CN104014287B - A kind of thermal expansion type foam microspheres and preparation method thereof - Google Patents
A kind of thermal expansion type foam microspheres and preparation method thereof Download PDFInfo
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- CN104014287B CN104014287B CN201410261388.0A CN201410261388A CN104014287B CN 104014287 B CN104014287 B CN 104014287B CN 201410261388 A CN201410261388 A CN 201410261388A CN 104014287 B CN104014287 B CN 104014287B
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Abstract
The invention discloses a kind of thermal expansion type foam microspheres and preparation method thereof, 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; Described capsule-core, mass ratio between inner layer case and outer shell are 100:125-330:1-15.The preparation of described thermal expansion type foam microspheres comprises each unit process of preparation of the preparation of inner layer case prepolymer, the preparation of outer shell prepolymer, the preparation of outer shell and inner layer case.Thermal expansion type foam microspheres uniform particle sizes of the present invention, good with the adhesive strength of base material, can blowing temperature be reduced, reduce energy consumption, avoid temperature on the impact of poor heat resistance base material.
Description
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 main be the microsphere with nucleocapsid structure that core is formed with thermoplastic polymer for shell with blowing agent, the boiling point of blowing agent is lower than the glass transition temperature of thermoplastic polymer.During heating, pressure in blowing agent gasifies and increases, thermoplastic polymer is softening simultaneously, thus causes microsphere expansion.The temperature that thermal expansion type foam microspheres starts to expand is called T
start, temperature when 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, lightweighting materials.Different thermal expansion type microballoons and the detailed description of preparation thereof can be found.
US 20110123807 proposes a kind of preparation method with the thermal expansion type foam microspheres of nucleocapsid structure, take blowing agent as core, is greater than the long-chain crosslinking agent of 500 for shell with thermoplastic resin and the number-average molecular weight that has between crosslink sites.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, add the crosslink density in sheath polymers strand, improve the mechanical strength of shell, but also reduce simultaneously and surely steep temperature range.
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, by the adhesive force of shell layer surface silicone functionalities to inorganic particulate, adhere to a certain amount of inorganic particulate at microsphere surface by chemical bond, avoid the agglomeration traits that foam microspheres particle produces in preparation process and foaming process.But use polymerizable organo-silicon compound to add 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, and the adhesion in solution thermal-initiated polymerization process between dispersed phase drop, obtained 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, obtained have low T
startthermal expansion type microballoon, improve elasticity and the mechanical property of wall material, obtained better, can have the thermal expansion type foam microspheres of excellent compatibility with base material than the foaming of acrylate shell and foam stability.
Thermal expansion type foam microspheres prepared by the present invention is for capsule-core with more lower boiling aliphatic alkane blowing agent, at room temperature first carry out pre-wrapped sizing with gelatin modified low crosslinking degree amino resins and form outer shell, branched structure polyurethane/olefinic can gather monomer and form the high inner layer case of the good expansion rate of resistance to hermetic by the initiation copolymerization that heats up 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 by thermal softening, in the gasification of blowing agent, depress undergoes rapid expansion.
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; Described capsule-core, mass ratio between inner layer case and outer shell are 100:125-330:1-15.
The particle diameter of described thermal expansion type foam microspheres is 3-20 μm.
The preparation method of thermal expansion type foam microspheres of the present invention, comprises each unit process of preparation of the preparation of inner layer case prepolymer, the preparation of outer shell prepolymer, the preparation of outer shell and inner layer case:
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 catalyst subsequently, in 70 DEG C of insulation reaction 40min, reactant liquor is cooled to 60 DEG C, adds the acrylic ester monomer of hydroxyl, branching agent, olefinic can gather monomer and blowing agent, in 60 DEG C of reaction 2h, be down to room temperature, obtain the capped branched structure polyurethane mixture solution of double bond after reaction terminates, 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 mixed amino resins class material, formaldehydes material and water, the quality of water is 7-14 times of amino resins class material mass, with lye pH adjustment value 7-10, gelatin and gelatin quality 6-12 water is doubly added after being warming up to 60-90 DEG C of reaction to reactant liquor clarification, insulation reaction 20-40min, be down to room temperature after reaction terminates, obtain gelatin modified amino resin 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, preferred 5-10%;
The preparation of described outer shell initator, the capped branched structure polyurethane mixture solution of double bond and dispersant is added to the water to carry out emulsifying, the quality of water is 3-10 times of the capped branched structure polyurethane mixture solution of double bond and dispersant quality sum, add gelatin modified amino resin prepolymer subsequently, 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 double bond capped branched structure polyurethane mixture solution quality, and the quality of double bond capped branched structure polyurethane mixture, the quality of gelatin modified amino resin prepolymer and the mass ratio of blowing agent are (125-330): (1-15): 100;
The preparation of described inner layer case 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 be formed, and namely 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 diols, 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 one or more that monomer is selected from 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 watersoluble organic polymer or inorganic particle; Described watersoluble 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, being the degree of cross linking in order to reduce amino resins on the one hand, reducing the mechanical strength of amino resins outer shell, not affecting the foaming process of inner layer case.Double bond on the other hand on gelatin can gather the graft copolymerization of monomer generating portion with polyurethane/olefinic, and guide free radicals copolymerization reaction to carry out to amino resins outer shell direction, obtained capsule-core is the microballoon of blowing agent.
In the present invention, gelatin modified amino resin prepolymer plays three kinds of effects simultaneously: in dispersion process, with conventional dispersant synergistic, forms compound dispersing agent, makes dispersed phase drop even particle size distribution; Gelatin and amino resins generation condensation reaction, can reduce the degree of cross linking of amino resins, and regulation and control amino resins breaks capsule temperature and mechanical strength; When the branching terminal double bond polyurethane/olefinic of capsule-core drop can gather monomer radical copolymerization, double bond on gelatin becomes graft crosslinking point, impel capsule-core drop can gather monomer copolymerization at branching terminal double bond polyurethane/olefinic to be separated to external migration and blowing agent, obtained capsule-core is the nucleocapsid structure microballoon of blowing agent.
The present invention's amino resins carries out pre-wrapped, can wrap large, the low-boiling blowing agent of volatility, and obtained have lower T
startthermal expansion type microballoon.
In the present invention, the synthesis preferred number average molecular weight of the capped branched structure polyurethane of double bond is the polymer polyatomic alcohol of 1000-2000 and molecular weight is the polyisocyanates of 160-250, add branching agent and form branched structure, the acrylate adding hydroxyl is formed with the branched structure of double bond end-blocking.Owing to containing unsaturated bond in isocyanate structural, there is high activity, after reacting with polymer polyol alcoholic compound, strand two ends are with isocyanates (-NCO) group end capping, react with the acrylic ester monomer of branching agent and hydroxyl again, form the capped branched structure polyurethane of double bond.Synthesize the capped branched structure polyurethane of double bond in the present invention, shell air-tightness can be improved; Add blowing agent and olefinic can gather monomer as solvent, can viscosity be reduced.
The present invention increases it by branched structure polyurethane can to gather solubility in monomer and blowing agent system at olefinic, more can increase the viscosity of dispersed phase drop, be more conducive to the stable dispersion in aqueous phase than acrylic ester cross-linking agent.Branched structure polyurethane can improve elasticity and the mechanical property of esters of acrylic acid wall material, improves foaming and foam stability energy, obtained can low-temp foaming, and the better microspheres of substrate compatibility.
In the present invention, the acrylate of hydroxyl can gather between monomer and the capped branched structure polyurethane of double bond at olefinic and plays bridging action, and polyurethane has excellent low temperature flexibility and good elasticity, elasticity and the mechanical property of interior cyst wall can being improved, good expansion character can be kept when foaming.
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 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 3-10 times of the capped branched structure polyurethane mixture solution of double bond and dispersant quality sum, and preferred 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 steady bubble temperature range expands 70-80 DEG C to;
2, amino resins outer shell avoids the agglomeration traits that foam microspheres particle produces in preparation process and foaming process, thermal expansion type foam microspheres outward appearance of the present invention is the powdery product of mobility, domain size distribution is at 3-20 μm, easier to be 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, lightweighting materials etc., avoid high temperature to the adverse effect of 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 and 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, BASF Corp. of Germany 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: mass concentration is the formalin of 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, add 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, and in 60 DEG C of reaction 2h, obtain the capped branched structure polyurethane mixture solution of double bond, it is for subsequent use to be down to room temperature;
2, the preparation of outer shell prepolymer: add 3.2g melamine, the formalin of 2.6g mass concentration 37% and 38g water in the 250ml there-necked flask that thermometer, agitator and reflux condensing tube be housed, with the sodium bicarbonate solution adjust pH 8.0 of mass concentration 5%, be warming up to 78 DEG C of reactions and add 0.26g gelatin and 2g water to reactant liquor clarification, insulation reaction 0.5h, obtain gelatin modified amino resin prepolymer, it is for subsequent use to be down to room temperature;
3, the preparation of outer shell: add the obtained capped branched structure polyurethane mixture solution of double bond of step 1 and initator 0.6g AIBN in 1000ml beaker successively, 640g water, 11.2g silica and 2.4g PVP is added after dissolving, open homogenized milk agent machine (ESR, Shanghai Sample Model Factory), the obtained gelatin modified amino resin prepolymer of step 2 is added, obtained blowing agent emulsion after room temperature emulsified dispersion 20min; Joined by described blowing agent emulsion and be equipped with in the 1000ml there-necked flask of thermometer, 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 gelatin modified low crosslinking degree amino resins outer shell obtained for step 3 is warming up to 60 DEG C of reaction 18h, be cooled to room temperature after reaction terminates, filter, washing, 30-40 DEG C of dry 24h, the Powdered thermal expansion type foam microspheres of obtained 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 catalyst 0.01g DBTDL subsequently, 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 the capped branched structure polyurethane mixture solution of double bond, and it is for subsequent use to be down to room temperature;
2, the preparation of outer shell prepolymer: add 3.2g melamine, the formalin of 2.6g mass concentration 37% and 38g water in the 250ml there-necked flask that thermometer, agitator and reflux condensing tube be housed, with the sodium bicarbonate solution adjust pH 8.0 of mass concentration 5%, be warming up to 78 DEG C of reactions and add 0.26g gelatin and 2g water to reactant liquor clarification, insulation reaction 0.5h, obtain gelatin modified amino resin prepolymer, it is for subsequent use to be down to room temperature;
3, the preparation of outer shell: add the obtained capped branched structure polyurethane mixture solution of double bond of step 1 and initator 0.6g AIBN in 1000ml beaker successively, 620g water is added after dissolving, 10.8g silica and 2.2g PVP, open homogenized milk agent machine (ESR, Shanghai Sample Model Factory), the obtained gelatin modified amino resin prepolymer of step 2 is added after room temperature emulsified dispersion 20min, obtained 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 gelatin modified low crosslinking degree amino resins outer shell obtained for step 3 is warming up to 60 DEG C of reaction 18h, be cooled to room temperature after reaction terminates, filter, washing, 30-40 DEG C of dry 24h, the Powdered thermal expansion type foam microspheres of obtained 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 catalyst 0.01g DBTDL subsequently, 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 the capped branched structure polyurethane mixture solution of double bond, and it is for subsequent use to be down to room temperature;
2, the preparation of outer shell prepolymer: add 3.2g melamine, the formalin of 2.6g mass concentration 37% and 38g water in the 250ml there-necked flask that thermometer, agitator and reflux condensing tube be housed, with the sodium bicarbonate solution adjust pH 8.0 of mass concentration 5%, be warming up to 78 DEG C of reactions and add 0.26g gelatin and 2g water to reactant liquor clarification, insulation reaction 0.5h, obtain gelatin modified amino resin prepolymer, it is for subsequent use to be down to room temperature;
3, the preparation of outer shell: the capped branched structure polyurethane mixture solution of double bond and the initator 0.6g AIBN that add step 1 preparation in 1000ml beaker successively, 640g water and 1.0g Arabic gum is added after dissolving, open homogenized milk agent machine (ESR, Shanghai Sample Model Factory), the obtained gelatin modified amino resin prepolymer of step 2 is added after room temperature emulsified dispersion 20min, obtained 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 gelatin modified low crosslinking degree amino resins outer shell obtained for step 3 is warming up to 60 DEG C of reaction 18h, be cooled to room temperature after reaction terminates, filter, washing, 30-40 DEG C of dry 24h, the Powdered thermal expansion type foam microspheres of obtained 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 catalyst 0.01g DBTDL subsequently, 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, be down to room temperature, add 40.0g isopentane, obtain the capped branched structure polyurethane mixture solution of double bond, for subsequent use;
2, the preparation of outer shell prepolymer: add 3.2g melamine, the formalin of 2.6g mass concentration 37% and 38g water in the 250ml there-necked flask that thermometer, agitator and reflux condensing tube be housed, with the sodium bicarbonate solution adjust pH 8.0 of mass concentration 5%, be warming up to 78 DEG C of reactions and add 0.26g gelatin and 2g water to reactant liquor clarification, insulation reaction 0.5h, obtain gelatin modified amino resin prepolymer solution, it is for subsequent use to be down to room temperature;
3, the preparation of outer shell: add the obtained capped branched structure polyurethane mixture solution of double bond of step 1 and initator 0.6g AIBN in 1000ml beaker successively, 640g water is added after dissolving, 11.2g silica and 2.4g PVP, open homogenized milk agent machine (ESR, Shanghai Sample Model Factory), the gelatin modified amino resin prepolymer that step 2 is obtained is added after emulsion dispersion 20min, obtained 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 gelatin modified low crosslinking degree amino resins outer shell obtained for step 3 is warming up to 60 DEG C of reaction 18h, be cooled to room temperature after reaction terminates, filter, washing, 30-40 DEG C of dry 24h, the Powdered thermal expansion type foam microspheres of obtained 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, obtained blowing agent emulsion, for subsequent use;
2, thermal expansion type microballoon thermal-initiated polymerization preparation: described blowing agent emulsion is joined in the 1000ml there-necked flask that thermometer, agitator and reflux condensing tube are housed and be warming up to 60 DEG C of reaction 18h, room temperature is cooled to after reaction terminates, filter, washing, 30-40 DEG C of dry 24h, obtained thermal expansion type foam microspheres.
Comparative example 2:
1, the capped branched structure polyurethane synthesis of double bond: 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 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 the capped branched structure polyurethane mixture solution of double bond, and it is for subsequent use to be down to room temperature;
2, emulsion dispersion: add the capped branched structure polyurethane mixture solution of double bond and initator 0.6g AIBN in 1000ml beaker successively, 640g water and 1.0g Arabic gum is added after dissolving, open homogenized milk agent machine (ESR, Shanghai Sample Model Factory), room temperature emulsified dispersion 20min, obtained blowing agent emulsion, for subsequent use;
3, thermal expansion type microballoon thermal-initiated polymerization preparation: described blowing agent emulsion is joined in the 1000ml there-necked flask that thermometer, agitator and reflux condensing tube are housed and be warming up to 60 DEG C of reaction 18h, room temperature is cooled to after reaction terminates, filter, washing, 30-40 DEG C of dry 24h, obtained thermal expansion type foam microspheres.
By embodiment 1,2,3,4 compare its performance with comparative example 1,2 list, and result is as following table:
* there is part cluster caking phenomenon in polymerisation in comparative example 2 after 8 hours, cannot detect its foam characteristics and domain size distribution.
By embodiment 1,2,3,4 compared with comparative example 1, and result display embodiment products obtained therefrom has low T
start, wide steady bubble temperature journey and narrow domain size distribution.
Claims (7)
1. a preparation method for thermal expansion type foam microspheres, comprises each unit process of preparation of the preparation of inner layer case prepolymer, the preparation of outer shell prepolymer, the preparation of outer shell and inner layer case, 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 catalyst subsequently, in 70 DEG C of insulation reaction 40min, reactant liquor is cooled to 60 DEG C, adds the acrylic ester monomer of hydroxyl, branching agent, olefinic can gather monomer and blowing agent, in 60 DEG C of reaction 2h, be down to room temperature, obtain the capped branched structure polyurethane mixture solution of double bond after reaction terminates, 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,
In the preparation process of inner layer case prepolymer, described polymer polyatomic alcohol is selected from one or more in PolyTHF ethers polyalcohol, polycaprolactone diols, 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 one or more that monomer is selected from nitrile monomer, acrylic monomer, acrylic ester monomer, acrylamide monomers;
The preparation of described outer shell prepolymer is mixed amino resins class material, formaldehydes material and water, the quality of water is 7-14 times of amino resins class material mass, with lye pH adjustment value 7-10, gelatin and gelatin quality 6-12 water is doubly added after being warming up to 60-90 DEG C of reaction to reactant liquor clarification, insulation reaction 20-40min, be down to room temperature after reaction terminates, obtain gelatin modified amino resin 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 initator, the capped branched structure polyurethane mixture solution of double bond and dispersant is added to the water to carry out emulsifying, adds gelatin modified amino resin prepolymer subsequently, 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 double bond capped branched structure polyurethane mixture solution quality, and the quality of double bond capped branched structure polyurethane mixture, the quality of gelatin modified amino resin prepolymer and the mass ratio of blowing agent are (125-330): (1-15): 100;
The preparation of described inner layer case 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 be formed, and namely obtains thermal expansion type foam microspheres;
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; Described capsule-core, mass ratio between inner layer case and outer shell are 100:125-330:1-15; The particle diameter of described thermal expansion type foam microspheres is 3-20 μm.
2. preparation method according to claim 1, 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.
3. preparation method according to claim 1, 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.
4. preparation method according to claim 1, 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.
5. preparation method according to claim 4, is characterized in that:
Described amino resins class material is melamine;
Described alkali lye is sodium bicarbonate solution.
6. preparation method according to claim 1, is characterized in that:
In the preparation process of outer shell, described initator is azo-initiator; Described dispersant is watersoluble organic polymer or inorganic particle; Described watersoluble 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.
7. preparation method according to claim 1, is characterized in that:
Described initator is azodiisobutyronitrile;
Described acid conditioning agent is hydrochloric acid or acetic acid.
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| CN113174104A (en) * | 2021-03-03 | 2021-07-27 | 快思瑞科技(上海)有限公司 | Master batch material, foaming master batch preparation method and foaming material preparation method |
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| CN117264130A (en) * | 2023-11-21 | 2023-12-22 | 山东鑫鼎化工科技有限公司 | Expandable microsphere for low-temperature environment and preparation method thereof |
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| DE10326138A1 (en) * | 2003-06-06 | 2004-12-23 | Basf Ag | Process for the production of expandable thermoplastic elastomers |
| CN101827911B (en) * | 2007-10-16 | 2013-03-27 | 松本油脂制药株式会社 | Heat-expandable microspheres, process for production of the same and uses thereof |
| CN103554428B (en) * | 2013-11-18 | 2015-05-13 | 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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