに［分散性試験］を行った。結果を表１に示す。 Using the polymer compositions A1 to A16, B1, C1 and A51 to A54 obtained in the production examples of the polymer composition, Examples 1 to 18 and Comparative Examples 1 to 4 described above [Measurement of amount of precipitate] And [Dispersibility test]. Further, as Comparative Example 5, [Dispersibility Test] was performed without using the polymer composition. The results are shown in Table 1.
工程１に一般式（Ｉ）で表される化合物を用い、工程２でアルカリ金属水酸化物を用いて得られた重合体組成物を使用した実施例１〜１８は、比較例１〜４に比べて沈殿物質量が少なく、中和工程での凝集を抑制する効果が優れていることが示された。また、比較例１〜５に比べて透明層の高さが小さく、重合体組成物の分散剤としての性能が優れていることが示された。 Examples 1 to 18 using the compound represented by the general formula (I) in Step 1 and using the polymer composition obtained in Step 2 using an alkali metal hydroxide were used in Comparative Examples 1 to 4. Compared with the amount of the precipitated substance, it was shown that the effect of suppressing aggregation in the neutralization step was excellent. Moreover, the height of the transparent layer was small compared with Comparative Examples 1-5, and it was shown that the performance as a dispersing agent of a polymer composition is excellent.
本発明はジイソブチレンと無水マレイン酸共重合体の中和を容易に行う方法を提供する。また、本発明の方法によって得られる重合体組成物は無機粒子、有機顔料などの粉体用の水系分散剤として有用である。 The present invention provides a method for easily neutralizing diisobutylene and a maleic anhydride copolymer. The polymer composition obtained by the method of the present invention is useful as an aqueous dispersant for powders such as inorganic particles and organic pigments.
Claims (5)
工程１ 前記共重合体及び水を含有する組成物と、一般式（Ｉ）で表される化合物からなる第１の中和剤とを、混合する工程
工程２ 工程１で得られた混合物と、アルカリ金属水酸化物からなる第２の中和剤とを、混合する工程
を含み、前記工程１における一般式（Ｉ）で表される化合物を混合する量が、前記共重合体に含まれる無水マレイン酸由来の構成単位１００ｍｏｌに対し１〜１５ｍｏｌである、重合体組成物の製造方法。 A method for producing a polymer composition obtained by mixing a copolymer of maleic anhydride and diisobutylene and a neutralizing agent,
Process 1 The process of mixing the composition containing the said copolymer and water, and the 1st neutralizing agent which consists of a compound represented by general formula (I).
Mixing the mixture obtained in Step 2 Step 1, a second neutralizing agent consisting of alkali metal hydroxide, the mixing process seen containing a compound represented by the general formula (I) in the step 1 The manufacturing method of the polymer composition whose quantity to do is 1-15 mol with respect to 100 mol of structural units derived from the maleic anhydride contained in the said copolymer .
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