JPS63175636A - Inorganic solid substance coated with polymer and preparation thereof - Google Patents
Inorganic solid substance coated with polymer and preparation thereofInfo
- Publication number
- JPS63175636A JPS63175636A JP455987A JP455987A JPS63175636A JP S63175636 A JPS63175636 A JP S63175636A JP 455987 A JP455987 A JP 455987A JP 455987 A JP455987 A JP 455987A JP S63175636 A JPS63175636 A JP S63175636A
- Authority
- JP
- Japan
- Prior art keywords
- solid substance
- inorganic solid
- monomer
- inorg
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000126 substance Substances 0.000 title claims abstract description 36
- 229920000642 polymer Polymers 0.000 title claims abstract description 22
- 229910003480 inorganic solid Inorganic materials 0.000 title claims description 29
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 239000004094 surface-active agent Substances 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 239000011343 solid material Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims 2
- 238000004581 coalescence Methods 0.000 claims 1
- 239000007787 solid Substances 0.000 abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 15
- 239000000741 silica gel Substances 0.000 abstract description 7
- 229910002027 silica gel Inorganic materials 0.000 abstract description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 abstract description 2
- 239000005909 Kieselgur Substances 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 abstract description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 abstract description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010425 asbestos Substances 0.000 abstract description 2
- 239000000440 bentonite Substances 0.000 abstract description 2
- 229910000278 bentonite Inorganic materials 0.000 abstract description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004927 clay Substances 0.000 abstract description 2
- 229910052895 riebeckite Inorganic materials 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- -1 polyoxyethylene Polymers 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-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
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000010431 corundum Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 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
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying 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
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920000847 nonoxynol Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は充填剤、触媒、吸着剤及び壁剤等に利用可能な
単量体を重合させて得られた重合体によって被覆された
固体物質及びその製造方法に関するものである。Detailed Description of the Invention (Industrial Application Field) The present invention relates to a solid material coated with a polymer obtained by polymerizing monomers that can be used as fillers, catalysts, adsorbents, wall materials, etc. and its manufacturing method.
（従来の技術）
従来、無機粉体の基体として有する優れた特性である例
えば、多孔性、耐圧性、耐薬品性等に着目し、それら基
体をベースとして特殊性能を有するポリマーで被覆する
ことにより、新規な性能を有する材料や、ポリマー粒子
の表面に異種のポリマーを被覆することによって、従来
にない性能ををする成形体、或いはエマルジョン等を製
造する試みがなされている。(Prior art) Conventionally, by focusing on the excellent properties of an inorganic powder base material, such as porosity, pressure resistance, and chemical resistance, and coating these base materials with a polymer having special properties, Attempts have been made to produce molded bodies, emulsions, etc. that exhibit unprecedented performance by using materials with novel performance or by coating the surfaces of polymer particles with different types of polymers.
その代表的な例として、ビニル基をもつ有機スルホン酸
またはその塩の共存下に、ラジカル重合可能な不飽和結
合を有する単量体及び重合開始剤を接触させて固形物質
を被覆する方法があり、例えば特公昭５４−８５４８号
公報及び特開昭５７−１１５１４２号公報等で開示され
ている。A typical example is a method in which a monomer having a radically polymerizable unsaturated bond and a polymerization initiator are brought into contact with each other in the coexistence of an organic sulfonic acid having a vinyl group or a salt thereof to coat a solid substance. , for example, are disclosed in Japanese Patent Publication No. 54-8548 and Japanese Patent Application Laid-Open No. 57-115142.
また近年において、ラジカル重合可能な不飽和結合を有
する単量体と、不飽和アミドフェニル置換アルカンスル
ホン酸基含有単量体を共重合して得られる重合体により
、固形物質を被覆する方法として、例えば特開昭６０−
１２１０号公報の発明などで開示されている。In addition, in recent years, a method of coating a solid substance with a polymer obtained by copolymerizing a monomer having a radically polymerizable unsaturated bond and a monomer containing an unsaturated amidophenyl-substituted alkanesulfonic acid group has been developed. For example, JP-A-60-
This invention is disclosed in the invention of Japanese Patent No. 1210.
その他、ゴム、ポリエステル樹脂等の有機物の充填剤と
して、カーボンブラック、シリカ等の無機物質が使用さ
れている例も公知である。In addition, examples in which inorganic substances such as carbon black and silica are used as fillers for organic substances such as rubber and polyester resins are also known.
（発明が解決しようとする問題点）
しかしながら、前記特公昭５４−８５４８号公報及び特
開昭５７−１１５１４２号公報において開示された発明
においては、実際に使用されている単量体が主にメタク
ル酸メチルに限られており、また適用される固体物質に
も汎用性がなく、実用性のあるものになっていない。(Problems to be Solved by the Invention) However, in the inventions disclosed in Japanese Patent Publication No. 54-8548 and Japanese Patent Application Laid-Open No. 57-115142, the monomers actually used are mainly metaclyl It is limited to methyl acid, and the solid substances to which it is applied are not versatile, so it is not practical.
また、特開昭６０−１２１０号公報に示す発明にあって
は、単量体の種類に限定はないが、特定のスルホン酸基
含有単量体と共重合した重合体でのみ被覆するため、無
機固体表面に特定のスルホン酸基含有重合体が残留し、
被覆する前の無機固体に比べその比表面積が極端に低下
する。そのため、充填剤、触媒及び吸着剤として利用す
る場合には実用性に乏しい。また、更に高性能化を図る
ため、官能基を有する重合体で被覆し、官能基への反応
を行うような場合に、その特定のスルホン酸基含有重合
体が反応の障害となり、高性能化にはどうしても限界が
ある。In addition, in the invention shown in JP-A-60-1210, although there is no limitation on the type of monomer, since the coating is performed only with a polymer copolymerized with a specific sulfonic acid group-containing monomer, A specific sulfonic acid group-containing polymer remains on the surface of an inorganic solid,
Its specific surface area is extremely reduced compared to the inorganic solid before coating. Therefore, it is impractical when used as a filler, catalyst, or adsorbent. In addition, in order to further improve performance, when coating with a polymer having a functional group and reacting to the functional group, the specific sulfonic acid group-containing polymer becomes an obstacle to the reaction, making it difficult to improve performance. There are definitely limits.
更に、ゴム、ポリエステル樹脂等の有機物の充填剤とし
て、カーボンブラック、シリカ等の無機物を使用する場
合には、これらの無機物は親和性に乏しいため、界面活
性剤、アルコール類、シランカップリング剤等を使用し
て無機物表面を親油化し、親和性を持たせる手段が施さ
れているが、この方法では、低分子で単分子的に表面を
処理するため、安定性に欠けているといった問題点があ
る。Furthermore, when using inorganic substances such as carbon black and silica as fillers for organic substances such as rubber and polyester resins, these inorganic substances have poor affinity, so surfactants, alcohols, silane coupling agents, etc. A method has been used to make the inorganic surface lipophilic and give it affinity, but this method has problems such as a lack of stability because the surface is monomolecularly treated with low molecules. There is.
（問題点を解決するための手段）
本発明は、上記の如き種々の問題点を解決した新規な固
体物質及びその製造方法を提供せんとするものであり、
その要旨は、界面活性剤を液体に溶解することにより、
ラジカル重合可能な不飽和結合を有する単量体を無機固
体物質表面で重合させ、それによって得られた重合体で
無機固体物質を被覆する方法及び製造された固体物質に
ある。(Means for Solving the Problems) The present invention aims to provide a novel solid substance that solves the various problems described above and a method for producing the same.
The gist is that by dissolving a surfactant in a liquid,
The present invention relates to a method of polymerizing a monomer having a radically polymerizable unsaturated bond on the surface of an inorganic solid material and coating the inorganic solid material with the resulting polymer, and the produced solid material.
以下、本発明について詳細に説明するに、本発明に係る
無機固体物質としては、シリカゲル、アルミナ、酸化チ
タン、ベントナイト酸性白土。The present invention will be described in detail below. Examples of the inorganic solid materials according to the present invention include silica gel, alumina, titanium oxide, and bentonite acid clay.
ケイソウ土、アスベストアランダム、コランダム、レン
ガ、軽石、マグネシア、ケイ石、ケイ酸カルシウム、ケ
イ酸アルミニウム、鉄粉、銅粉。Diatomaceous earth, asbestos alundum, corundum, brick, pumice, magnesia, silica, calcium silicate, aluminum silicate, iron powder, copper powder.
アルミ粉、炭酸カルシウム、カーボンブランク。Aluminum powder, calcium carbonate, carbon blank.
ゼオライト、セッコウ、ガラスフレーク、セメント等を
掲げることができる。Zeolite, gypsum, glass flakes, cement, etc. can be listed.
また界面活性剤としては、非イオン性界面活性剤である
ポリエチレングリコール、ポリオキシエチレンアルキル
エーテル、ポリオキシエチレン脂肪酸エステル等、カチ
オン型界面活性剤であるセチルトリエチルアンモニアブ
ロマイド、ハロゲン化トリノチルアミノエチルアルキル
アミド、アルキルピリジニウム硫酸塩、ハロゲン化アル
キルトリメチルアンモニウム等、及びアニオン型界面活
性剤であるジアルキルスルホコハク酸ナトリウム（Ａｅ
ｒｏｓｏｌ） 、アルキル硫酸エステルナトリウム。Examples of surfactants include nonionic surfactants such as polyethylene glycol, polyoxyethylene alkyl ether, and polyoxyethylene fatty acid ester, and cationic surfactants such as cetyltriethylammonia bromide and trinotylaminoethyl alkyl halides. amide, alkylpyridinium sulfate, alkyltrimethylammonium halide, etc., and anionic surfactant sodium dialkylsulfosuccinate (Ae
rosol), sodium alkyl sulfate.
オレフィン硫酸エステルナトリウム、アルキルベンゼン
スルホン酸ナトリウムなどを言う。Refers to sodium olefin sulfate, sodium alkylbenzene sulfonate, etc.
一方、ラジカル重合可能な不飽和結合を有する単量体と
しては、重合体が水不溶性であれば良く、重合すべき少
なくとも一種が疎水性単量体であることが望ましい。こ
の疎水性単量体としては、例えばスチレン、α−メチル
スチレン、酢酸ビニル。On the other hand, as the monomer having an unsaturated bond capable of radical polymerization, it is sufficient that the polymer is water-insoluble, and it is desirable that at least one type of monomer to be polymerized is a hydrophobic monomer. Examples of the hydrophobic monomer include styrene, α-methylstyrene, and vinyl acetate.
塩化ビニル、アクリロニトリル、アクリル酸エチル、ア
クリル酸ブチル、アクリル酸グリシジル。Vinyl chloride, acrylonitrile, ethyl acrylate, butyl acrylate, glycidyl acrylate.
ＭＭＡ、メタクリル酸ブチル、メタクリル酸グリシジル
、クロロメチルスチレン、ジビニルベンゼン、エチレン
、プロピレン、エチレングリコールジメタクルレート、
ジビニルエーテル、ブタジェン、クロロプレン等である
。MMA, butyl methacrylate, glycidyl methacrylate, chloromethylstyrene, divinylbenzene, ethylene, propylene, ethylene glycol dimethacrylate,
These include divinyl ether, butadiene, and chloroprene.
本発明で重合を開始する場合、加熱のみによっても行い
うるが、通常重合開始剤を使用した方が良好な結果が得
られる。この重合開始剤としてはラジカル重合を開始す
る能力を有するものであればよく、例えば無機過酸化物
である過硫酸アンモニウム、過硫酸カリ、過酸化水素、
亜硫酸水素ナトリウム及び有機過酸化物であるベルオキ
ソニ硫酸カリウム、ｔ−ブチルパーオキシド、アゾ系開
始剤であるアブビスイソブチロニトリル等がある。When initiating polymerization in the present invention, it can be carried out by heating alone, but better results are usually obtained by using a polymerization initiator. The polymerization initiator may be any initiator as long as it has the ability to initiate radical polymerization, such as inorganic peroxides such as ammonium persulfate, potassium persulfate, hydrogen peroxide,
Examples include sodium bisulfite, potassium peroxonisulfate which is an organic peroxide, t-butyl peroxide, and abisisobutyronitrile which is an azo initiator.
次に固体物質を分散する液状媒体であるが、固体物質を
分散できるものであれば良く、一般には水が使用される
。液状媒体の添加量は、固体物質を分散できる量であれ
ば十分である。Next, regarding the liquid medium in which the solid substance is dispersed, any liquid medium that can disperse the solid substance may be used, and water is generally used. The amount of liquid medium added is sufficient as long as it can disperse the solid substance.
このようにして、液状媒体中で重合反応と同時に固体物
質を被覆するものであるが、この最大の特徴は、極性で
ある無機固体物質を処理するに当たり、極性であるため
無極性の単量体とは親和性が乏しい故、界面活性剤を使
用して無機固体物質表面を親油化し、単量体を無機固体
物質表面に取り込み、そこで重合することによって無機
固体物質を被覆することができることにある。即ち、低
モノマー含量において、無機固体物質表面をぼり完全に
被覆することができ、しかも重合率が高いため、モノマ
ーのロスも少ない。また、無機固体物質表面の親油化に
使用される量以上の界面活性剤を添加することにより、
分散剤としても作用するため単粒体としても取り扱うこ
とができる点にある。なお、界面活性剤は低分子である
ため、無機固体物質表面に残ることはないが、必要に応
じてメタノールあるいは熱メタノールで洗浄すれば完全
に取り除くことができる。In this way, a solid substance is coated simultaneously with the polymerization reaction in a liquid medium.The most important feature of this method is that when treating a polar inorganic solid substance, it is possible to coat a non-polar monomer because it is polar. Since the surface of the inorganic solid substance has poor affinity with the monomer, it is possible to coat the inorganic solid substance by using a surfactant to make the surface of the inorganic solid substance lipophilic, incorporating the monomer onto the surface of the inorganic solid substance, and polymerizing there. be. That is, when the monomer content is low, the surface of the inorganic solid material can be completely coated, and since the polymerization rate is high, there is little loss of monomer. In addition, by adding a surfactant in an amount greater than the amount used to make the surface of an inorganic solid substance lipophilic,
Since it also acts as a dispersant, it can be handled as a single particle. Since the surfactant has a low molecular weight, it will not remain on the surface of the inorganic solid material, but it can be completely removed by washing with methanol or hot methanol if necessary.
〔実施例１〕
水５０ｇに非イオン性界面活性剤ポリエチレングリコー
ル−ノニルフェニルエーテル０．８ｇ、 シリカゲル
５ｇを入れ、窒素雰囲気下で５０℃で十分分散するため
攪拌した後、スチレン１．３ｇを添加してベルオキソニ
硫酸カリウム、亜硫酸水素ナトリウムをそれぞれ０．１
ｇ同時に添加する。そして５０℃に保ちながら５時間重
合を行った。重合はシリカゲルが均一に分散した状態で
進行した。[Example 1] Add 0.8 g of nonionic surfactant polyethylene glycol-nonylphenyl ether and 5 g of silica gel to 50 g of water, stir at 50°C under nitrogen atmosphere to sufficiently disperse, and then add 1.3 g of styrene. and 0.1% each of potassium peroxonisulfate and sodium bisulfite.
g Add at the same time. Then, polymerization was carried out for 5 hours while maintaining the temperature at 50°C. Polymerization proceeded with the silica gel uniformly dispersed.
重合後、混合物を濾別したところ、ポリスチレンは単独
では存在せず、生成物は全てポリスチレンに被覆された
シリカゲルであり、しかも粒子は均一であった。真空乾
燥後秤量したところ、５．９ｇの収量が得られ、定性的
には、生成物の表面を走査型電子顕微鏡で、メチレンプ
ル染色後については実体顕微鏡でそれぞれ観察した結果
、シリカゲルの表面がポリスチレンで被覆されているこ
とが６１ Ｅ’２−された。表面改質に使用された界面
活性剤は、赤外分光光度計によりシリカゲル表面から洗
い流されたことを確認することができた。After the polymerization, the mixture was filtered to find that polystyrene was not present alone, and the product was all silica gel coated with polystyrene, and the particles were uniform. When weighed after vacuum drying, a yield of 5.9 g was obtained. Qualitatively, the surface of the product was observed with a scanning electron microscope, and the surface of the product after methylene pull staining was observed with a stereomicroscope, and it was found that the surface of the silica gel was polystyrene. 61 E'2- was found to be coated with. It was confirmed by an infrared spectrophotometer that the surfactant used for surface modification was washed away from the silica gel surface.
〔実施例２〕
カチオン型界面活性剤セチルトリエチルアンモニアブロ
マイドを使用して、実施例１と同様に重合を行った結果
、生成物は６．１ｇであった。[Example 2] Polymerization was carried out in the same manner as in Example 1 using the cationic surfactant cetyltriethylammonia bromide, and the product was 6.1 g.
また実施例１と同じ方法で表面を観察したところ、生成
物表面はポリスチレンに被覆されていることが確認され
た。Further, when the surface was observed in the same manner as in Example 1, it was confirmed that the surface of the product was coated with polystyrene.
〔実施例３〕
アニオン型界面活性剤Ａｅｒｏｓｏｌ （高品名）につ
いても実施例１と同様に重合を行った結果、生成物は５
．７ｇであった。また実施例１と同じ方法で表面を観察
したところ、同様に生成物表面はポリスチレンにより被
覆されていることが確認された。[Example 3] As a result of polymerizing the anionic surfactant Aerosol (high quality brand) in the same manner as in Example 1, the product was 5
．． It was 7g. Further, when the surface was observed in the same manner as in Example 1, it was confirmed that the surface of the product was similarly coated with polystyrene.
（発明の効果）
以上のように、本発明は従来問題とされていた単量体の
汎用性、あるいは無機固体表面での特定のスルホン酸基
含有重合体の残存により固体表面の比表面積を低下せし
め、触媒や吸着剤等に利用する固体表面の機能が悪く、
効率が極めて低いのに対して、本発明つまり界面活性剤
を利用して、無機固体物質の表面改質を行なっているた
め、華独重合体により被覆することが可能であり、しか
も無機固体の比表面積をあまり低下させることがない。(Effects of the Invention) As described above, the present invention improves the versatility of the monomer, which has been a problem in the past, or reduces the specific surface area of the solid surface by remaining a specific sulfonic acid group-containing polymer on the surface of the inorganic solid. However, the functionality of solid surfaces used as catalysts and adsorbents is poor.
However, since the present invention utilizes surfactants to modify the surface of inorganic solid materials, it is possible to coat them with German-Chinese polymers, and moreover, it is possible to coat inorganic solid materials with The specific surface area does not decrease much.
そのため、用途としては表面積に大きく影響する触媒や
吸着剤等に使用した場合には、顕著な性能効果を発揮す
る。また、低モノマー含量において無機固体物質表面を
ほぼ完全に被覆することができ、しかも重合率が高いた
め七ツマ−のロスも少ない。さらには、製造工程からみ
ても、従来はまず無機固体物質の表面処理を行い、次に
ポリマーと混練をし、そして分離するという３工程を踏
んでいたが、本発明では、界面活性剤を溶解した水系媒
体中で無機固体物質、モノマーをｇ５し、重合を行うこ
とにより、無機固体物を重合により被覆することができ
、分離は乾燥することにより容易にできるため、工程も
短縮され、操作も簡便であり、より実用的である。Therefore, when used in catalysts, adsorbents, etc. that have a large effect on surface area, they exhibit remarkable performance effects. Further, at a low monomer content, the surface of the inorganic solid material can be almost completely covered, and since the polymerization rate is high, there is little loss of monomers. Furthermore, in terms of the manufacturing process, conventionally there were three steps: first surface-treating the inorganic solid material, then kneading it with a polymer, and then separating it, but in the present invention, the surfactant is dissolved. By combining the inorganic solid substance and the monomer in an aqueous medium and performing polymerization, the inorganic solid substance can be coated by polymerization, and separation can be easily performed by drying, so the process is shortened and the operation is easy. It is simple and more practical.
Claims (2)
ル重合可能な不飽和結合を有する単量体を重合させて得
られた重合体により前記無機固体物質の表面を被覆して
なる重合体により被覆された無機固体物質。(1) A polymer obtained by coating the surface of the inorganic solid substance with a polymer obtained by polymerizing a monomer having a radically polymerizable unsaturated bond in suspension of a surfactant and an inorganic solid substance. An inorganic solid substance coated by coalescence.
を使用し、ラジカル重合可能な不飽和結合を有する単量
体を無機固体物質表面で重合させ、この重合体によって
無機固体物質の表面を被覆することを特徴とする重合体
により被覆された無機固体物質の製造方法。(2) Using a surfactant under suspension of an inorganic solid substance in a liquid medium, a monomer having a radically polymerizable unsaturated bond is polymerized on the surface of the inorganic solid substance, and this polymer is used to form an inorganic solid substance. 1. A method for producing an inorganic solid material coated with a polymer, the method comprising: coating the surface of an inorganic solid substance coated with a polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP455987A JPS63175636A (en) | 1987-01-12 | 1987-01-12 | Inorganic solid substance coated with polymer and preparation thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP455987A JPS63175636A (en) | 1987-01-12 | 1987-01-12 | Inorganic solid substance coated with polymer and preparation thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63175636A true JPS63175636A (en) | 1988-07-20 |
Family
ID=11587399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP455987A Pending JPS63175636A (en) | 1987-01-12 | 1987-01-12 | Inorganic solid substance coated with polymer and preparation thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63175636A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100375438B1 (en) * | 2000-12-06 | 2003-03-10 | 제일모직주식회사 | Thermoplastic Composition and Method of Preparing the same |
| WO2006137393A1 (en) * | 2005-06-20 | 2006-12-28 | Seiko Epson Corporation | Microencapsulated material, microencapsulated color material, process for production of the material, ink composition, ink-jet recording method, and recorded material |
| JP2014509248A (en) * | 2011-01-10 | 2014-04-17 | コチ・ウニヴェルシテシ | Encapsulated hydrophobic and hydrophilic airgels with PEG hydrogels via surface-initiated photopolymerization |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4931552A (en) * | 1972-07-20 | 1974-03-22 | ||
| JPS5339977A (en) * | 1976-09-24 | 1978-04-12 | Sumitomo Chem Co Ltd | Preparation of microcapsule |
-
1987
- 1987-01-12 JP JP455987A patent/JPS63175636A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4931552A (en) * | 1972-07-20 | 1974-03-22 | ||
| JPS5339977A (en) * | 1976-09-24 | 1978-04-12 | Sumitomo Chem Co Ltd | Preparation of microcapsule |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100375438B1 (en) * | 2000-12-06 | 2003-03-10 | 제일모직주식회사 | Thermoplastic Composition and Method of Preparing the same |
| WO2006137393A1 (en) * | 2005-06-20 | 2006-12-28 | Seiko Epson Corporation | Microencapsulated material, microencapsulated color material, process for production of the material, ink composition, ink-jet recording method, and recorded material |
| JP5219511B2 (en) * | 2005-06-20 | 2013-06-26 | セイコーエプソン株式会社 | Microencapsulated product, microencapsulated color material, method for producing the same, ink composition, ink jet recording method, and recorded product |
| JP2014509248A (en) * | 2011-01-10 | 2014-04-17 | コチ・ウニヴェルシテシ | Encapsulated hydrophobic and hydrophilic airgels with PEG hydrogels via surface-initiated photopolymerization |
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