CN102702449B - Preparation method of heat-resistant foamed microcapsule - Google Patents
Preparation method of heat-resistant foamed microcapsule Download PDFInfo
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- CN102702449B CN102702449B CN 201210194252 CN201210194252A CN102702449B CN 102702449 B CN102702449 B CN 102702449B CN 201210194252 CN201210194252 CN 201210194252 CN 201210194252 A CN201210194252 A CN 201210194252A CN 102702449 B CN102702449 B CN 102702449B
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000839 emulsion Substances 0.000 claims abstract description 39
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 31
- 239000010703 silicon Substances 0.000 claims abstract description 31
- 239000000725 suspension Substances 0.000 claims abstract description 28
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 23
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007822 coupling agent Substances 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 20
- 239000002270 dispersing agent Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 9
- 206010011732 Cyst Diseases 0.000 claims abstract description 7
- 208000031513 cyst Diseases 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000000178 monomer Substances 0.000 claims description 88
- 239000003795 chemical substances by application Substances 0.000 claims description 59
- 238000007664 blowing Methods 0.000 claims description 47
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 33
- 239000006185 dispersion Substances 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 28
- 239000011259 mixed solution Substances 0.000 claims description 26
- 239000003999 initiator Substances 0.000 claims description 25
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 21
- -1 acrylic ester Chemical class 0.000 claims description 20
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 claims description 19
- 239000003921 oil Substances 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 150000003376 silicon Chemical class 0.000 claims description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 13
- 230000009477 glass transition Effects 0.000 claims description 13
- 229910000077 silane Inorganic materials 0.000 claims description 13
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 12
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 11
- 239000002775 capsule Substances 0.000 claims description 11
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 11
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 238000009736 wetting Methods 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 9
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 claims description 8
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 claims description 8
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 8
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 8
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 8
- 238000010907 mechanical stirring Methods 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical group COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 239000001117 sulphuric acid Substances 0.000 claims description 7
- 235000011149 sulphuric acid Nutrition 0.000 claims description 7
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 claims description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 6
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 claims description 6
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- HLOLETUOZGAKMT-UHFFFAOYSA-N trimethoxysilyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)OC(=O)C(C)=C HLOLETUOZGAKMT-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 125000004386 diacrylate group Chemical group 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 claims description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004258 Ethoxyquin Substances 0.000 claims description 3
- 230000009286 beneficial effect Effects 0.000 claims description 3
- 239000001273 butane Substances 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 230000003750 conditioning effect Effects 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 claims description 3
- 229940093500 ethoxyquin Drugs 0.000 claims description 3
- 235000019285 ethoxyquin Nutrition 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 230000006641 stabilisation Effects 0.000 claims description 3
- 238000011105 stabilization Methods 0.000 claims description 3
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 claims description 2
- 125000000746 allylic group Chemical group 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- ZHSXANMFVCDUJW-UHFFFAOYSA-N prop-1-ene trimethoxysilane Chemical compound CO[SiH](OC)OC.C=CC ZHSXANMFVCDUJW-UHFFFAOYSA-N 0.000 claims description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 2
- 238000005187 foaming Methods 0.000 abstract description 7
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- 238000004140 cleaning Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 239000011162 core material Substances 0.000 abstract 1
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- 239000004088 foaming agent Substances 0.000 abstract 1
- 238000007873 sieving Methods 0.000 abstract 1
- 238000009987 spinning Methods 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- LEJBBGNFPAFPKQ-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethoxy)ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOC(=O)C=C LEJBBGNFPAFPKQ-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
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- 230000000052 comparative effect Effects 0.000 description 8
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- 238000012360 testing method Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 4
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 3
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 3
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- VFZKVQVQOMDJEG-UHFFFAOYSA-N 2-prop-2-enoyloxypropyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(=O)C=C VFZKVQVQOMDJEG-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 2
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- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 1
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
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- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
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Abstract
The invention provides a preparation method of a heat-resistant foamed microcapsule. The heat-resistant foamed microcapsule is prepared through suspension polymerization by taking an acrylonitrile monomer polymer as a cyst wall and taking a low-boiling-point alkane foaming agent as a core material. The method comprises the following steps of: (1) generating a main dispersing agent: adding silica sol into a reflowing and stirrinreaction kettle, and dripping an organic silicon coupling agent at a constant temperature for reacting to obtain a main dispersing agent; (2) generating a suspension emulsion: dispersing an aqueous mixed liquid and an oil-phase mixed liquid into small liquid drops under the action of a high-speed homogenizer to obtain a suspension emulsion; and (3) preparing a foamed microcapsule: transferring the suspension emulsion into a stirring reaction kettle, performing suspension polymerization at a constant temperature, reacting, naturally cooling to the room temperature, filtering, cleaning, drying and sieving to obtain a foamed microcapsule product. A product obtained with the preparation method implemented in the invention has the characteristics of high foaming rate, high heat resistance and uniform particle diameters, and can be applied in the fields of spinning, papermaking, ink, plastic, rubber and the like.
Description
Technical field
The present invention relates to coat pneumatogen by polymer shell and prepare the blowing microcapsule technology, particularly a kind of thermotolerance blowing microcapsule preparation method.This thermotolerance blowing microcapsule can be applicable to fields such as the higher weaving of blowing temperature, papermaking, printing ink, plastics and rubber.
Background technology
Blowing microcapsule is called the thermal expansivity microcapsule again, is the microcapsule that formed by gas barrier property good thermoplastic polymer shell parcel lower boiling pneumatogen, generally forms through suspension polymerization by the polymerisable monomer in the water-soluble dispersion system and whipping agent.
When blowing microcapsule heated, the whipping agent gasification produced bulging force and acts on polymer shell, its modulus is reduced, and when being elevated to certain temperature, capsule takes place sharply to expand, it is original several times and even tens times that its volume increases, and the temperature of this moment is referred to as initial blowing temperature; Further rising temperature, the pressure in the capsule increases, and the capsule volume increases, and the cyst wall attenuation reaches maximum expansion ratio, continues intensification, and whipping agent can see through cyst wall and overflow, and its internal drop is low, and expanded particle shrinks, and the temperature of this moment is called heat resisting temperature.The purposes different according to blowing microcapsule can be divided into ranks such as low temperature, middle temperature, high temperature.In some occasion, need its initial blowing temperature higher, heat resisting temperature is bigger, as the footwear material, wish that the foaming capsule does not foam in mixing process, and in moulding process, foam, be that processing temperature needs high-temperature, therefore, these occasions are that blowing microcapsule has proposed the thermotolerance requirement.
In the prior art, the bibliographical information of the blowing microcapsule that forms about vinyl cyanide and acrylic ester monomer copolymerization system is as follows: the patent No. proposes for the ZL0180821.3 name is called " heat-expandable macrosphere body and manufacture method thereof ", adopt the two key bifunctional crosslinking agents of flexible unsaturated C=C to substitute the two keys of rigidity C=C or triple bond functional group cross-linking monomer, make its cyst wall under blowing temperature keep its elasticity, namely reduce its rigidity; But test finds that expanded particle has adhesion, and blowing temperature reaches about 200 ℃ contraction.The patent No. proposes for the Chinese invention patent that the ZL02811733.6 name is called " heat-expandable macrosphere body and manufacture method thereof ", in the same polymeric system, after certain moment of suspension polymerization, add the technical scheme of silane coupling agent in polymerization system, can reduce the adhesion of expanded particle and the foaming behavior that wide cut appears in lesser temps; The main coupling agent that adds that exists is inhomogeneous in the suspension system dispersion, contains gel group phenomenon in the thick product thereby cause.Number of patent application is called for the 200680047764.X name in the Chinese invention patent application of " heat-expandable macrosphere and manufacture method thereof and purposes " and proposes, adopt the copolymerization scheme of methacrylonitrile and methacrylic acid, owing to form the polymer shell of Polymethacrylimide structure, its heat resisting temperature can be more than 220 ℃, but test finds that there is the problem of following two aspects in this scheme: the polymer shell after (1) foaming does not almost have elasticity or elasticity little; (2) it can not be miscible with alkaline matter (needing to add sodium bicarbonate in the processing of footwear material usually), if miscible, shrinks immediately after the foaming.
Summary of the invention
The objective of the invention is provides a kind of excellent heat resistance, expansion ratio height in order to overcome above-mentioned deficiency, shows the preparation method of the thermotolerance blowing microcapsule of stablizing the foaming behavior.
For solving the problems of the technologies described above, technical scheme provided by the invention is: a kind of preparation method of thermotolerance blowing microcapsule, wherein, be cyst wall with the vinyl cyanide monomer-polymer, be core with lower boiling alkane whipping agent, form through suspension polymerization, may further comprise the steps:
(1) generation of main dispersant, described main dispersant are silane coupler modified silicon sol, the generation method for take back stream, the stirring reactor in add silicon sol, constant temperature splash into organo-silicon coupling agent react main dispersant; (2) generation of suspension emulsion is dispersed into small droplets by aqueous mixture and oil phase mixed solution and gets suspension emulsion under high-shear homogenizer, wherein aqueous mixture is formed by dispersion agent, pH value conditioning agent, inorganic salt and deionized water mechanical stirring; The oil phase mixed solution comprises that by polymerisable monomer vinyl cyanide monomer, comonomer, linking agent, whipping agent and initiator mechanical stirring form;
(3) preparation of blowing microcapsule is transferred to suspension emulsion that constant temperature carries out suspension polymerization in the reactor that band stirs, and reaction finishes and naturally cools to room temperature, after filtration, clean, dry and screening obtains the blowing microcapsule product;
Wherein, in the described step (1):
Described modified silicasol consumption is 0.4～1% of the suspension emulsion gross weight described in step (2) and (3); Wherein, the silane coupling agent consumption is 2～10% of silicon sol solid consumption; Described silicon sol is acidity, neutrality or alkaline silica sol;
Wherein, in the described step (2):
Described dispersion agent also comprises dispersion aids except comprising the main dispersant described in the step (1), dispersion aids is polyvinylpyrrolidone, any in the polyvinyl alcohol; The dispersion aids consumption is 0.2～0.5% of suspension emulsion gross weight;
Described whipping agent is that the lower boiling carbonatoms is 4～8 alkane, comprise butane, Trimethylmethane, pentane, iso-pentane, neopentane, hexane, isohexane, heptane, isoheptane, octane, any or arbitrary combination constitute the core of blowing microcapsule in the octane-iso, and its consumption is 20～40% of polymerisable monomer weight;
Described vinyl cyanide monomer, comonomer and linking agent as polymerisable monomer in proportion polymerization constitute the shell of blowing microcapsule, by the polymerisable monomer weight percent: described vinyl cyanide monomer accounts for 80～94.5%, comonomer accounts for 5～18%, the linking agent monomer accounts for 0.5～2%, described vinyl cyanide monomer is the mixture of vinyl cyanide and methacrylonitrile, and both quality proportionings are 1.5～4:1;
Described comonomer comprises that the unsaturated vinyl monomer of wetting ability and polymkeric substance have the unsaturated vinyl monomer of high glass-transition temperature, the wetting ability unsaturated monomer is hydroxyethyl methylacrylate or Rocryl 410, its consumption is 5～20% of comonomer weight, the unsaturated vinyl monomer that polymkeric substance has a high glass-transition temperature is any in isobornyl methacrylate, acrylamide, Methacrylamide, the dicyclopentadiene acrylate, and its consumption is 80～95% of comonomer weight;
Described linking agent is binary, the ternary acrylic ester monomer with soft segment, specifically is in diethyl (third) glycol two-(methyl) acrylate, three second (third) glycol, two-(methyl) acrylate, polyethyleneglycol diacrylate, second (third) oxidation trimethylolpropane tris-(methyl) acrylate any;
Described pH regulator agent is acidic substance.
Further, in the described step (1), silane coupling agent is the silicoorganic compound that contain the polymerizable reactive group, comprise and have vinyl, propenyl, methylpropenyl, allylic silicoorganic compound, particularly, be trimethylammonium propenyloxy group propyl trimethoxy silicane, trimethylammonium propenyloxy group propyl group methyl dimethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, the vinyl methyl dimethoxysilane, the methacryloxy Trimethoxy silane, 3-propylene oxide base propylene Trimethoxy silane, a kind of in the 3-propylene oxide base acroloyl methyl dimethoxysilane.
Further, from modified silicasol stability and suspension polymerization dispersion effect, described silane coupling agent is preferably any in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl methyl dimethoxysilane, the methacryloxy Trimethoxy silane; Described silicon sol is preferably acidic silicasol.
Further, in the described step (2), from dispersion agent polymerisate dispersion stabilization and particle evenness suspension polymerization system, being preferably the modified silicasol add-on is 0.5～0.8% of suspension liquid gross weight, the coupling agent consumption is 3～8% of silicon sol consumption, and the dispersion aids add-on is 0.3～0.5% of suspension emulsion gross weight.
Further, consider that from whipping agent expansion ratio and heat-resistant stability in the described step (2), the quality proportioning of vinyl cyanide and methacrylonitrile is for being preferably as follows ratio: 2～4:1, both total consumptions are 83～93% of polymerisable monomer weight; Comonomer accounts for 6.2～15%, the linking agent monomer accounts for 0.8～2%, wherein, the consumption of wetting ability unsaturated monomer accounts for 10～20% of comonomer weight, and the consumption that polymkeric substance has the unsaturated vinyl monomer of high glass-transition temperature accounts for 80～90% of comonomer weight.
Further, consider from expansion ratio and initial blowing temperature that preferred whipping agent is iso-pentane, pentane, isohexane, hexane, any or arbitrary combination in octane-iso, the octane.
Further, consider that from capsule expansion ratio and thermotolerance the consumption of preferred described whipping agent is 25～35% of polymerisable monomer weight.
Further, in the described step (2), described initiator is preferably oil-soluble initiator, comprise azo class or peroxide initiator, such initiator and polymerisable monomer can form the homogeneous phase oily liquid, and are beneficial to it and carry out suspension polymerization, particularly, described initiator is any in Diisopropyl azodicarboxylate, azo two eyeball in different heptan, the own ester of peroxy dicarbonate two (2-ethyl), peroxy dicarbonate two (the 4-tertiary butyl) cyclohexyl, and its consumption is 0.2～1% of polymerisable monomer weight.
Further, preferred described initiator amount is 0.5～1% of polymerisable monomer weight, and under this initiator amount, capsule has high expansion ratio and productive rate.
Further, in the described step (2), described pH regulator agent is dilute hydrochloric acid or dilute sulphuric acid, and the pH value scope of suspension emulsion is 1～5.
Description of drawings
Fig. 1 is the diagram of blowing microcapsule of the present invention expansion ratio under differing temps.
Embodiment
By describing technology contents of the present invention in detail, realized purpose and effect, give explanation below in conjunction with preferred embodiments and conjunction with figs. are detailed.
The artificial the object of the invention that realizes of application is furtherd investigate, and finds to have the resistance toheat of following factor restriction microcapsule: particle diameter form and the distribution of (1) microcapsule, if microcapsule are spheroidal particle of uniform size, its thermotolerance strengthens; (2) adopt silicon-dioxide as the dispersion agent of polymerization system, add-on is more, system is uniformly dispersed, during the capsule heat foamable that forms, the particle adhesion is few, still, its expansion ratio reduces, the silicon-dioxide inorganics of fragility easily forms crackle in polymer shell simultaneously, and its thermotolerance is relatively poor; (3) add silane coupling agent, owing to deposit at the polymer shell layer, can reduce the usage quantity of silicon-dioxide, but, in the reactor of band pressure, because add-on is less, stir speed (S.S.) is low at the certain coupling agent that constantly just adds of polymerization for this arts demand on the one hand, in the suspended emulsion system, disperse to be difficult to guarantee evenly, easily produce the gel block.
For this reason, the applicant attempts following technical thought: (1) at first will have silane coupling agent and the polymerization of dispersion agent silicon sol of the two keys of C=C, form stable coupling agent modified silicon sol; Then it being joined the water high speed homogenization disperses, because modifying process easy (being stirred to certain moment as long as under constant temperature, add coupling agent), coupling agent be uniformly dispersed (high speed dispersion), unsaturated group can participate in reaction in suspension polymerization simultaneously, therefore, product quality control is stable, thereby improves its resistance toheat; (2) add a small amount of hydrophilic polymerized monomer such as hydroxyethyl methylacrylate etc., make that the polymkeric substance that forms is difficult to gather and be macrobead, even the microcapsule particle diameter is even; (3) add acrylic ester monomer that small amount of polymer is high glass transition temperature such as isobornyl methacrylate etc., the adding of this monomer strengthens its thermotolerance.
According to above technical thought, the preparation method who the invention provides a kind of thermotolerance blowing microcapsule is cyst wall with the vinyl cyanide monomer-polymer, is core with lower boiling alkane whipping agent, forms through suspension polymerization, may further comprise the steps:
(1) generation of main dispersant, described main dispersant are silane coupler modified silicon sol, the generation method for take back stream, the stirring reactor in add silicon sol, constant temperature splash into organo-silicon coupling agent react main dispersant;
(2) generation of suspension emulsion is dispersed into small droplets by aqueous mixture and oil phase mixed solution and gets suspension emulsion under high-shear homogenizer, wherein aqueous mixture by dispersion agent, pH value conditioning agent, inorganic salt and deionized water by a certain percentage mechanical stirring form; The oil phase mixed solution by polymerisable monomer comprise vinyl cyanide monomer, comonomer, linking agent, whipping agent and initiator by a certain percentage mechanical stirring form;
In the step (2), described dispersion agent also comprises dispersion aids except comprising the main dispersant described in the step (1), and dispersion aids is polyvinylpyrrolidone, any in the polyvinyl alcohol; The dispersion aids consumption be in the polymerization system suspension emulsion gross weight 0.2～0.5%;
Described modified silicasol consumption be in the polymerization system suspension emulsion gross weight 0.4～1%; Wherein, the silane coupling agent consumption is 2～10% of silicon sol solid consumption; Described silicon sol is acidity, neutrality or alkaline silica sol;
Described whipping agent is that the lower boiling carbonatoms is 4～8 alkane, comprises butane, Trimethylmethane, and pentane, iso-pentane, neopentane, hexane, isohexane, heptane, isoheptane, octane, any or arbitrary combination constitute the core of blowing microcapsule in the octane-iso;
Described vinyl cyanide monomer, comonomer and linking agent as polymerisable monomer in proportion polymerization constitute the shell of blowing microcapsule, by the polymerisable monomer weight percent:
Described vinyl cyanide monomer accounts for 80～94.5%, and comonomer accounts for 5～18%, and the linking agent monomer accounts for 0.5～2%, and described vinyl cyanide monomer is the mixture of vinyl cyanide and methacrylonitrile, and both quality proportionings are 1.5～4:1; Described comonomer comprises that the unsaturated vinyl monomer of wetting ability and polymkeric substance have the unsaturated vinyl monomer of high glass-transition temperature, the wetting ability unsaturated monomer is hydroxyethyl methylacrylate or Rocryl 410, its consumption is 5～20% of comonomer weight, the unsaturated vinyl monomer that polymkeric substance has a high glass-transition temperature is any in isobornyl methacrylate, acrylamide, Methacrylamide, the dicyclopentadiene acrylate, and its consumption is 80～95% of comonomer weight;
Described linking agent is binary, the ternary acrylic ester monomer with soft segment, specifically is in diethyl (third) glycol two-(methyl) acrylate, three second (third) glycol, two-(methyl) acrylate, polyethyleneglycol diacrylate, second (third) oxidation trimethylolpropane tris-(methyl) acrylate any.
(3) preparation of blowing microcapsule is transferred to suspension emulsion that constant temperature carries out suspension polymerization in the reactor that band stirs, and reaction finishes and naturally cools to room temperature, after filtration, clean, dry and screening obtains the blowing microcapsule product.
In the step (2), dispersion aids is high molecular weight water soluble polymer; Linking agent is the binary with soft segment, the ternary acrylic ester monomer, it specifically is diethyl (third) glycol two (methyl) acrylate, three second (third) glycol two (methyl) acrylate, polyethyleneglycol diacrylate, in second (third) oxidation trimethylolpropane tris (methyl) acrylate any, specifically such as being diethylene glycol diacrylate, Diethylene Glycol two-methacrylic ester, propylene glycol diacrylate, dipropylene glycol two-methacrylic ester, triethylene glycol diacrylate, triethylene glycol two-methacrylic ester, tripropylene glycol two-methacrylic ester, tripropylene glycol diacrylate, polyethyleneglycol diacrylate, polyoxyethylene glycol two-methacrylic ester, the ethoxyquin Viscoat 295, the third oxidation Viscoat 295, the ethoxyquin trimethylolpropane trimethacrylate, in the third oxidation trimethylolpropane trimethacrylate any, its consumption are 0.5～2% of polymerisable monomer weight;
In the step (2), whipping agent is that the lower boiling carbonatoms is 4～8 alkane, constitutes the core of blowing microcapsule, and whipping agent can be iso-pentane, pentane, isohexane, hexane, any or arbitrary combination in octane-iso, the octane, its consumption is 20～40% of alkene class polymerisable monomer weight;
In the step (2), initiator is oil-soluble initiator, comprise azo class or peroxide initiator, particularly, initiator is any in Diisopropyl azodicarboxylate, azo two eyeball in different heptan, the own ester of peroxy dicarbonate two (2-ethyl), peroxy dicarbonate two (the 4-tertiary butyl) cyclohexyl, its consumption is 0.2～1% of alkene class polymerisable monomer weight, particularly, such as being in peroxy dicarbonate dihexyl, peroxy dicarbonate two-2-ethylhexyl, di-cyclohexylperoxy dicarbonate, the peroxy dicarbonate two-4-tertiary butyl cyclohexyl any; The pH regulator agent is acidic substance, particularly, is dilute hydrochloric acid or dilute sulphuric acid, and the pH value scope of suspension emulsion is 1～5.
Among the above-mentioned preparation method, preferred scheme reaches preferably be the reasons are as follows:
In the step (1), main dispersant is silane coupler modified silicon sol dispersion, and add-on is few, disperses inhomogeneously, and add-on is many, polymkeric substance thermotolerance variation, and the preferred silicon sol amount (amount of solid) that adds is 0.5～0.8% of suspension liquid gross weight.Silane coupling agent is the silane that contains the two keys of C=C, as vinyltrimethoxy silane (A-171), vinyltriethoxysilane (A-151), vinyl methyl dimethoxysilane (A-2171), methacryloxy Trimethoxy silane (A-174), its preferable amount are 3～8% of silicon sol (solid) consumption; Consider the stability of emulsion (easily lump, condense under alkaline condition) behind the coupling agent modified silicon sol, the silicon sol that uses is acidic silicasol.
In the step (2), microcapsule shell is polymerized in proportion by vinyl cyanide monomer, comonomer and linking agent.Select for use the vinyl cyanide monomer to be because they have higher anti-solvent, high obstructing performance, test is found, select vinyl cyanide, methacrylonitrile polymerization of mixtures for use, its foam performance is better, and the methacrylonitrile activity is greater than vinyl cyanide but methacrylonitrile price height, and therefore, the consumption of vinyl cyanide should be greater than methacrylonitrile in the monomer ratio, both quality proportionings are 1.5～4:1, preferred 2～4:1; The preferred total consumption of vinyl cyanide monomer is 83～93% of polymerisable monomer weight; Comonomer comprises that the unsaturated vinyl monomer of wetting ability and its polymkeric substance have the unsaturated vinyl monomer of high glass-transition temperature, add the dispersion stabilization that hydrophilic monomer strengthens polymerisate, adding polymkeric substance is the vinyl monomer of high glass transition temperature, reduce the crystal property of product, improve the product thermotolerance.Wetting ability unsaturated monomer consumption is few, weak effect, and consumption is many, and product viscosity is big, and it is too many that filtration difficulty, polymkeric substance have the unsaturated vinyl monomer consumption of high glass-transition temperature, and its product fragility increases; The preferred hydrophilic amount of monomer accounts for the 10-20% of amount of comonomers, and the high glass transition temperature monomer scale of construction accounts for the 80-90% of amount of comonomers; The comonomer total amount increases, and the product solvent resistance descends, and the total consumption of preferred comonomers is 6.2～15% of polymerisable monomer weight.Add linking agent and improve product resistance toheat and solvent resistance, dosage of crosslinking agent is few, and the whipping agent solvent resistance is poor, and the capsule parcel is imperfect, and encapsulation ratio is low, and productive rate is low, and consumption is big, the productive rate height, but expansion ratio reduces.Dosage of crosslinking agent is few; The dosage of crosslinking agent height, the whipping agent expansion ratio is low; Preferable amount is 0.8～2% of polymerisable monomer weight;
In the step (2), the microcapsule core by the lower boiling carbonatoms be 4～8 alkane separately or mix and forms, the test discovery, carbonatoms is little, initial blowing temperature is low, carbonatoms is big, initial blowing temperature height; If adopt different carbon atom alkane to mix, owing to can reduce initial blow(ing) pressure, slowly expand in constantly heating up, its foam performance is better, and the core consumption is few, expansion ratio is low, consumption is many, the expansion ratio height, but because its capsule wall is thin, thermotolerance reduces, and its preferable amount is 25～35% of alkene class polymerisable monomer weight;
In step (2) or (3), initiator is oil-soluble initiator, and the polymerization temperature of suspension polymerization is relevant with the initiator of its use, served as to investigate object with 10 hours transformation period, test finds, adopts Diisopropyl azodicarboxylate (65 ℃ of polymerization temperatures), azo two different eyeballs in heptan (53 ℃ of polymerization temperatures) comparatively suitable, and initiator amount is few, productive rate is low, consumption is big, chain takes place shift greatly, and bridging property strengthens, its expansion ratio is lower, and its preferable amount is 0.5～1% of polymerisable monomer weight; Consider stability of emulsion (under alkaline condition, easily lump, condense) behind the coupling agent modified silicon sol, suspension polymerization should be carried out under acidic conditions, adding acidic substance such as dilute hydrochloric acid, dilute sulphuric acid wait to regulate pH value of water solution, and the pH value is low, and speed of reaction is fast, the productive rate height, the product particle diameter is little, and the pH value is high, and speed of reaction is slow, productive rate is low, and preferred pH value scope is 2～4; Because vinyl cyanide water solubility of monomer height is easy to be unfavorable for that at water homogeneous nucleation (formation solid sphere) whipping agent is encapsulated, add sodium-chlor etc., can reduce the water-soluble of monomer, be beneficial to and form the whipping agent microcapsule.
The present invention has a lot of successful implementation examples, for thermotolerance, granular size and distribution that thermotolerance blowing microcapsule of the present invention is described better and expansion ratio etc., enumerate comparative example and several embodiments of the present invention below, and be described in conjunction with Fig. 1 and a pair of its technical performance index of Biao.
Comparative example 1
Be the implementation method of ZL0180821.3 according to the patent No., its basic embodiment is as follows:
Water mixed solution: get in the plastic beaker that 600g distilled water joins 1000mL, under mechanical stirring, add 150g sodium-chlor, 30% silicon sol 16g, polyvinylpyrrolidone 2.4g etc. respectively, the back that stirs drips dilute sulphuric acid, and regulator solution pH value is 1.5 must water-based emulsion.
Oil phase mixed solution: under ventilation condition, 150g vinyl cyanide, 50g methacrylonitrile, the 20g methyl methacrylate that deepfreeze is good join in the plastic beaker of 300mL, drip diethylene glycol diacrylate 2.5g, add Diisopropyl azodicarboxylate 2g, pentane 30g then, isohexane 30g, stir oil phase liquid.
Water-based emulsion and oil phase mixed solution are dispersed into the small droplets suspended emulsion under high-shear homogenizer, change it over to band and stir the 1000ml reactor.65 ℃ of water bath with thermostatic control polyreaction 22h, reaction finishes, and naturally cools to room temperature, discharging, it is transferred to filtration in the pressure filter, washed with de-ionized water, filter residue cryodrying and under 200 purpose vibratory screening apparatuss, sieve Comparative Examples 1 product.
Embodiment 1
Silane coupler modified silicon sol: backflow is housed, stir in the 250mL flask, add 100g silicon sol (solid content 30%) and be warming up to 60 ℃, under agitation splash into 1.0g methacryloxy Trimethoxy silane A-174 organo-silicon coupling agent, insulated and stirred 6h, last thin up to effective solid content are that 30% aqueous solution is standby.
Water mixed solution: get in the plastic beaker that 600g distilled water joins 1000mL, under mechanical stirring, add 150g sodium-chlor, modified silicasol 16g, polyvinylpyrrolidone 2.4g etc. respectively, the back that stirs drips dilute sulphuric acid, and regulator solution pH value is 1.5 must water-based emulsion.
Oil phase mixed solution: under ventilation condition, with refrigerator and cooled good 150g vinyl cyanide, 50g methacrylonitrile, 20g isobornyl methacrylate join in the plastic beaker of 300mL, drip Rocryl 410 1.88g, diethylene glycol diacrylate 2.5g, add Diisopropyl azodicarboxylate 2g, pentane 30g, isohexane 30g then, stir oil phase liquid.
Water-based emulsion and oil phase mixed solution are dispersed into the small droplets suspension emulsion under high-shear homogenizer, change it over to band and stir the 1000ml reactor.65 ℃ of water bath with thermostatic control polyreaction 22h, reaction finishes, and naturally cools to room temperature, discharging, it is transferred to filtration in the pressure filter, washed with de-ionized water, filter residue cryodrying and under 200 purpose vibratory screening apparatuss, sieve the embodiment product.
Embodiment 2
With different among the embodiment 1 be:
Silane coupler modified silicon sol: organo-silicon coupling agent is vinyltrimethoxy silane (A-171), and the amount of splashing into is 1.4g.
The water mixed solution: modified silicasol 24g, polyvinylpyrrolidone 4g, regulator solution pH value be 2 water-based emulsion.
The oil phase mixed solution: each material consumption is as follows, 130g vinyl cyanide, 70g methacrylonitrile, 18g isobornyl methacrylate, drip Rocryl 410 2g, propylene glycol diacrylate 3.0g, add Diisopropyl azodicarboxylate 2.2g, pentane 25g, isohexane 35g then.
Embodiment 3
With different among the embodiment 1 be:
Silane coupler modified silicon sol: organo-silicon coupling agent is vinyltriethoxysilane (A-151), the amount of splashing into 1.5g.
The water mixed solution: modified silicasol 28g, polyvinylpyrrolidone 2.8g, regulator solution pH value be 3 water-based emulsion.
The oil phase mixed solution: each material consumption is as follows, 120g vinyl cyanide, 80g methacrylonitrile, 12g Methacrylamide, drip Rocryl 410 3.0g, Diethylene Glycol dimethacrylate 3.5g, add 2,2'-Azobis(2,4-dimethylvaleronitrile) 1.8g, pentane 25g, octane-iso 35g then.
In the suspension polymerization of polymerization system, be warming up to 53 ℃ of reaction 22h.
Embodiment 4
With different among the embodiment 1 be:
Silane coupler modified silicon sol: organo-silicon coupling agent is A-174, the amount of splashing into 2.2g.
The water mixed solution: modified silicasol 34g, polyvinylpyrrolidone 5g etc., regulator solution pH value be 1 water-based emulsion.
The oil phase mixed solution: each material consumption is as follows, 125g vinyl cyanide, 75g methacrylonitrile, 30g isobornyl methacrylate, drip hydroxyethyl methylacrylate 1.88, triethylene glycol diacrylate 4.5g, add Diisopropyl azodicarboxylate 1.2g, pentane 15g, hexane 45g then.
Embodiment 5
With different among the embodiment 1 be:
Silane coupler modified silicon sol: organo-silicon coupling agent is vinyl methyl dimethoxysilane (A-1271), and the amount of splashing into is 2.3g.
The water mixed solution: modified silicasol 14g, polyvinyl alcohol 2.5g etc., regulator solution pH value be 4 water-based emulsion.
The oil phase mixed solution: each material consumption is as follows, 130g vinyl cyanide, 70g methacrylonitrile, 40g acrylamide, drip hydroxyethyl methylacrylate 2.88g, triethylene glycol dimethacrylate 3.0g, add 2,2'-Azobis(2,4-dimethylvaleronitrile) 1.0g, pentane 25g, octane 25g then.
In the suspension polymerization of polymerization system, heat temperature raising to 53 ℃ reaction 22h.
Embodiment 6
With different among the embodiment 1 be:
Silane coupler modified silicon sol: organo-silicon coupling agent is A-151, the amount of splashing into 2.5g.
The water mixed solution: modified silicasol 15g, polyvinyl alcohol 2.2g etc., regulator solution pH value be 5 water-based emulsion.
The oil phase mixed solution: each material consumption is as follows, 160g vinyl cyanide, 40g methacrylonitrile, 20g dicyclopentadiene acrylate, drip Rocryl 410 3.2g, diethylene glycol diacrylate 2.0g adds Diisopropyl azodicarboxylate 0.8g, pentane 40g, isohexane 40g then.
Embodiment 7
With different among the embodiment 1 be:
Silane coupler modified silicon sol: organo-silicon coupling agent is A-151, the amount of splashing into 3.0g.
The water mixed solution: modified silicasol 22g, polyvinyl alcohol 3g etc., regulator solution pH value be 1.5 water-based emulsion.
The oil phase mixed solution: each material consumption is as follows, 155g vinyl cyanide, 45g methacrylonitrile, 30g isobornyl methacrylate, drip hydroxyethyl methylacrylate 2.0g, diethylene glycol diacrylate 1.6g adds Diisopropyl azodicarboxylate 0.6g, pentane 30g, isohexane 60g then.
Embodiment 8
With different among the embodiment 1 be:
Silane coupler modified silicon sol: organo-silicon coupling agent is A-151, the amount of splashing into 0.6g.
The water mixed solution: modified silicasol 28g, polyvinyl alcohol 4.5g etc., regulator solution pH value be 3 water-based emulsion.
The oil phase mixed solution: each material consumption is as follows, 130g vinyl cyanide, 70g methacrylonitrile, 40g methacrylic acid acid amides, drip Rocryl 410 3.88g, 3 third ethylene glycol dimethacrylate 1.4g, add Diisopropyl azodicarboxylate 0.8g, pentane 30g, octane-iso 40g then.
Next, by introducing definition and the experiment condition of the test of expansion ratio and particle diameter earlier, describe the comparison result of comparative example and embodiment again in detail.
Expansion ratio
Get blowing microcapsule 2g and put into baking oven, since 130 ℃, do once experiment every 5 ℃, each sample thermostatically heating 2min pours the sample after the foaming in the graduated cylinder into, measures its volume, with the ratio of foamable microcapsule volume not, be the expansion ratio of blowing microcapsule under this temperature; Its temperature that sharply expands is decided to be initial blowing temperature, and the temperature that its back of expanding is obviously shunk is called heat resisting temperature; Temperature was defined as maximum expansion ratio temperature when its expansion ratio is the highest.
The particle diameter test
Get blowing microcapsule 0.05g, be placed on the slide glass, drip glycerol liquids face thereon, be coated with flatly gently, its particle image analyser in America and Europe gram instrument company is analyzed.Usually pass through cumulative calculation, particle (the containing the weight meter) content that begins to calculate these particle size values from maximum particle diameter is respectively 10%, the size value of 50%, 90% o'clock correspondence corresponds respectively to D10, D50, the data of D90 are wherein represented its median size size with D50, by comparing D10, the D90 data roughly can be analyzed its size distribution.
See also Fig. 1 then, as seen from Figure 1, (embodiment 1 to adopt the present invention program, embodiment 2, embodiment 3), use through the coupling agent modified modified silicasol that obtains of acidic silicasol as suspension polymerization dispersant, by adding water-soluble vinyl monomer and the higher acrylic ester monomer of polymer glass temperature, the blowing microcapsule product that obtains, compare its expansion ratio with comparative example 1, initial blowing temperature and maximum blowing temperature are close, but its heat resisting temperature the former apparently higher than the latter (nearly 20 ℃), therefore, can be applied in the occasion that to use blowing microcapsule than high processing temperature.
The hot physical property measurement result (seeing Table one) of 8 embodiment and comparative example 1 gained blowing microcapsule product shows, with comparative example 1 relatively, embodiment 1-8 resistance toheat is all higher, and embodies identical Changing Pattern.From size, their particle diameter close (15～20 μ m) is subjected to the influence of suspension polymerization acidity, and the pH value is lower, and particle diameter is smaller; The pH value is higher, and particle diameter is bigger, the difference to some extent but it distributes, and comparative example 1 distributes wideer, embodiment 1-8 narrow distribution (seeing D10 and, D90 data and D50 difference mutually).
Table one
In sum, adopt the blowing microcapsule of the present invention's preparation, its thermotolerance strengthens, and size distribution is narrower.
In the technique scheme, described acidic substance are not limited to dilute hydrochloric acid, dilute sulphuric acid, can regulate the material of pH value for other; It can be other inorganic salt such as sodium sulfate that described inorganic salt also are not limited to sodium-chlor, sodium phosphate etc.; Rare gas element is not limited to N
2, can also be other rare gas element, mainly provide inert environments.
The above only is embodiments of the invention; be not so limit claim of the present invention; every equivalent structure or equivalent flow process conversion that utilizes specification sheets of the present invention and accompanying drawing content to do; or directly or indirectly be used in other relevant technical fields, all in like manner be included in the scope of patent protection of the present invention.
Claims (10)
1. the preparation method of a thermotolerance blowing microcapsule is characterized in that: being cyst wall with the vinyl cyanide monomer-polymer, is core with lower boiling alkane whipping agent, forms through suspension polymerization, may further comprise the steps:
(1) generation of main dispersant, described main dispersant are silane coupler modified silicon sol, the generation method for take back stream, the stirring reactor in add silicon sol, constant temperature splash into organo-silicon coupling agent react main dispersant;
(2) generation of suspension emulsion is dispersed into small droplets by aqueous mixture and oil phase mixed solution and gets suspension emulsion under high-shear homogenizer, wherein aqueous mixture is formed by dispersion agent, pH value conditioning agent, inorganic salt and deionized water mechanical stirring; The oil phase mixed solution comprises that by polymerisable monomer vinyl cyanide monomer, comonomer, linking agent, whipping agent and initiator mechanical stirring form;
(3) preparation of blowing microcapsule is transferred to suspension emulsion that constant temperature carries out suspension polymerization in the reactor that band stirs, and reaction finishes and naturally cools to room temperature, after filtration, clean, dry and screening obtains the blowing microcapsule product;
Wherein, in the described step (1):
Described modified silicasol consumption is 0.4～1% of the suspension emulsion gross weight described in step (2) and (3); Wherein, the silane coupling agent consumption is 2～10% of silicon sol solid consumption, and described silicon sol is acidity, neutrality or alkaline silica sol;
Wherein, in the described step (2):
Described dispersion agent also comprises dispersion aids except comprising the main dispersant described in the step (1), dispersion aids is polyvinylpyrrolidone, and any in the polyvinyl alcohol, dispersion aids consumption are 0.2～0.5% of suspension emulsion gross weight;
Described whipping agent is that the lower boiling carbonatoms is 4～8 alkane, comprise butane, Trimethylmethane, pentane, iso-pentane, neopentane, hexane, isohexane, heptane, isoheptane, octane, any or arbitrary combination in the octane-iso constitute the core of blowing microcapsule, and its consumption is 20～40% of polymerisable monomer weight;
Described vinyl cyanide monomer, comonomer and linking agent as polymerisable monomer in proportion polymerization constitute the shell of blowing microcapsule, by the polymerisable monomer weight percent: the vinyl cyanide monomer accounts for 80～94.5%, comonomer accounts for 5～18%, the linking agent monomer accounts for 0.5～2%, described vinyl cyanide monomer is the mixture of vinyl cyanide and methacrylonitrile, and both quality proportionings are 1.5～4:1;
Described comonomer comprises that the unsaturated vinyl monomer of wetting ability and polymkeric substance have the unsaturated vinyl monomer of high glass-transition temperature, the wetting ability unsaturated monomer is hydroxyethyl methylacrylate or Rocryl 410, its consumption is 5～20% of comonomer weight, the unsaturated vinyl monomer that polymkeric substance has a high glass-transition temperature is any in isobornyl methacrylate, acrylamide, Methacrylamide, the dicyclopentadiene acrylate, and its consumption is 80～95% of comonomer weight;
Described linking agent is binary, the ternary acrylic ester monomer with soft segment, specifically is in Diethylene Glycol two-(methyl) acrylate, dipropylene glycol two-(methyl) acrylate, triethylene glycol two-(methyl) acrylate, tripropylene glycol two-(methyl) acrylate, polyethyleneglycol diacrylate, ethoxyquin trimethylolpropane tris-(methyl) acrylate, the third oxidation trimethylolpropane tris-(methyl) acrylate any;
Described pH regulator agent is acidic substance.
2. preparation method according to claim 1, it is characterized in that: in the described step (1), silane coupling agent is the silicoorganic compound that contain the polymerizable reactive group, comprise and have vinyl, propenyl, methylpropenyl, allylic silicoorganic compound, particularly, be trimethylammonium propenyloxy group propyl trimethoxy silicane, trimethylammonium propenyloxy group propyl group methyl dimethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, the vinyl methyl dimethoxysilane, the methacryloxy Trimethoxy silane, 3-propylene oxide base propylene Trimethoxy silane, a kind of in the 3-propylene oxide base acroloyl methyl dimethoxysilane.
3. preparation method according to claim 2, it is characterized in that: from modified silicasol stability and suspension polymerization dispersion effect, described silane coupling agent is preferably any in vinyltrimethoxy silane, vinyltriethoxysilane, vinyl methyl dimethoxysilane, the methacryloxy Trimethoxy silane; Described silicon sol is preferably acidic silicasol.
4. preparation method according to claim 2, it is characterized in that: in the described step (2), from dispersion agent polymerisate dispersion stabilization and particle evenness suspension polymerization system, being preferably the modified silicasol add-on is 0.5～0.8% of suspension emulsion gross weight, the coupling agent consumption is 3～8% of silicon sol consumption, and the dispersion aids add-on is 0.3～0.5% of suspension liquid gross weight.
5. preparation method according to claim 2, it is characterized in that: consider from whipping agent expansion ratio and heat-resistant stability, in the described step (2), the quality proportioning of vinyl cyanide and methacrylonitrile is for being preferably as follows ratio: 2～4:1, and both total consumptions are 83～93% of polymerisable monomer weight; Comonomer accounts for 6.2～15%, the linking agent monomer accounts for 0.8～2%, wherein, the consumption of wetting ability unsaturated monomer accounts for 10～20% of comonomer weight, and the consumption that polymkeric substance has the unsaturated vinyl monomer of high glass-transition temperature accounts for 80～90% of comonomer weight.
6. preparation method according to claim 2, it is characterized in that: consider from expansion ratio and initial blowing temperature, in the described step (2), preferred whipping agent is iso-pentane, pentane, isohexane, hexane, any or arbitrary combination in octane-iso, the octane.
7. preparation method according to claim 6 is characterized in that: consider that from capsule expansion ratio and thermotolerance the consumption of preferred described whipping agent is 25～35% of polymerisable monomer weight.
8. preparation method according to claim 2, it is characterized in that: in the described step (2), described initiator is preferably oil-soluble initiator, comprise azo class or peroxide initiator, such initiator and polymerisable monomer can form the homogeneous phase oily liquid, and be beneficial to it and carry out suspension polymerization, particularly, described initiator is any in Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), the own ester of peroxy dicarbonate two (2-ethyl), peroxy dicarbonate two (the 4-tertiary butyl) cyclohexyl, and its consumption is 0.2～1% of polymerisable monomer weight.
9. preparation method according to claim 8, it is characterized in that: preferred described initiator amount is 0.5～1% of polymerisable monomer weight, under this initiator amount, capsule has high expansion ratio and productive rate.
10. preparation method according to claim 2, it is characterized in that: in the described step (2), the pH regulator agent is dilute hydrochloric acid or dilute sulphuric acid, the pH value scope of suspension emulsion is 1～5.
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| CN104744660B (en) * | 2013-12-31 | 2018-02-02 | 财团法人纺织产业综合研究所 | Aqueous polyurethane resin and its manufacture method and its in the application of synthetic leather |
| CN105924667B (en) * | 2016-05-11 | 2019-02-26 | 合肥工业大学 | A kind of environmental-friendly microcapsule foaming agent and preparation method thereof |
| JP6774547B2 (en) | 2016-07-14 | 2020-10-28 | ヌーリオン ケミカルズ インターナショナル ベスローテン フェノーツハップＮｏｕｒｙｏｎ Ｃｈｅｍｉｃａｌｓ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｂ．Ｖ． | Thermally expandable thermoplastic microspheres and how to prepare them |
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| US11332595B2 (en) * | 2017-09-04 | 2022-05-17 | Nouryon Chemicals International B.V. | Thermally expandable microspheres prepared from bio-based monomers |
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| CN112625295A (en) * | 2020-12-16 | 2021-04-09 | 南京工业大学 | Polymer foaming microsphere and preparation method and application thereof |
| CN115197519B (en) * | 2022-07-27 | 2024-06-25 | 万华化学集团股份有限公司 | Preparation method of thermally expandable microspheres containing hydrophilic organic modified colloidal silica |
| CN116375498B (en) * | 2023-03-16 | 2024-06-25 | 中建商品混凝土有限公司 | Foam concrete and preparation method thereof |
| CN117144561B (en) * | 2023-09-20 | 2024-03-26 | 武汉中科先进材料科技有限公司 | Fibrous membrane loaded with microcapsules with different foaming rates, preparation method thereof and light thermal fabric |
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