CN101245120B - Process for producing cross-linked polymer microsphere with even grain diameter - Google Patents
Process for producing cross-linked polymer microsphere with even grain diameter Download PDFInfo
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- CN101245120B CN101245120B CN2008100151805A CN200810015180A CN101245120B CN 101245120 B CN101245120 B CN 101245120B CN 2008100151805 A CN2008100151805 A CN 2008100151805A CN 200810015180 A CN200810015180 A CN 200810015180A CN 101245120 B CN101245120 B CN 101245120B
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Abstract
The invention relates to a preparation method of crosslinked polymer microphere with uniform particle size. By adopting the process of dispersion and polymerization, styrene or acrylic ester is taken as a monomer; a monodisperse crosslinked polymer microphere with uniform particle size is prepared by steric hindrance dispersant and multi-functional crosslinker. The microphere has regular spherical and solid, a smooth surface, no damage or defect, and the strength and flexibility meet the requirements of producing ACF.
Description
Technical field
The present invention relates to the preparation method of a kind of uniform particle diameter, monodisperse cross-linked micrograde polymer microsphere.This polymer microballoon is mainly used in the conducting particles of preparation anisotropic conductive film (ACF).ACF is mainly used in being connected of electronic calculator, liquid crystal, plasma body and various semi-conductive display pannel and flexible PCB.
Background technology
The development that information, communication industry are advanced by leaps and bounds drives the electronic circuit board circuit and becomes more meticulous with integrated, and increasing unicircuit need assemble with wiring board, and traditional tin lead welding connects and can not meet the demands.Anisotropic conductive film is that nickel plating/metal/polymer microballoon (particle diameter 1.0 μ m～5.0 μ m) is dispersed in the thermosetting resin, is coated on to form on the thick polyester film of 12.5 μ m.Anisotropic conductive film has been save welding, has simplified technology, has improved reliability, has greatly promoted electronics to develop to light, thin, little direction.At present anisotropic conductive film has been widely used in being connected of liquid-crystal display and flexible PCB.
The technological core of anisotropic conductive film is the preparation of the monodisperse polymer microsphere in micro level of uniform particle diameter.The traditional method of preparation polymer microballoon is letex polymerization, suspension polymerization.Though emulsion polymerizing preparation compound microballoon distribution range is narrower, it can only synthesize the particulate less than 0.5 μ m; And the polymer microballoon of suspension polymerization is between 0.1 μ m～1 μ m, but the homogeneity of particle is difficult to control.
Japanese Patent JP 58-106554 and JP 63-191818 have proposed the method for seeding polymerization.Promptly obtain seed by letex polymerization earlier, increase then, enlarge particle.The shortcoming of present method is to need the polystep reaction step, operability and less economical.JP63-191805 has proposed by special dispersion stabilizer is being arranged, under the situation of organic solvent or water/organic solvent system, and the method for one or more vinyl monomer one-step polymerization, however the particle diameter that JP 63-191805 obtains is unsatisfactory.JP4-323213 and JP10-310603 have reported in non-aqueous solvent, preparation N-vinylcarboxylic acid ammonia resin, and the finished product median size is at 10 μ m or following.JP 4-323213 does not mention size distribution; JP10-310603 has mentioned the size distribution of broad.Therefore, to disperse to have crosslinked polymer microballoon particle be unusual difficulty to the micron order list that obtain uniform particle diameter.
Summary of the invention
Technical problem to be solved by this invention is, a kind of preparation method of cross-linked polymer microsphere of uniform particle diameter is provided, linking agent and stablizer are carried out preferably, and selection appropriate solvent, prepare uniform particle diameter, heat-resisting, monodisperse polymer micro-sphere by specific processing condition, make and satisfy the requirement of making ACF better, to overcome above-mentioned existing methods defective.
The technical solution adopted for the present invention to solve the technical problems is as follows:
A kind of preparation method of cross-linked polymer microsphere of uniform particle diameter is characterized in that:
The set of dispense ratio is: monomer concentration: 5～15%, and a polyfunctional crosslinking agent: 1.0～10.0% of amount of monomer, the steric dispersion agent: 5.0～10.0% of amount of monomer, initiator: 0.5～2.0% of amount of monomer, surplus are solvent; Described per-cent is part by weight;
Wherein, monomer is styrenic or esters of acrylic acid;
Described a polyfunctional crosslinking agent is any in the following compound: glycidyl methacrylate, allyl methacrylate(AMA), dimethylaminoethyl methacrylate, dipentaerythrityl ether six propylene esters, dimethacrylate DOPCP, Viscoat 295, polyethyleneglycol diacrylate, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, γ-propyl methacrylate base Trimethoxy silane;
The steric dispersion agent is for being in the following compound any: polyacrylic acid, polyoxyethylene glycol, dextrin, polyvinyl alcohol, partly-hydrolysed polyvinyl acetate, Polyvinylpyrolidone (PVP), polymethyl acrylic acid, vinyl ether copolymers, polystyrolsulfon acid, methylcellulose gum, ethyl cellulose, Natvosol, hydroxypropylcellulose, carboxymethyl cellulose;
Initiator is any in azo-bis-isobutyl cyanide, benzoyl peroxide, di-cyclohexylperoxy dicarbonate, the benzoyl peroxide tert-butyl ester, the dicumyl peroxide;
Solvent is a water-soluble solvent;
1), at 65 ℃～75 ℃ following reactive polymeric 16～24h, stirring velocity 50～150rpm the polymerization technique step comprises:; 2), use washing with alcohol; 3), centrifugal or filtration under diminished pressure; 4), vacuum-drying.
Described styrene monomer is any in the following compound: vinylbenzene, vinyl toluene, dimethyl styrene, ethyl styrene, chloro-styrene, styrene sulfonic acid; Described acrylic ester monomer is any in the following compound: methyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, methacrylic acid 2-ethylhexyl, the methacrylic dodecyl gallate, dimethylaminoethyl methacrylate, the methacrylic acid group ethyl ester, monomethyl vinylformic acid diethyl glycol ester, monomethyl polyalkylene glycol acrylate ester, monomethyl vinylformic acid butanediol ester, methacrylic acid, Methacrylamide, propylene cyanogen, N-methacryloxypropyl succinimide.
Described styrene monomer is a vinylbenzene, and monomer concentration is 7.0～10.0%; Described acrylic ester monomer is methyl methacrylate or N-methacryloxypropyl succinimide, and monomer concentration is 7.0～10.0%.
Water-soluble solvent is a kind of in the following compound or two or morely mixes by arbitrary proportion: water, methyl alcohol, ethanol, propyl alcohol, propyl carbinol, the trimethyl carbinol, ethylene glycol monomethyl ether, ethylene glycol bis methyl ether.
A polyfunctional crosslinking agent is any in glycidyl methacrylate, dipentaerythrityl ether six propylene esters, the Viscoat 295; Consumption is 4.0～6.0% of a monomer weight.
Initiator is azo-bis-isobutyl cyanide or benzoyl peroxide; Consumption is 1.0～1.5% of a monomer weight.
Polymer microballoon requirement as ACF is crosslinked, single dispersion, uniform particle diameter.The performance requriements of particle is regular spherical but also require size evenly not only, and requires to have certain intensity and thermostability.If polymer particle is a non-crosslinked, as styrene polymer, because physical strength is not enough with simple single functional group, under certain pressure, be easy to destroyed, and non-refractory, in ACF making processes, to stand the thermal process that is subjected to more than 150 ℃, particle is easy to be melted, and therefore will satisfy the requirement of making ACF, must prepare crosslinked polymer particle, but general is crosslinked, can make between the particle to produce crosslinkedly, can not obtain monodispersed particle, can not satisfy the requirement of ACF equally.
Positively effect of the present invention is: adopt dispersion polymerization process, with styrenic or acrylate is monomer, adopt steric dispersion agent and a polyfunctional crosslinking agent, the microspherulite diameter of preparing is at 1～2 μ m, uniform particle diameter, single disperse, solid, smooth surface, anti-180 ℃, intensity and toughness reach the requirement of making ACF.
Compare with other polymerization process, the dispersion copolymerization method production technique is simple relatively, can rationally solve heat dissipation problem, can a step obtain micron order, even-grained product, and be applicable to dissimilar monomeric polymerizations, product cut size is controlled, narrow particle size distribution adapts to suitability for industrialized production.
The polymer microballoon sample ethanol ultra-sonic dispersion that description of drawings will make covers on the slide glass equably, uses observation by light microscope; After ethanol disperses dilution, sample preparation, electron microscope is observed down, takes pictures.Wherein Fig. 1～Fig. 6 is respectively the microballoon picture of example one～example six.
Embodiment
Further specify the present invention below in conjunction with accompanying drawing and specific examples.
Example one
The four neck flasks that reaction vessel uses the poly-tetrafluoro of 250mL band to stir, logical water of condensation is used N
2Thermometer is inserted in protection.Use heating in water bath.
Vinylbenzene: 10g; Viscoat 295 0.6g; PVPK30:0.8g; AIBN:0.1g; Ethanol: 120g.With N
2Inlet is inserted under the liquid phase, displaced air 1h, and then mentioning the logical N of gas phase continuation
2Be warming up to 70 ℃, stirring velocity 80rpm, polymerization 24h.With washing with alcohol three times, filtration under diminished pressure, product vacuum-drying.The resulting polymers microspherulite diameter is 1.6 μ m, and 180 ℃ placement 5min is undeformed down.Microballoon TEM sees Fig. 1.
Example two
The four neck flasks that reaction vessel uses the poly-tetrafluoro of 250mL band to stir, logical water of condensation is used N
2Thermometer is inserted in protection.Use heating in water bath.Vinylbenzene: 10g; Glycidyl methacrylate: 0.5g; PVPK30:0.8g; AIBN:0.1g; Ethanol: 120g; Ethylene glycol monomethyl ether: 10g.With N
2Inlet is inserted under the liquid phase, displaced air 1h, and then mentioning the logical N of gas phase continuation
2Be warming up to 65 ℃, stirring velocity 60rpm, polymerization 20h.With washing with alcohol three times, filtration under diminished pressure, product vacuum-drying.The resulting polymers microspherulite diameter is 1.7 μ m, and 180 ℃ placement 5min is undeformed down.Microballoon TEM sees Fig. 2.
Example three
The four neck flasks that reaction vessel uses the poly-tetrafluoro of 250mL band to stir, logical water of condensation is used N
2Thermometer is inserted in protection.Use heating in water bath.Vinylbenzene: 10g; Dipentaerythrityl ether six propylene ester 0.6g; PVPK30:0.8g; AIBN:0.1g; Ethanol: 120.With N
2Inlet is inserted into the following displaced air 1h of liquid level, and then mentions gas phase and continue logical N
2Be warming up to 75 ℃, stirring velocity 80rpm, polymerization 22h.With washing with alcohol three times, filtration under diminished pressure, product vacuum-drying.The resulting polymers microspherulite diameter is 1.65 μ m, and 180 ℃ placement 5min is undeformed down.Microballoon TEM sees Fig. 3.
Example four
The four neck flasks that reaction vessel uses the poly-tetrafluoro of 250mL band to stir, logical water of condensation is used N
2Thermometer is inserted in protection.Use heating in water bath.Methyl methacrylate: 10g; Viscoat 295 0.6g; PVPK30:0.8g; AIBN:0.1g; Ethanol: 120g.Ethylene glycol monomethyl ether: 10g.With N
2Inlet is inserted into the following displaced air 1h of liquid level, and then mentions gas phase and continue logical N
2Be warming up to 70 ℃, stirring velocity 80rpm, polymerization 24h.With washing with alcohol three times, filtration under diminished pressure, product vacuum-drying.The resulting polymers microspherulite diameter is 1.75 μ m, and 180 ℃ placement 5min is undeformed down.Microballoon TEM sees Fig. 4.
Example five
The four neck flasks that reaction vessel uses the poly-tetrafluoro of 250mL band to stir, logical water of condensation is used N
2Thermometer is inserted in protection.Use heating in water bath.Methyl methacrylate: 10g; Glycidyl methacrylate 0.5g; PVPK30:0.8g; AIBN:0.1g; Ethanol 50g; Methyl alcohol: 50g; Ethylene glycol monomethyl ether: 30g.With N
2Inlet is inserted into the following displaced air 1h of liquid level, and then mentions gas phase and continue logical N
2Be warming up to 70 ℃, stirring velocity 150rpm, polymerization 20h.With washing with alcohol three times, filtration under diminished pressure, product vacuum-drying.The resulting polymers microspherulite diameter is 2.0 μ m, and 180 ℃ placement 5min is undeformed down.Microballoon TEM sees Fig. 5.
Example six
The four neck flasks that reaction vessel uses the poly-tetrafluoro of 250mL band to stir, logical water of condensation is used N
2Thermometer is inserted in protection.Use heating in water bath.Prescription: n-BMA: 10g; Glycidyl methacrylate: 0.5g; PVPK30:0.8g; AIBN:0.1g; Methyl alcohol: 100g; Ethylene glycol monomethyl ether: 30g.With N
2Inlet is inserted into the following displaced air 1h of liquid level, and then mentions gas phase and continue logical N
2Be warming up to 75 ℃, stirring velocity 50rpm, polymerization 16h.With washing with alcohol three times, centrifuging, product vacuum-drying.The resulting polymers microspherulite diameter is 2.1 μ m, and 180 ℃ placement 5min is undeformed down.Microballoon TEM sees Fig. 6.
Claims (1)
1. the preparation method of the cross-linked polymer microsphere of a uniform particle diameter is characterized in that:
The set of dispense ratio is: monomer concentration: 7.0～10.0%, and a polyfunctional crosslinking agent: 4.0～6.0% of amount of monomer, the steric dispersion agent: 5.0～10.0% of amount of monomer, initiator: 1.0～1.5% of amount of monomer, surplus are solvent; Described per-cent is part by weight;
Wherein, monomer is vinylbenzene or methyl methacrylate or N-methacryloxypropyl succinimide;
A polyfunctional crosslinking agent is any in glycidyl methacrylate, dipentaerythrityl ether six propylene esters, the Viscoat 295;
The steric dispersion agent is Polyvinylpyrolidone (PVP) PVPK30;
Initiator is Diisopropyl azodicarboxylate or benzoyl peroxide;
Solvent is a water-soluble solvent; Described water-soluble solvent is a kind of in the following compound or two or morely mixes by arbitrary proportion: water, methyl alcohol, ethanol, propyl alcohol, propyl carbinol, the trimethyl carbinol, ethylene glycol monomethyl ether, ethylene glycol bis methyl ether;
1), at 65 ℃～75 ℃ following reactive polymeric 16～24h, stirring velocity 50～150rpm the polymerization technique step comprises:; 2), use washing with alcohol; 3), centrifugal or filtration under diminished pressure; 4), vacuum-drying.
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