JPH0248038A - Surface treatment of inorganic powder by polymerization with depositing initiator - Google Patents
Surface treatment of inorganic powder by polymerization with depositing initiatorInfo
- Publication number
- JPH0248038A JPH0248038A JP19738088A JP19738088A JPH0248038A JP H0248038 A JPH0248038 A JP H0248038A JP 19738088 A JP19738088 A JP 19738088A JP 19738088 A JP19738088 A JP 19738088A JP H0248038 A JPH0248038 A JP H0248038A
- Authority
- JP
- Japan
- Prior art keywords
- inorganic powder
- polymer
- pores
- initiator
- polymerization
- 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
- 239000000843 powder Substances 0.000 title claims abstract description 47
- 239000003999 initiator Substances 0.000 title claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 title claims description 25
- 238000004381 surface treatment Methods 0.000 title claims description 12
- 238000000151 deposition Methods 0.000 title claims description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 24
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- 238000000576 coating method Methods 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 19
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 125000005210 alkyl ammonium group Chemical group 0.000 claims abstract description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims description 50
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 7
- 239000012736 aqueous medium Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 58
- 239000000377 silicon dioxide Substances 0.000 abstract description 29
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 10
- 229920000620 organic polymer Polymers 0.000 abstract description 5
- 239000004793 Polystyrene Substances 0.000 abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 3
- 150000004706 metal oxides Chemical class 0.000 abstract description 3
- 229920002223 polystyrene Polymers 0.000 abstract description 3
- 239000011324 bead Substances 0.000 abstract description 2
- 239000011521 glass Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 abstract 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract 2
- 239000011591 potassium Substances 0.000 abstract 2
- 229910052939 potassium sulfate Inorganic materials 0.000 abstract 2
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 abstract 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 abstract 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- XCOHAFVJQZPUKF-UHFFFAOYSA-M octyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](C)(C)C XCOHAFVJQZPUKF-UHFFFAOYSA-M 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002335 surface treatment layer Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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】
［産業上の利用分野コ
本発明は、無機粉体の表面処理方法に関し、特にビニル
モノマを用いた開始剤沈着重合法による無機粉体の表面
処理方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for surface treatment of inorganic powder, and more particularly to a method for surface treatment of inorganic powder by an initiator deposition polymerization method using a vinyl monomer.
［従来の技術及びその課題］
従来より、例えは吸着剤又は酵素の担体等としては、各
種の球状樹脂が提案されている。この種の樹脂は素材が
有機ポリマのみであるので、耐熱性、耐有機溶剤性９機
械的強度等に問題がある。[Prior Art and its Problems] Various spherical resins have been proposed as, for example, adsorbents or enzyme carriers. Since this type of resin is made only of organic polymers, it has problems in heat resistance, organic solvent resistance, mechanical strength, etc.
この様な欠点を補うために、金属酸化物等からなる無機
粉体に表面処理を施したものが提案されている。この表
面処理の一つの方法としては、シラン系等のカップリン
グ剤を用いて無機粉体の表面を有機物で被覆する方法が
知られている。ところがこの方法では、表面処理層が不
安定であること、表面処理部位の制御が不可能であるこ
と、更に工程が複雑になりコストが高くなることなどの
欠点があった。In order to compensate for these drawbacks, it has been proposed that an inorganic powder made of metal oxide or the like is subjected to surface treatment. As one method for this surface treatment, a method is known in which the surface of an inorganic powder is coated with an organic substance using a coupling agent such as a silane type. However, this method has the disadvantages that the surface treatment layer is unstable, the surface treatment region cannot be controlled, and the process becomes complicated and costs increase.
また、上記カップリング剤を使用する代わりに、ビニル
モノマを用いて無機粉体の表面を有機ポリマで被覆しよ
うとすると、重合が進むにつれて無機粉体同志が有機ポ
リマによって結び付けられて凝集してしまい、境状とな
った無機粉体しか得られないという課題があった。Furthermore, if an attempt is made to coat the surface of an inorganic powder with an organic polymer using a vinyl monomer instead of using the above-mentioned coupling agent, as the polymerization progresses, the inorganic powder will be bound together by the organic polymer and aggregate. The problem was that only marginal inorganic powder could be obtained.
また特ｔこ、ビニルモノマを用いる場合の問題点は、無
機粉体が多孔体である場合に顕著に現れ、上記の凝集に
よって多孔体の細孔が塞がれてしまうので、細孔の種々
の利用ができなくなるという課題が生じていた。In particular, the problem when using a vinyl monomer becomes noticeable when the inorganic powder is porous, and the pores of the porous material are blocked by the above-mentioned agglomeration. There was a problem that it became unusable.
本発明は、無機粉体の個々の表面に、有機高分子の被膜
を形成することを目的とする。The object of the present invention is to form an organic polymer film on each surface of an inorganic powder.
［課題を解決するための手段］
即ち上記目的を達するためになされた請求項１の発明は
、
水媒体中に無機粉体を入れて懸濁させた懸濁液に、０６
〜Ｃ＋８程度の長鎖のアルキルアンモニウム四級塩と過
硫酸カリウム又は過硫酸アンモニウムとを加え、上記無
機粉体の表面上に重合反応の開始剤となる難溶性の複塩
を沈着して形成し、更にこの懸濁液にビニルモノマを添
加して、重合を開始し上記無機粉体表面をポリマで被覆
することを特徴とする開始剤沈着重合法による無機粉体
の表面処理方法を要旨とする。[Means for Solving the Problem] That is, the invention of claim 1 made to achieve the above object is as follows.
Adding a long-chain alkyl ammonium quaternary salt of about ~C+8 and potassium persulfate or ammonium persulfate, depositing a sparingly soluble double salt that serves as an initiator for the polymerization reaction on the surface of the inorganic powder, forming the The gist of the present invention is a method for surface treatment of inorganic powder by an initiator deposition polymerization method, which further comprises adding a vinyl monomer to this suspension to initiate polymerization and coating the surface of the inorganic powder with the polymer.
また、請求項２の発明は、
上記無機粉体として、上記ビニルモノマの径より大きな
径の細孔を多数備えた多孔体を用いて、上記細孔内部ま
でポリマで被覆することを特徴とする請求項１記載の開
始剤沈着重合法による無機粉体の表面処理方法を要旨と
する。Further, the invention according to claim 2 is characterized in that, as the inorganic powder, a porous body having a large number of pores having a diameter larger than the diameter of the vinyl monomer is used, and the inside of the pores are coated with a polymer. The gist of the present invention is a method for surface treatment of inorganic powder using the initiator deposition polymerization method described in Section 1.
更に、請求項３の発明は、
多数の細孔を備えた無機粉体の多孔体に、ｃ６〜Ｃ＋ｅ
程度の長鎖のアルキルアンモニウム四級塩と過硫酸カリ
ウム又は過硫酸アンモニウムとを添加した水系分散剤を
、上記多孔体の細孔容積の合計以下の量供給することに
より、上記細孔内部に上記水系分散剤を吸蔵させて、上
記細孔内部の表面上に重合反応の開始剤となる難溶性の
複塩を沈着して形成し、その後ビニルモノマを加えるこ
とによって重合を開始して上記細孔内部をポリマで被覆
することを特徴とする開始剤沈着重合法による無機粉体
の表面処理方法を要旨とする。Furthermore, the invention of claim 3 provides that a porous body of inorganic powder with a large number of pores has c6 to C+e.
By supplying an aqueous dispersant containing a long-chain alkyl ammonium quaternary salt and potassium persulfate or ammonium persulfate in an amount equal to or less than the total pore volume of the porous body, the aqueous dispersant is added to the inside of the pores. The dispersant is occluded to deposit and form a sparingly soluble double salt that serves as an initiator for the polymerization reaction on the surface inside the pores, and then polymerization is initiated by adding a vinyl monomer to the inside of the pores. The gist of this paper is a method for surface treatment of inorganic powder using an initiator deposition polymerization method, which is characterized by coating with a polymer.
ここで、上記無機粉体としては、粒径約ＩＪ１ｍ〜１０
ｍｍのシリカの他に、チタン、アルミニウム、鉄等の金
属酸化物や、金属粉、ガラスピーズ等を用いることがで
き、その無機粉体が多孔体の場合ここは、細孔の内径約
１０人〜１ｏＪＬｍのものを用いることができる。Here, the inorganic powder has a particle size of approximately IJ1m to 10
In addition to silica, metal oxides such as titanium, aluminum, iron, metal powder, glass beads, etc. can be used.If the inorganic powder is porous, the inner diameter of the pores is approximately 10 mm. ~1oJLm can be used.
また、Ｃ６〜Ｃ＋８程度の長鎖のアルキルアンモニウム
四級塩としては、セチルトリメチルアンモニウムブロミ
ド（ＣＴＡＢｒ）、 オクチルトリメチルアンモニウム
プロミド、ラウリルトリメチルアンモニウムプロミド、
ステアリルトリメチルアンモニウムプロミド等を用いる
ことができる。In addition, as long-chain alkyl ammonium quaternary salts of about C6 to C+8, cetyltrimethylammonium bromide (CTABr), octyltrimethylammonium bromide, lauryltrimethylammonium bromide,
Stearyltrimethylammonium bromide and the like can be used.
また、上記長鎖のアルキルアンモニウム四級塩と過硫酸
カリウム又は過６Ｒ酸アンモニウムとのモル比を、１：
２〜１：４に設定すると、反応が好適に行われ、均一な
被覆が行われるので望ましい。Further, the molar ratio of the long-chain alkyl ammonium quaternary salt and potassium persulfate or ammonium per6R acid was set to 1:
Setting the ratio to be 2 to 1:4 is desirable because the reaction is carried out suitably and uniform coating is carried out.
上記難溶性の複塩とは、例えは、過５Ｍ酸シ（七チルト
リメチルアンモニウム）（［Ｃ＋６８３３Ｎ” （ＣＨ
３）３コ２Ｓ２０Ｂ） である。The above-mentioned sparingly soluble double salt is, for example, per5M acid cyclo(7tyltrimethylammonium) ([C+6833N" (CH
3) 3 pieces 2 S 20 B).
更に、上記ビニルモノマの原料としては、スチレン、メ
タクリル酸メチル、アクリロニトリル。Furthermore, the raw materials for the vinyl monomer include styrene, methyl methacrylate, and acrylonitrile.
酢酸ビニル、塩化ビニル、ブタジェン、イソプレン等を
用いることができる。Vinyl acetate, vinyl chloride, butadiene, isoprene, etc. can be used.
そして、重合によって生成されるポリマとしては、例え
はポリスチレン、ポリメタクリル酸メチル、ポリ塩化ビ
ニル、ポリ酢酸ビニル、ポリブタジェン、ポリイソプレ
ン等がある。Examples of polymers produced by polymerization include polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinyl acetate, polybutadiene, and polyisoprene.
また、重合の際に通常の加熱による方法ではなく、ＲＥ
ＤＯＸ系の開始剤として、還元剤を添加して反応を開始
させてもよい。このＲＥＤＯＸ系の開始剤を用いる場合
の還元剤としては、ＮａＨ３Ｏ３やアミン類が好適であ
る。In addition, instead of the usual heating method during polymerization, RE
As a DOX-based initiator, a reducing agent may be added to initiate the reaction. Suitable reducing agents when using this REDOX-based initiator are NaH3O3 and amines.
［作用コ
請求項１の発明は、
まず無機粉体を水媒体中に入れることによって、無機粉
体が浮遊する懸濁液を作成する。そしてこの懸濁液に、
０６〜０１８程度の長鎖のアルキルアンモニウム四級塩
と過硫酸カリウムとを加え、或は過硫酸カリウムに代わ
りに過硫酸アンモニウムを加えることにより、無機粉体
の表面上に難溶性の複塩を沈着して形成する。次に、こ
の懸濁液にビニルモノマを添加すると、上記無機粉体の
表面上の複塩が重合を開始する開始剤の役割をして、無
機粉体の表面上でビニルモノマの重合が行われる。[Function] The invention of claim 1 first creates a suspension in which the inorganic powder floats by placing the inorganic powder in an aqueous medium. And in this suspension,
By adding a long-chain alkyl ammonium quaternary salt of about 06 to 018 and potassium persulfate, or by adding ammonium persulfate instead of potassium persulfate, a sparingly soluble double salt is deposited on the surface of the inorganic powder. and form it. Next, when a vinyl monomer is added to this suspension, the double salt on the surface of the inorganic powder acts as an initiator to initiate polymerization, and the vinyl monomer is polymerized on the surface of the inorganic powder.
それによって無機粉体の表面はビニルポリマによって被
覆される。Thereby, the surface of the inorganic powder is coated with the vinyl polymer.
また、請求項２の発明は、
無Ｓ扮体として多数の細孔を備えた多孔体を用いる方法
であり、この多孔体として細孔の径がビニルモノマの径
より大きな径なものを採用する。Further, the invention of claim 2 is a method of using a porous body having a large number of pores as the S-free disguise body, and the porous body employs a porous body whose pore diameter is larger than the diameter of the vinyl monomer.
従って、細孔内までビニルモノマが入り込むので、多孔
体の外側の表面だけでなく細孔の表面でも重合が行われ
る。それによって、細孔の表面を含む多孔体の全ての表
面がビニルポリマによって被覆される。Therefore, since the vinyl monomer penetrates into the pores, polymerization occurs not only on the outer surface of the porous body but also on the surface of the pores. Thereby, all surfaces of the porous body, including the surfaces of the pores, are coated with vinyl polymer.
請求項３の発明は、
無機粉体として、多数の細孔を備えた多孔体を用いる方
法であり、この多孔体に対して、上記０６〜（、＋ｅ程
度の長鎖のアルキルアンモニウム四級塩と過硫酸カリウ
ム又は１ＦｔＬ酸アンモニウムとを加えた水系分散剤を
、多数の細孔容積の合計以下の量だけ供給する。それに
よって、水系分散剤は多孔体の細孔内部に毛細管現象に
よって吸蔵されてしまうので、多孔体の外側の表面にお
いては複塩が沈着せずに、細孔の表面のみで複塩が沈着
する。The invention of claim 3 is a method of using a porous body having a large number of pores as the inorganic powder, and adding the above-mentioned long-chain alkyl ammonium quaternary salt of about 06 to (, +e) to the porous body. An aqueous dispersant containing potassium persulfate or ammonium persulfate or ammonium persulfate is supplied in an amount less than the total volume of many pores.Thereby, the aqueous dispersant is occluded inside the pores of the porous body by capillary action. Therefore, the double salt is not deposited on the outer surface of the porous body, but is deposited only on the surface of the pores.
従って、との複塩が沈着した多孔体にビニルポリマを加
えると、細孔の表面のみで重合が起こり、細孔内のみが
ビニルポリマで被覆される。Therefore, when a vinyl polymer is added to a porous body on which a double salt of .
［実施例コ 以下に本発明の詳細な説明する。[Example code] The present invention will be explained in detail below.
（第１実施例）
本実施例は、無機粉体として、多数の細孔を有する多孔
体のシリカを用い、多孔体の細孔の内部の表面だけでな
く多孔体の外側の表面もポリマで被覆するものである。(First Example) In this example, porous silica having many pores is used as the inorganic powder, and not only the inner surface of the pores of the porous body but also the outer surface of the porous body is made of polymer. It is something to cover.
本実施例に用いる物質を第１表に示し、特にその中のシ
リカの特徴を第２表に示す。このシリカの測定は周知の
分析方法で行った。このうち表面積は窒素吸着法を、細
孔容積は水銀ポロシメータを用いて測定した。The substances used in this example are shown in Table 1, and the characteristics of silica among them are shown in Table 2. The silica was measured using a well-known analytical method. Among these, the surface area was measured using a nitrogen adsorption method, and the pore volume was measured using a mercury porosimeter.
第１表
第２表
上記物質を用いてシリカにポリマを被覆する処理として
、まず蒸留水にシリカを加えて懸濁液を製造し、次に、
その懸濁液に長鎖のアルキルアンモニウム四級塩である
セチルトリメチルアンモニウムプロミド（ＣＴＡＢｒ）
を加え、更に攪拌しながら過硫酸カリウムを加えた。次
いでビニルモノマであるスチレンを加えて、５０℃の恒
温槽の中で２４時間重合を行った。その後、クペロンを
加えて重合を停止させ、沈澱物をメタノール蒸留水で洗
った後に乾燥させた。Table 1 Table 2 As a process for coating silica with a polymer using the above substances, first add silica to distilled water to produce a suspension, then:
Cetyltrimethylammonium bromide (CTABr), a long-chain alkyl ammonium quaternary salt, is added to the suspension.
was added, and potassium persulfate was further added while stirring. Next, styrene, which is a vinyl monomer, was added and polymerization was carried out for 24 hours in a constant temperature bath at 50°C. Thereafter, cuperone was added to stop the polymerization, and the precipitate was washed with methanol-distilled water and dried.
この様にしてポリスチレンで被覆した多孔体について上
記と同様に測定を行った。その測定結果をシリカベース
で第３表に示す。Measurements were carried out in the same manner as above for the porous body coated with polystyrene in this manner. The measurement results are shown in Table 3 on a silica basis.
第３表
上記処理の後のポリマの被覆状態を調べるために、メチ
レンブルー水溶液で原料のシリカ及び実施例のシリカを
着色したところ、ポリマの被覆前の原料のシリカは着色
されたが、被覆後のシリカは全く着色されなかった。こ
れによって、ポリマの被覆は多孔体のシリカの全表面に
わたって十分に行われていることが明かである。Table 3 In order to examine the coating state of the polymer after the above treatment, the raw silica and the silica of the example were colored with a methylene blue aqueous solution.The raw silica before being coated with the polymer was colored, but after the coating The silica was not colored at all. It is clear from this that the polymer coating was sufficiently carried out over the entire surface of the silica of the porous body.
また、ポリマの被覆前の状態を示す第２表と被覆後の状
態を示す第３表とから明らかなように、被覆後では細孔
容積が減少しているので、細孔内にもポリマの被覆が行
われていることが確認される。In addition, as is clear from Table 2 showing the state before polymer coating and Table 3 showing the state after coating, the pore volume has decreased after coating, so there is no polymer in the pores. It is confirmed that the coating is applied.
この様にして製造された本実施例のシリカは、各々のシ
リカの表面上で重合が行われ、また系中に存在するＣＴ
ＡＢｒが分散剤としても作用するので、ポリマの被覆の
処理中に凝集することがなく、流動性が良好であるとい
う顕著な効果がある。The silica of this example produced in this way was polymerized on the surface of each silica, and CT present in the system
Since ABr also acts as a dispersant, it has the remarkable effect of not agglomerating during the processing of the polymer coating and having good fluidity.
（第２実施例）
本実施例は、無機粉末として、第１実施例と同様にシリ
カの多孔体を用い、その細孔内以外の多孔体の表面をポ
リマで被覆するが、細孔内の表面はポリマの被覆を行わ
ないものである。そのための構成として、ビニルモノマ
の径（約３０人）よりも小さな径（約２５人）を有する
細孔を備えた第４表に示すシリカの多孔体を用いる。(Second Example) In this example, a porous silica body is used as the inorganic powder as in the first example, and the surface of the porous body other than the inside of the pores is coated with a polymer. The surface is not coated with polymer. As a structure for this purpose, a porous silica body shown in Table 4 is used, which has pores having a diameter (about 25 pores) smaller than the diameter of the vinyl monomer (about 30 pores).
第４表
上記シリカに対するポリマの被覆の処理は、ＣＴＡＢｒ
を０． ６ｍｍｏｌｅ用いる以外は、上記第１実施例と
同量の、シリカ、過硫酸カリウム、スチレン等を用い、
同様な手順で重合を行った。次にこのシリカの多孔体の
被覆の状態を調べ、シリカベースで第５表に示す測定結
果を得た。Table 4 The treatment of polymer coating on the above silica is CTABr
0. The same amounts of silica, potassium persulfate, styrene, etc. as in the first example were used, except that 6 mmole was used.
Polymerization was carried out in a similar manner. Next, the state of the coating of this porous silica body was examined, and the measurement results shown in Table 5 were obtained on a silica basis.
第５表
本実施例は、第６衷乙こ示すよう乙こ第１実施例の１０
倍のスケールで処理を行った。尚、この球状シリカの多
孔体の特徴を第７表に示す。Table 5 This example is as shown in Table 6.
Processing was performed on twice the scale. The characteristics of this spherical silica porous body are shown in Table 7.
第６表
上記第４表及び第５表から明らかなように、ポリマの被
覆後においても細孔容積が変化していないので、細孔内
はポリマで被覆されていないことが明かである。即ち、
適当な細孔径の多孔体を選択することしこよって、細孔
以外の多孔体の表面のみを選択的にポリマで被覆するこ
とができる。Table 6 As is clear from Tables 4 and 5 above, the pore volume did not change even after coating with the polymer, so it is clear that the insides of the pores were not coated with the polymer. That is,
By selecting a porous body with an appropriate pore size, only the surface of the porous body other than the pores can be selectively coated with the polymer.
（第３実施例）
本実施例は、微細なシリカではなく大型の球状シリカの
多孔体を用いたものであり、細孔内を含めて全表面にポ
リマを被覆するものである。(Third Example) In this example, a large spherical silica porous body is used instead of fine silica, and the entire surface including the inside of the pores is coated with a polymer.
第７表
そして、上記物質を用いて、第１実施例と同様に重合等
の処理を行って、球状シリカに対するボリマの被覆を行
った。その処理後に、ポリマが被覆された多孔体を２つ
に割って調べると、多孔体の細孔内の表面及び細孔内以
外の表面にもポリマが被覆されていた。Table 7 Using the above substances, polymerization and other treatments were carried out in the same manner as in Example 1 to coat spherical silica with volima. After the treatment, the porous body coated with the polymer was divided into two parts and examined, and it was found that the surface inside the pores of the porous body and the surface other than the inside of the pores were also coated with the polymer.
（第４実施例）
本実施例は、上記第３実施例と同様な球状シリカを用い
るが、細孔内のみをポリマで被覆するものである。(Fourth Example) In this example, the same spherical silica as in the third example is used, but only the inside of the pores are coated with a polymer.
そのために、以下の第８表に示す分量の物質を調整した
。To this end, the amounts of substances shown in Table 8 below were prepared.
第８表
そして、まずＣＴ Ａ Ｂ ｒ及び過硫酸カリウムを含
んだ水媒体の量を、細孔容積の総計よりも少ない１０ｍ
０調整する。この水溶液中に球状シリカを加えて混合す
ることにより、水溶液を球状シリカの細孔内に吸蔵させ
、そのままの状態で約１時間放置する。その後、第３実
施例と同様にスチレンを加えて重合を行なってポリマの
被覆を行う。Table 8 Then, first, the amount of aqueous medium containing CT A B r and potassium persulfate was adjusted to 10 ml, which is less than the total pore volume.
Adjust to 0. By adding and mixing spherical silica to this aqueous solution, the aqueous solution is occluded into the pores of the spherical silica, and is left as is for about 1 hour. Thereafter, styrene is added and polymerized to form a polymer coating in the same manner as in the third embodiment.
この様にしてポリマを被覆した球状シリカの多孔体を２
つに割って調べると、細孔内のみがポリマで被覆されて
いた。即ち、上記複塩を生成する水媒体の量を調整する
ことにより、多孔体の細孔内のみを選択的にポリマで被
覆することができる。In this way, two porous bodies of spherical silica coated with polymer were
When it was cut into two parts and examined, only the inside of the pores were coated with polymer. That is, by adjusting the amount of the aqueous medium that produces the double salt, only the inside of the pores of the porous body can be selectively coated with the polymer.
［発明の効果コ
本発明は、無機粉体の表面に開始剤を沈着させた後に、
ビニルモノマを添加して重合を行うので、径の小さな無
機粉体の表面に容易にポリマの被覆を施すことができる
。更に無機粉体として多孔体を用いる場合には、多孔体
の細孔や開始剤の沈着の際に用いる水媒体の量を調節す
ることにより、細孔内以外をポリマで被覆したり、細孔
内のみを選択的に被覆することができる。[Effects of the Invention] The present invention provides that after depositing an initiator on the surface of an inorganic powder,
Since polymerization is carried out by adding a vinyl monomer, the surface of a small diameter inorganic powder can be easily coated with a polymer. Furthermore, when using a porous material as an inorganic powder, by adjusting the pores of the porous material and the amount of the aqueous medium used during the deposition of the initiator, it is possible to cover areas other than the inside of the pores with the polymer, or to Only the inside can be selectively coated.
Claims (1)
Ｃ＿６〜Ｃ＿１＿８程度の長鎖のアルキルアンモニウム
四級塩と過硫酸カリウム又は過硫酸アンモニウムとを加
え、上記無機粉体の表面上に重合反応の開始剤となる難
溶性の複塩を沈着して形成し、更にこの懸濁液にビニル
モノマを添加して、重合を開始し上記無機粉体表面をポ
リマで被覆することを特徴とする開始剤沈着重合法によ
る無機粉体の表面処理方法。 ２ 上記無機粉体として、上記ビニルモノマの径より大
きな径の細孔を多数備えた多孔体を用いて、上記細孔内
部までポリマで被覆することを特徴とする請求項１記載
の開始剤沈着重合法による無機粉体の表面処理方法。 ３ 多数の細孔を備えた無機粉体の多孔体に、Ｃ＿６〜
Ｃ＿１＿８程度の長鎖のアルキルアンモニウム四級塩と
過硫酸カリウム又は過硫酸アンモニウムとを添加した水
系分散剤を、上記多孔体の細孔容積の合計以下の量供給
することにより、上記細孔内部に上記水系分散剤を吸蔵
させて、上記細孔内部の表面上に重合反応の開始剤とな
る難溶性の複塩を沈着して形成し、その後ビニルモノマ
を加えることによって重合を開始して上記細孔内部をポ
リマで被覆することを特徴とする開始剤沈着重合法によ
る無機粉体の表面処理方法。[Claims] 1. A suspension of inorganic powder in an aqueous medium,
Formed by adding a long-chain alkylammonium quaternary salt of about C_6 to C_1_8 and potassium persulfate or ammonium persulfate, and depositing a sparingly soluble double salt that becomes an initiator for the polymerization reaction on the surface of the inorganic powder. A method for surface treatment of inorganic powder by an initiator deposition polymerization method, which further comprises adding a vinyl monomer to this suspension to initiate polymerization and coating the surface of the inorganic powder with the polymer. 2. The initiator-deposited polymer according to claim 1, wherein the inorganic powder is a porous body having a large number of pores with a diameter larger than that of the vinyl monomer, and the inside of the pores are coated with a polymer. Legal surface treatment method for inorganic powder. 3 C_6~ in a porous body of inorganic powder with many pores
By supplying an aqueous dispersant containing a long-chain alkyl ammonium quaternary salt of approximately C_1_8 and potassium persulfate or ammonium persulfate in an amount equal to or less than the total pore volume of the porous body, the above-mentioned The aqueous dispersant is occluded to deposit and form a sparingly soluble double salt that serves as an initiator for the polymerization reaction on the surface inside the pores, and then polymerization is initiated by adding a vinyl monomer to the inside of the pores. A method for surface treatment of inorganic powder by an initiator deposition polymerization method, which comprises coating with a polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19738088A JPH0248038A (en) | 1988-08-08 | 1988-08-08 | Surface treatment of inorganic powder by polymerization with depositing initiator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19738088A JPH0248038A (en) | 1988-08-08 | 1988-08-08 | Surface treatment of inorganic powder by polymerization with depositing initiator |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0248038A true JPH0248038A (en) | 1990-02-16 |
Family
ID=16373553
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19738088A Pending JPH0248038A (en) | 1988-08-08 | 1988-08-08 | Surface treatment of inorganic powder by polymerization with depositing initiator |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0248038A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100399817B1 (en) * | 2000-12-18 | 2003-09-29 | 제일모직주식회사 | Method for the Encapsulation of Inorganic Particles |
| KR100496201B1 (en) * | 2002-12-04 | 2005-06-17 | 나노스피어 주식회사 | Process for preparing multi-functional organic-inorganic microcapsule |
| JP2005290036A (en) * | 2004-03-31 | 2005-10-20 | Kao Corp | Cosmetic |
| US7063213B2 (en) | 2002-07-22 | 2006-06-20 | Mba Polymers, Inc. | Mediating electrostatic separation |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5394581A (en) * | 1977-01-31 | 1978-08-18 | Sinloihi Co Ltd | Process for preparing polymerrcovered carbon black particle |
| JPS61247763A (en) * | 1985-04-26 | 1986-11-05 | Mitsui Toatsu Chem Inc | Method for coating inorganic solid material with polymer |
-
1988
- 1988-08-08 JP JP19738088A patent/JPH0248038A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5394581A (en) * | 1977-01-31 | 1978-08-18 | Sinloihi Co Ltd | Process for preparing polymerrcovered carbon black particle |
| JPS61247763A (en) * | 1985-04-26 | 1986-11-05 | Mitsui Toatsu Chem Inc | Method for coating inorganic solid material with polymer |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100399817B1 (en) * | 2000-12-18 | 2003-09-29 | 제일모직주식회사 | Method for the Encapsulation of Inorganic Particles |
| US7063213B2 (en) | 2002-07-22 | 2006-06-20 | Mba Polymers, Inc. | Mediating electrostatic separation |
| KR100496201B1 (en) * | 2002-12-04 | 2005-06-17 | 나노스피어 주식회사 | Process for preparing multi-functional organic-inorganic microcapsule |
| JP2005290036A (en) * | 2004-03-31 | 2005-10-20 | Kao Corp | Cosmetic |
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