CN104014287A - Thermal expansion type foaming micro-sphere and preparation method thereof - Google Patents

Thermal expansion type foaming micro-sphere and preparation method thereof Download PDF

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CN104014287A
CN104014287A CN201410261388.0A CN201410261388A CN104014287A CN 104014287 A CN104014287 A CN 104014287A CN 201410261388 A CN201410261388 A CN 201410261388A CN 104014287 A CN104014287 A CN 104014287A
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preparation
monomer
amino resins
inner layer
thermal expansion
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CN104014287B (en
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吕建平
刘姣姣
周凯军
李嵩
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Hefei University of Technology
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Hefei University of Technology
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Abstract

The invention discloses a thermal expansion type foaming micro-sphere and a preparation method thereof. The thermal expansion type foaming micro-sphere is composed of an outer layer shell, an inner layer shell and a capsule core in sequence from outside to inside, wherein the outer layer shell is made of gelatin modified low-cross-linking-degree amino resin; the inner layer shell is a branched structure polyurethane/alkene polymerizable monomer; the capsule core is made of low-boiling-point aliphatic alkane; the mass ratio of the capsule core to the inner layer shell to the outer layer shell is 100 to (125-330) to (1-15). The preparation method for the thermal expansion type foaming micro-sphere comprises unit processes including preparation of an inner layer shell pre-polymer, preparation of an outer layer shell pre-polymer, preparation of the outer layer shell and preparation of the inner layer shell. The thermal expansion type foaming micro-sphere disclosed by the invention is uniform in grain diameter and has good adhesive strength with a base material; the foaming temperature can be reduced and the energy consumption is reduced; the influences on the base material with poor heat resistance by the temperatures are avoided.

Description

A kind of thermal expansion type foam microspheres and preparation method thereof
One, technical field
The present invention relates to a kind of foam microspheres and preparation method thereof, specifically a kind of thermal expansion type foam microspheres and preparation method thereof.
Two, background technology
Thermal expansion type foam microspheres be a kind of mainly with thermoplastic polymer for shell and with blowing agent for the microsphere with nucleocapsid structure that core was formed, the boiling point of blowing agent is lower than the glass transition temperature of thermoplastic polymer.When heating, blowing agent gasifies and presses in increasing, and thermoplastic polymer softens simultaneously, thereby causes microballoon to expand.The temperature that thermal expansion type foam microspheres starts to expand is called T start, the temperature while reaching maximum swelling is called T maximum.
Thermal expansion type foam microspheres can be used for the fields such as coating, weaving, plastic processing, adhesive, sealing ring, synthetic leather, insulation, lightweight material.Can find different thermal expansion type microballoons and the detailed description of preparation thereof.
US 20110123807 proposes a kind of preparation method of the thermal expansion type foam microspheres with nucleocapsid structure, and taking blowing agent as core, it is shell that the number-average molecular weight having taking thermoplastic resin with between crosslink sites is greater than 500 long-chain crosslinking agent.The method can increase the viscosity of monomer and blowing agent blends, prepares the thermal expansion type microballoon with homogeneous diameter.But adding of esters of acrylic acid long-chain crosslinking agent, has increased the crosslink density in shell polymer molecular chain, improve the mechanical strength of shell, but also dwindled steady bubble temperature range simultaneously.
US 7931967B2 prepares a kind of thermal expansion type microballoon with suspension polymerization under the existence of polymerizable organo-silicon compound, shell composition comprises polymerisable monomer copolymer and organo-silicon compound, adhesive force by shell surface organosilicon functional group to inorganic particulate, adhere to a certain amount of inorganic particulate at microsphere surface by chemical bond, the agglomeration traits of avoiding foam microspheres particle to produce in preparation process and foaming process.But use polymerizable organo-silicon compound to increase cost of material, affect the polymerisation of acrylate monomer, the inorganic particulate of microsphere surface bonding affects the purity of microballoon.
Three, summary of the invention
The present invention aims to provide a kind of thermal expansion type foam microspheres and preparation method thereof, by gelatin modified low crosslinking degree amino resins outer shell, solves the adhesion between dispersed phase drop in thermal-initiated polymerization process, makes that clad ratio is high, the foam microspheres of narrow diameter distribution; By branched structure polyurethane, improve the viscosity of dispersed phase drop, improve dispersion stability; Can gather monomer with branched structure polyurethane/olefinic and form inner layer case, make and there is low T startthermal expansion type microballoon, improve elasticity and the mechanical property of wall material, making can be better than the foaming of acrylate shell and foam stability, has the thermal expansion type foam microspheres of excellent compatibility with base material.
Thermal expansion type foam microspheres prepared by the present invention is taking more lower boiling aliphatic alkane blowing agent as capsule-core, at room temperature first carry out pre-parcel sizing with gelatin modified low crosslinking degree amino resins and form outer shell, branched structure polyurethane/olefinic can gather monomer to be caused copolymerization by intensification and forms the high inner layer case of the good expansion rate of heat-resisting air-tightness in capsule-core, reduces T start, be applied to the base material foaming that heat resisting temperature is low.In foamable process, the first broken capsule of low-intensity amino resins outer shell, then polyurethane/olefinic can gather monomer inner layer case and is subject to thermal softening, depresses rapid expansion in the gasification of blowing agent.
Thermal expansion type foam microspheres of the present invention is made up of outer shell, inner layer case and capsule-core from outside to inside successively; Described outer shell is gelatin modified low crosslinking degree amino resins; Described inner layer case is that branched structure polyurethane/olefinic can gather monomer; Described capsule-core is low boiling aliphatic alkane; Mass ratio between described capsule-core, inner layer case and outer shell is 100:125-330:1-15.
The particle diameter of described thermal expansion type foam microspheres is 3-20 μ m.
The preparation method of thermal expansion type foam microspheres of the present invention, comprises the preparation of inner layer case prepolymer, preparation, the preparation of outer shell and the each unit process of the preparation of inner layer case of outer shell prepolymer:
The preparation of described inner layer case prepolymer be first by polymer polyatomic alcohol at 95-110 DEG C of vacuum dehydration 1-2h, be then cooled to 50 DEG C, add polyisocyanates, be warming up to 70 DEG C of insulation reaction 2h, add subsequently catalyst, in 70 DEG C of insulation reaction 40min, reactant liquor is cooled to 60 DEG C, adds acrylic ester monomer, branching agent, the olefinic of hydroxyl can gather monomer and blowing agent, in 60 DEG C of reaction 2h, after reaction finishes, is down to room temperature, obtains two key end-blocking branched structure polyurethane mixture solution, wherein polymer polyatomic alcohol, polyisocyanates, the mol ratio of the acrylic ester monomer of branching agent and hydroxyl is (0.8-1.1): (2.8-3.2): (0.3-0.5): (1.5-1.8), the quality of catalyst is polymer polyatomic alcohol, polyisocyanates, the 0.01-0.4% of the gross mass of the acrylic ester monomer of branching agent and hydroxyl, the quality of blowing agent is polymer polyatomic alcohol, polyisocyanates, branching agent, the acrylic ester monomer of hydroxyl and olefinic can gather the 30-80% of the gross mass of monomer, polymer polyatomic alcohol, polyisocyanates, the mass ratio that the gross mass of the acrylic ester monomer of branching agent and hydroxyl and olefinic can gather monomer is 0.25-1:1,
The preparation of described outer shell prepolymer is that amino resins class material, formaldehydes material and water are mixed, the quality of water is 7-14 times of amino resins class material mass, with lye pH adjustment value 7-10, being warming up to 60-90 DEG C reacts to reactant liquor clarification and adds gelatin and gelatin quality 6-12 water doubly, insulation reaction 20-40min, after reaction finishes, be down to room temperature, obtain gelatin modified amino resins prepolymer; The quality of amino resins class material is the 1-10% of blowing agent quality; The quality of formaldehydes material is the 10-40% of amino resins class material mass; The quality of gelatin accounts for the 3-16% of amino resins class material mass, preferably 5-10%;
The preparation of described outer shell is that initator, two key end-blocking branched structure polyurethane mixture solution and dispersant are added to the water and carry out emulsifying, the quality of water is two key end-blocking branched structure polyurethane mixture solution and dispersant quality sum 3-10 times, add subsequently gelatin modified amino resins prepolymer, obtain blowing agent emulsion; In described blowing agent emulsion, add acid conditioning agent adjust pH 4-6, in 20-25 DEG C of reaction 2-4h, obtain the dispersion liquid of gelatin modified low crosslinking degree amino resins outer shell; The quality of initator is the 0.1-3% of two key end-blocking branched structure polyurethane mixture solution qualities, and quality, the quality of gelatin modified amino resins prepolymer and the mass ratio of blowing agent of two key end-blocking branched structure polyurethane mixtures are (125-330): (1-15): 100;
The preparation of described inner layer case is that the dispersion liquid of described gelatin modified low crosslinking degree amino resins outer shell is warming up to 50-80 DEG C of reaction 5-24h, and branched structure polyurethane/olefinic can gather monomer inner layer case and form, and obtains thermal expansion type foam microspheres.
In the preparation process of inner layer case prepolymer, described polymer polyatomic alcohol is selected from one or more in PolyTHF ethers polyalcohol, polycaprolactone dihydroxylic alcohols, PCDL, Polyoxypropylene diol, and the number-average molecular weight of described polymer polyatomic alcohol is 600-4000;
Described polyisocyanates is selected from one or more in 1,6-hexamethylene diisocyanate, toluene di-isocyanate(TDI), isofoer diisocyanate, cyclohexane diisocyanate, methyl diphenylene diisocyanate;
Described catalyst is trimethylamine class catalyst or organic tin catalyst, described trimethylamine class catalyst is selected from triethylenediamine, triethylamine, tetramethyl butane diamine or triethanolamine, and described organic tin catalyst is selected from dibutyl tin dilaurate, stannous octoate or dienoic acid dibutyl tin;
The acrylic ester monomer of described hydroxyl is hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxy propyl methacrylate;
Described branching agent is trimethylolpropane, pentaerythrite or glycerine;
Described blowing agent is C 5-C 12straight or branched saturated hydrocarbons compound;
Described olefinic can gather monomer and be selected from one or more in nitrile monomer, acrylic monomer, acrylic ester monomer, acrylamide monomers.
Described olefinic can gather monomer and be configured to by mass percentage: nitrile monomer 20-80%, acrylic monomer 0-10%, acrylic ester monomer 20-60%, acrylamide monomers 0-10%;
Described nitrile monomer is acrylonitrile and/or methacrylonitrile;
Described acrylic monomer is acrylic acid and/or methacrylic acid;
Described acrylic ester monomer is one or more in methyl acrylate, methyl methacrylate, ethyl acrylate, EMA, n propyl methacrylate, butyl acrylate, butyl methacrylate, Isooctyl acrylate monomer, vinylacetate;
Described acrylamide monomers is N,N-DMAA.
The number-average molecular weight of described polymer polyatomic alcohol is 1000-2000;
Described blowing agent is C 5-C 8straight or branched saturated hydrocarbons compound, is preferably iso-butane, pentane, isopentane, n-hexane or isooctane.
In the preparation process of outer shell prepolymer, described amino resins class material is selected from one or more in melamine, urea, dicyandiamide; Described formaldehydes material is selected from formaldehyde or paraformaldehyde;
Described alkali lye is one or more in sodium hydroxide solution, potassium hydroxide solution, aqua calcis, sodium carbonate liquor, sodium bicarbonate solution or triethanolamine.
Described amino resins class material is melamine;
Described alkali lye is sodium bicarbonate solution.
In the preparation process of outer shell, described initator is azo-initiator; Described dispersant is water-soluble organic polymer or inorganic particle; Described water-soluble organic polymer is selected from polyvinylpyrrolidone, Arabic gum, starch, PEO, polyvinyl alcohol, Ludox, carboxy methyl cellulose, methylcellulose or agaropectin, and described inorganic particle is selected from magnesium salts, calcium salt, molysite, barium salt, nickel salt, manganese salt, zinc salt or silica; Described acid conditioning agent is selected from one or more in hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetic acid or ammonium chloride.
Described initator is azodiisobutyronitrile;
Described acid conditioning agent is hydrochloric acid or acetic acid.
The present invention adopts gelatin modified, is the degree of cross linking in order to reduce amino resins on the one hand, reduces the mechanical strength of amino resins outer shell, does not affect the foaming process of inner layer case.Two keys on gelatin can gather with polyurethane/olefinic the graft copolymerization of monomer generation part on the other hand, and guiding free radicals copolymerization reaction carries out to amino resins outer shell direction, makes the microballoon that capsule-core is blowing agent.
In the present invention, gelatin modified amino resins prepolymer plays three kinds of effects simultaneously: in dispersion process, with conventional dispersant synergistic, form compound dispersing agent, dispersed phase drop particle diameter is evenly distributed; Gelatin and amino resins generation condensation reaction, can reduce the degree of cross linking of amino resins, the broken capsule temperature of regulation and control amino resins and mechanical strength; When the branching terminal double bond polyurethane/olefinic of capsule-core drop can gather monomer when free-radical polymerized, two keys on gelatin become graft crosslinking point, impel capsule-core drop can gather monomer copolymerization at branching terminal double bond polyurethane/olefinic and be separated to external migration and blowing agent, making capsule-core is the nucleocapsid structure microballoon of blowing agent.
The present invention wraps up in advance with amino resins, can wrap large, the low-boiling blowing agent of volatility, makes and has lower T startthermal expansion type microballoon.
The polyisocyanates that the polymer polyatomic alcohol that in the present invention, the synthetic preferred number average molecular weight of two key end-blocking branched structure polyurethane is 1000-2000 and molecular weight are 160-250, add branching agent to form branched structure, add the acrylate of hydroxyl to form the branched structure with two key end-blockings.Owing to containing unsaturated bond in isocyanates structure, there is high activity, after reacting with polymer polyatomic alcohol compound, strand two ends are with isocyanates (NCO) group end capping, react with the acrylic ester monomer of branching agent and hydroxyl again, form two key end-blocking branched structure polyurethane.In the present invention, synthetic two key end-blocking branched structure polyurethane, can improve shell air-tightness; Add blowing agent and olefinic can gather monomer as solvent, can reduce viscosity.
The present invention increases it by branched structure polyurethane can gather the solubility in monomer and blowing agent system at olefinic, more can increase the viscosity of dispersed phase drop than acrylic ester cross-linking agent, is more conducive to the stable dispersion in water.Branched structure polyurethane can improve elasticity and the mechanical property of esters of acrylic acid wall material, improves foaming and foam stability energy, and making can low-temp foaming, and the better microspheres of base material compatibility.
In the present invention, the acrylate of hydroxyl can gather between monomer and two key end-blocking branched structure polyurethane and play bridging action at olefinic, and polyurethane has good low temperature flexibility and good elasticity, elasticity and the mechanical property of interior cyst wall can be improved, in the time of foaming, good expansion character can be kept.
In the present invention, blowing agent emulsion dispersion carries out in water, and the consumption of water has a certain impact to operation.When the water yield is less than normal, emulsification is insufficient, can be at reactor surface knot wall in course of reaction; When the water yield is bigger than normal, clad ratio declines, and production efficiency is low.Consider operation and production efficiency factor, the consumption of water is two key end-blocking branched structure polyurethane mixture solution and dispersant quality sum 3-10 times, and preferably 4-7 doubly.The T of thermal expansion type foam microspheres start70-140 DEG C, T maximum140-220 DEG C.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, thermal expansion type foam microspheres of the present invention is after polyurethane-modified, and shell toughness, elasticity and mechanical property are improved, and foaming and foam stability can improve, and surely steep temperature range and expand 70-80 DEG C to;
2, amino resins outer shell has been avoided the agglomeration traits that foam microspheres particle produces in preparation process and foaming process, the powdery product that thermal expansion type foam microspheres outward appearance of the present invention is mobility, particle diameter is distributed in 3-20 μ m, easily more dispersed in macromolecular material, the compatibility of microballoon and base material improves;
3, thermal expansion type foam microspheres of the present invention has low T start, reach 70 DEG C, can be applicable to coating, weaving, plastic processing, adhesive, sealing ring, synthetic leather, insulation, lightweight material etc., avoid the adverse effect of high temperature to base material and reduce the energy consumption of foaming process.
Four, detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.
Embodiment primary raw material used is as follows:
Polymer polyatomic alcohol: polyether polyols is Polyoxypropylene diol (PPG), industrial goods, the Zhong Mountain, Jiangsu petrochemical plant is produced;
Polyisocyanates: toluene diisocynate (TDI), 1,6-hexamethylene diisocyanate (HDI), industrial goods, Bayer A.G produces;
Catalyst: dibutyl tin laurate (DBTDL), chemical pure, Tianjin Chemical Reagents Factory No.1 produces;
The acrylic ester monomer of hydroxyl: hydroxy-ethyl acrylate (HEA), industrial goods, Beijing Orient Chemical Manufacture;
Branching agent: trimethylolpropane (TMP), industrial goods, German BASF AG produces;
Olefinic can gather monomer: methyl methacrylate (MMA), butyl acrylate (BA), ethyl acrylate (EA), propylene fine (AN), methacrylonitrile (MAN), acrylic acid (AA), methacrylic acid-β-hydroxypropyl acrylate (HPMA), methacrylic acid-beta-hydroxy ethyl ester (HEMA), is industrial goods, Beijing Orient Chemical Manufacture (production of chemical reagents corporation of traditional Chinese medicines group);
Blowing agent: n-hexane, isopentane, industrial goods, chemical reagents corporation of traditional Chinese medicines group produces;
Amino resins class material: melamine, industrial goods, Guangzhou Zhong Ye Chemical Co., Ltd. produces;
Aldehyde material: the formalin that mass concentration is 37%, industrial goods, chemical reagents corporation of traditional Chinese medicines group produces;
Gelatin, industrial goods, Dongguan City Xin Cheng gelatin Co., Ltd produces;
Initator: azodiisobutyronitrile (AIBN), Shanghai Yong Zheng Chemical Co., Ltd. produces;
Dispersant: silica (SiO 2), industrial goods, Shanghai Jing Lian new material Co., Ltd; PVP (PVP), industrial goods, Shang nautical mile specialization work Science and Technology Ltd. produces; Arabic gum, industrial goods, Shanghai Shuan Sheng Chemical Co., Ltd. produces.
Embodiment 1:
1, the preparation of inner layer case prepolymer: add 15.2g PPG (number-average molecular weight 1000) in 250ml there-necked flask, at 100 DEG C of vacuum dehydration 1h; Be cooled to 50 DEG C, add 4.0g TDI, be warming up to 70 DEG C, insulation reaction 2h, adds catalyst 0.01g DBTDL subsequently, in 70 DEG C of insulation reaction 40min; Reactant liquor is cooled to 60 DEG C, adds 3.0g HEA, 0.12g TMP, 39.0g AN, 11.0g MAN, 24.0g MMA, 7.2g BA and 40.0g n-hexane, in 60 DEG C of reaction 2h, obtains two key end-blocking branched structure polyurethane mixture solution, is down to room temperature for subsequent use;
2, the preparation of outer shell prepolymer: to the formalin and the 38g water that add 3.2g melamine, 2.6g mass concentration 37% in the 250ml there-necked flask of thermometer, agitator and reflux condensing tube are housed, with the sodium bicarbonate solution adjust pH 8.0 of mass concentration 5%, being warming up to 78 DEG C reacts to reactant liquor clarification and adds 0.26g gelatin and 2g water, insulation reaction 0.5h, obtain gelatin modified amino resins prepolymer, be down to room temperature for subsequent use;
3, the preparation of outer shell: the two key end-blocking branched structure polyurethane mixture solution and the initator 0.6g AIBN that add successively step 1 to make in 1000ml beaker, after dissolving, add 640g water, 11.2g silica and 2.4g PVP, open homogenized milk agent machine (ESR, Shanghai Sample Model Factory), the gelatin modified amino resins prepolymer that adds step 2 to make under room temperature after emulsion dispersion 20min, makes blowing agent emulsion; Described blowing agent emulsion is joined in the 1000ml there-necked flask that thermometer, agitator and reflux condensing tube are housed, at room temperature add acetic acid, adjust pH 4-6, reacts 3h, obtains the dispersion liquid of gelatin modified low crosslinking degree amino resins outer shell;
4, the preparation of inner layer case: the dispersion liquid of the gelatin modified low crosslinking degree amino resins outer shell that step 3 is made is warming up to 60 DEG C of reaction 18h, after reaction finishes, be cooled to room temperature, filter, washing, 30-40 DEG C of dry 24h, makes the Powdered thermal expansion type foam microspheres of narrow diameter distribution.
Embodiment 2:
1, the preparation of inner layer case prepolymer: add 12.4g PPG (number-average molecular weight 1000) in 250ml there-necked flask, at 100 DEG C of vacuum dehydration 1h; Be cooled to 50 DEG C, add 3.2g HDI, be warming up to 70 DEG C, insulation reaction 2h; Add subsequently catalyst 0.01g DBTDL, insulation reaction 40min; Be cooled to 60 DEG C, add 2.4g HEA, 0.10g TMP, 39.6g AN, 8.8g MAN, 17.4g MMA, 4.4g BA and 1.5g DMAA and 36.0g n-hexane, reaction 2h, obtains two key end-blocking branched structure polyurethane mixture solution, is down to room temperature for subsequent use;
2, the preparation of outer shell prepolymer: to the formalin and the 38g water that add 3.2g melamine, 2.6g mass concentration 37% in the 250ml there-necked flask of thermometer, agitator and reflux condensing tube are housed, with the sodium bicarbonate solution adjust pH 8.0 of mass concentration 5%, being warming up to 78 DEG C reacts to reactant liquor clarification and adds 0.26g gelatin and 2g water, insulation reaction 0.5h, obtain gelatin modified amino resins prepolymer, be down to room temperature for subsequent use;
3, the preparation of outer shell: the two key end-blocking branched structure polyurethane mixture solution and the initator 0.6g AIBN that add successively step 1 to make in 1000ml beaker, after dissolving, add 620g water, 10.8g silica and 2.2g PVP, open homogenized milk agent machine (ESR, Shanghai Sample Model Factory), the gelatin modified amino resins prepolymer that adds step 2 to make under room temperature after emulsion dispersion 20min, make blowing agent emulsion, described blowing agent emulsion is joined thermometer is housed, in the 1000ml there-necked flask of agitator and reflux condensing tube, at room temperature add acetic acid, adjust pH 4-6, reaction 3h, obtain the dispersion liquid of gelatin modified low crosslinking degree amino resins outer shell,
4, the preparation of inner layer case: the dispersion liquid of the gelatin modified low crosslinking degree amino resins outer shell that step 3 is made is warming up to 60 DEG C of reaction 18h, after reaction finishes, be cooled to room temperature, filter, washing, 30-40 DEG C of dry 24h, makes the Powdered thermal expansion type foam microspheres of narrow diameter distribution.
Embodiment 3:
1, the preparation of inner layer case prepolymer: add 15.2g PPG (number-average molecular weight 1000) in 250ml there-necked flask, at 100 DEG C of vacuum dehydration 1h; Be cooled to 50 DEG C, add 4.0g TDI, be warming up to 70 DEG C, insulation reaction 2h; Add subsequently catalyst 0.01g DBTDL, insulation reaction 40min; Be cooled to 60 DEG C, add 3.0g HEA, 0.12g TMP, 39.0g AN, 11.0g MAN, 24.0g MMA, 7.2g BA and 40.0g n-hexane, reaction 2h, obtains two key end-blocking branched structure polyurethane mixture solution, is down to room temperature for subsequent use;
2, the preparation of outer shell prepolymer: to the formalin and the 38g water that add 3.2g melamine, 2.6g mass concentration 37% in the 250ml there-necked flask of thermometer, agitator and reflux condensing tube are housed, with the sodium bicarbonate solution adjust pH 8.0 of mass concentration 5%, being warming up to 78 DEG C reacts to reactant liquor clarification and adds 0.26g gelatin and 2g water, insulation reaction 0.5h, obtain gelatin modified amino resins prepolymer, be down to room temperature for subsequent use;
3, the preparation of outer shell: the two key end-blocking branched structure polyurethane mixture solution and the initator 0.6g AIBN that add successively step 1 to prepare in 1000ml beaker, after dissolving, add 640g water and 1.0g Arabic gum, open homogenized milk agent machine (ESR, Shanghai Sample Model Factory), the gelatin modified amino resins prepolymer that adds step 2 to make under room temperature after emulsion dispersion 20min, make blowing agent emulsion, described blowing agent emulsion is joined thermometer is housed, in the 1000ml there-necked flask of agitator and reflux condensing tube, at room temperature add acetic acid, adjust pH 4-6, reaction 3h, obtain the dispersion liquid of gelatin modified low crosslinking degree amino resins outer shell,
4, the preparation of inner layer case: the dispersion liquid of the gelatin modified low crosslinking degree amino resins outer shell that step 3 is made is warming up to 60 DEG C of reaction 18h, after reaction finishes, be cooled to room temperature, filter, washing, 30-40 DEG C of dry 24h, makes the Powdered thermal expansion type foam microspheres of narrow diameter distribution.
Embodiment 4:
1, the preparation of inner layer case prepolymer: add 15.2g PPG (number-average molecular weight 1000) in 250ml there-necked flask, at 100 DEG C of vacuum dehydration 1h; Be cooled to 50 DEG C, add 4.0g TDI, be warming up to 70 DEG C, insulation reaction 2h; Add subsequently catalyst 0.01g DBTDL, insulation reaction 40min; Be cooled to 60 DEG C, add 3.0g HEA, 0.12g TMP, 39.0g AN, 11.0g MAN, 24.0g MMA and 7.2g BA, insulation reaction 2h, is down to room temperature, adds 40.0g isopentane, obtains two key end-blocking branched structure polyurethane mixture solution, for subsequent use;
2, the preparation of outer shell prepolymer: to the formalin and the 38g water that add 3.2g melamine, 2.6g mass concentration 37% in the 250ml there-necked flask of thermometer, agitator and reflux condensing tube are housed, with the sodium bicarbonate solution adjust pH 8.0 of mass concentration 5%, being warming up to 78 DEG C reacts to reactant liquor clarification and adds 0.26g gelatin and 2g water, insulation reaction 0.5h, obtain gelatin modified amino resins prepolymer solution, be down to room temperature for subsequent use;
3, the preparation of outer shell: the two key end-blocking branched structure polyurethane mixture solution and the initator 0.6g AIBN that add successively step 1 to make in 1000ml beaker, after dissolving, add 640g water, 11.2g silica and 2.4g PVP, open homogenized milk agent machine (ESR, Shanghai Sample Model Factory), the gelatin modified amino resins prepolymer that adds step 2 to make after emulsion dispersion 20min, make blowing agent emulsion, described blowing agent emulsion is joined thermometer is housed, in the 1000ml there-necked flask of agitator and reflux condensing tube, at room temperature add acetic acid, adjust pH 4-6, reaction 3h obtains the dispersion liquid of gelatin modified low crosslinking degree amino resins outer shell,
4, the preparation of inner layer case: the dispersion liquid of the gelatin modified low crosslinking degree amino resins outer shell that step 3 is made is warming up to 60 DEG C of reaction 18h, after reaction finishes, be cooled to room temperature, filter, washing, 30-40 DEG C of dry 24h, makes the Powdered thermal expansion type foam microspheres of narrow diameter distribution.
Comparative example 1:
1, emulsion dispersion: add initator 0.6g AIBN, 39.0g AN, 11.0g MAN, 24.0g MMA, 7.2g BA in 1000ml beaker, initator is dissolved in monomer, add 640g water, 11.2g silica and 2.4g PVP, open homogenized milk agent machine (ESR, Shanghai Sample Model Factory), add 40.0g n-hexane, make blowing agent emulsion, for subsequent use;
2, thermal expansion type microballoon thermal-initiated polymerization preparation: described blowing agent emulsion is joined and be warming up to 60 DEG C of reaction 18h in the 1000ml there-necked flask that thermometer, agitator and reflux condensing tube are housed, after finishing, reaction is cooled to room temperature, filter, washing, 30-40 DEG C of dry 24h, makes thermal expansion type foam microspheres.
Comparative example 2:
1, two key end-blocking branched structure polyurethane is synthetic: in 250ml there-necked flask, add 15.2g PPG (number-average molecular weight 1000), at 100 DEG C of vacuum dehydration 1h; Be cooled to 50 DEG C, add 4.0g TDI, be warming up to 70 DEG C, insulation reaction 2h; Add catalyst 0.01g DBTDL, insulation reaction 40min; Be cooled to 60 DEG C, add 3.0g HEA, 0.12g TMP, 39.0gAN, 11.0g MAN, 24.0g MMA, 7.2g BA and 40.0g n-hexane, reaction 2h, obtains two key end-blocking branched structure polyurethane mixture solution, is down to room temperature for subsequent use;
2, emulsion dispersion: add successively two key end-blocking branched structure polyurethane mixture solution and initator 0.6g AIBN in 1000ml beaker, after dissolving, add 640g water and 1.0g Arabic gum, open homogenized milk agent machine (ESR, Shanghai Sample Model Factory), emulsion dispersion 20min under room temperature, make blowing agent emulsion, for subsequent use;
3, thermal expansion type microballoon thermal-initiated polymerization preparation: described blowing agent emulsion is joined and be warming up to 60 DEG C of reaction 18h in the 1000ml there-necked flask that thermometer, agitator and reflux condensing tube are housed, after finishing, reaction is cooled to room temperature, filter, washing, 30-40 DEG C of dry 24h, makes thermal expansion type foam microspheres.
By embodiment 1,2,3,4 with relatively its performances of comparative example 1,2 lists, result is as following table:
* there is part cluster caking phenomenon in comparative example 2 after 8 hours in polymerisation, cannot detect its foam characteristics and particle diameter and distribute.
By embodiment 1,2,3,4 compared with comparative example 1, and result shows that embodiment products obtained therefrom has low T start, wide steady bubble temperature journey and narrow particle diameter distribute.

Claims (10)

1. a thermal expansion type foam microspheres, is characterized in that: described thermal expansion type foam microspheres is made up of outer shell, inner layer case and capsule-core from outside to inside successively; Described outer shell is gelatin modified low crosslinking degree amino resins; Described inner layer case is that branched structure polyurethane/olefinic can gather monomer; Described capsule-core is low boiling aliphatic alkane; Mass ratio between described capsule-core, inner layer case and outer shell is 100:125-330:1-15.
2. thermal expansion type foam microspheres according to claim 1, is characterized in that: the particle diameter of described thermal expansion type foam microspheres is 3-20 μ m.
3. a preparation method for thermal expansion type foam microspheres claimed in claim 1, comprises the preparation of inner layer case prepolymer, preparation, the preparation of outer shell and the each unit process of the preparation of inner layer case of outer shell prepolymer, it is characterized in that:
The preparation of described inner layer case prepolymer be first by polymer polyatomic alcohol at 95-110 DEG C of vacuum dehydration 1-2h, be then cooled to 50 DEG C, add polyisocyanates, be warming up to 70 DEG C of insulation reaction 2h, add subsequently catalyst, in 70 DEG C of insulation reaction 40min, reactant liquor is cooled to 60 DEG C, adds acrylic ester monomer, branching agent, the olefinic of hydroxyl can gather monomer and blowing agent, in 60 DEG C of reaction 2h, after reaction finishes, is down to room temperature, obtains two key end-blocking branched structure polyurethane mixture solution, wherein polymer polyatomic alcohol, polyisocyanates, the mol ratio of the acrylic ester monomer of branching agent and hydroxyl is (0.8-1.1): (2.8-3.2): (0.3-0.5): (1.5-1.8), the quality of catalyst is polymer polyatomic alcohol, polyisocyanates, the 0.01-0.4% of the gross mass of the acrylic ester monomer of branching agent and hydroxyl, the quality of blowing agent is polymer polyatomic alcohol, polyisocyanates, branching agent, the acrylic ester monomer of hydroxyl and olefinic can gather the 30-80% of the gross mass of monomer, polymer polyatomic alcohol, polyisocyanates, the mass ratio that the gross mass of the acrylic ester monomer of branching agent and hydroxyl and olefinic can gather monomer is 0.25-1:1,
The preparation of described outer shell prepolymer is that amino resins class material, formaldehydes material and water are mixed, the quality of water is 7-14 times of amino resins class material mass, with lye pH adjustment value 7-10, being warming up to 60-90 DEG C reacts to reactant liquor clarification and adds gelatin and gelatin quality 6-12 water doubly, insulation reaction 20-40min, after reaction finishes, be down to room temperature, obtain gelatin modified amino resins prepolymer; The quality of amino resins class material is the 1-10% of blowing agent quality, and the quality of formaldehydes material is the 10-40% of amino resins class material mass, and the quality of gelatin accounts for the 3-16% of amino resins class material mass;
The preparation of described outer shell is that initator, two key end-blocking branched structure polyurethane mixture solution and dispersant are added to the water and carry out emulsifying, adds subsequently gelatin modified amino resins prepolymer, obtains blowing agent emulsion; In described blowing agent emulsion, add acid conditioning agent adjust pH 4-6, in 20-25 DEG C of reaction 2-4h, obtain the dispersion liquid of gelatin modified low crosslinking degree amino resins outer shell; The quality of initator is the 0.1-3% of two key end-blocking branched structure polyurethane mixture solution qualities, and quality, the quality of gelatin modified amino resins prepolymer and the mass ratio of blowing agent of two key end-blocking branched structure polyurethane mixtures are (125-330): (1-15): 100;
The preparation of described inner layer case is that the dispersion liquid of described gelatin modified low crosslinking degree amino resins outer shell is warming up to 50-80 DEG C of reaction 5-24h, and branched structure polyurethane/olefinic can gather monomer inner layer case and form, and obtains thermal expansion type foam microspheres.
4. preparation method according to claim 3, is characterized in that:
In the preparation process of inner layer case prepolymer, described polymer polyatomic alcohol is selected from one or more in PolyTHF ethers polyalcohol, polycaprolactone dihydroxylic alcohols, PCDL, Polyoxypropylene diol, and the number-average molecular weight of described polymer polyatomic alcohol is 600-4000;
Described polyisocyanates is selected from one or more in 1,6-hexamethylene diisocyanate, toluene di-isocyanate(TDI), isofoer diisocyanate, cyclohexane diisocyanate, methyl diphenylene diisocyanate;
Described catalyst is trimethylamine class catalyst or organic tin catalyst, described trimethylamine class catalyst is selected from triethylenediamine, triethylamine, tetramethyl butane diamine or triethanolamine, and described organic tin catalyst is selected from dibutyl tin dilaurate, stannous octoate or dienoic acid dibutyl tin;
The acrylic ester monomer of described hydroxyl is hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate or hydroxy propyl methacrylate;
Described branching agent is trimethylolpropane, pentaerythrite or glycerine;
Described blowing agent is C 5-C 12straight or branched saturated hydrocarbons compound;
Described olefinic can gather monomer and be selected from one or more in nitrile monomer, acrylic monomer, acrylic ester monomer, acrylamide monomers.
5. preparation method according to claim 4, is characterized in that:
Described olefinic can gather monomer and be configured to by mass percentage: nitrile monomer 20-80%, acrylic monomer 0-10%, acrylic ester monomer 20-60%, acrylamide monomers 0-10%;
Described nitrile monomer is acrylonitrile and/or methacrylonitrile;
Described acrylic monomer is acrylic acid and/or methacrylic acid;
Described acrylic ester monomer is one or more in methyl acrylate, methyl methacrylate, ethyl acrylate, EMA, n propyl methacrylate, butyl acrylate, butyl methacrylate, Isooctyl acrylate monomer, vinylacetate;
Described acrylamide monomers is N,N-DMAA.
6. preparation method according to claim 4, is characterized in that:
The number-average molecular weight of described polymer polyatomic alcohol is 1000-2000;
Described blowing agent is C 5-C 8straight or branched saturated hydrocarbons compound.
7. preparation method according to claim 3, is characterized in that:
In the preparation process of outer shell prepolymer, described amino resins class material is selected from one or more in melamine, urea, dicyandiamide; Described formaldehydes material is selected from formaldehyde or paraformaldehyde;
Described alkali lye is one or more in sodium hydroxide solution, potassium hydroxide solution, aqua calcis, sodium carbonate liquor, sodium bicarbonate solution or triethanolamine.
8. preparation method according to claim 7, is characterized in that:
Described amino resins class material is melamine;
Described alkali lye is sodium bicarbonate solution.
9. preparation method according to claim 3, is characterized in that:
In the preparation process of outer shell, described initator is azo-initiator; Described dispersant is water-soluble organic polymer or inorganic particle; Described water-soluble organic polymer is selected from polyvinylpyrrolidone, Arabic gum, starch, PEO, polyvinyl alcohol, Ludox, carboxy methyl cellulose, methylcellulose or agaropectin, and described inorganic particle is selected from magnesium salts, calcium salt, molysite, barium salt, nickel salt, manganese salt, zinc salt or silica; Described acid conditioning agent is selected from one or more in hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetic acid or ammonium chloride.
10. preparation method according to claim 9, is characterized in that:
Described initator is azodiisobutyronitrile;
Described acid conditioning agent is hydrochloric acid or acetic acid.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104844944A (en) * 2015-04-24 2015-08-19 范汝良 Foam microsphere pre-dispersion mother micelle, and preparation method and application thereof
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WO2019043235A1 (en) * 2017-09-04 2019-03-07 Akzo Nobel Chemicals International B.V. Thermally expandable microspheres prepared from bio-based monomers
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030198822A1 (en) * 2002-04-19 2003-10-23 Phillipp Schaefer Leather assembly and method of fabricating a leather assembly
WO2004108811A1 (en) * 2003-06-06 2004-12-16 Basf Aktiengesellschaft Method for the production of expanding thermoplastic elastomers
CN101827911A (en) * 2007-10-16 2010-09-08 松本油脂制药株式会社 Heat-expandable microspheres, process for production of the same and uses thereof
CN103554428A (en) * 2013-11-18 2014-02-05 中国林业科学研究院林产化学工业研究所 Core-shell synergistic flame retardant polyurethane microencapsulation expandable graphite and application thereof in rigid polyurethane foaming plastic

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030198822A1 (en) * 2002-04-19 2003-10-23 Phillipp Schaefer Leather assembly and method of fabricating a leather assembly
WO2004108811A1 (en) * 2003-06-06 2004-12-16 Basf Aktiengesellschaft Method for the production of expanding thermoplastic elastomers
CN101827911A (en) * 2007-10-16 2010-09-08 松本油脂制药株式会社 Heat-expandable microspheres, process for production of the same and uses thereof
CN103554428A (en) * 2013-11-18 2014-02-05 中国林业科学研究院林产化学工业研究所 Core-shell synergistic flame retardant polyurethane microencapsulation expandable graphite and application thereof in rigid polyurethane foaming plastic

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