CN1693317A - Process for preparing microcapsule by initiating active fine emulsion polymerization of water-soluble initiating agent - Google Patents
Process for preparing microcapsule by initiating active fine emulsion polymerization of water-soluble initiating agent Download PDFInfo
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- CN1693317A CN1693317A CN 200510049797 CN200510049797A CN1693317A CN 1693317 A CN1693317 A CN 1693317A CN 200510049797 CN200510049797 CN 200510049797 CN 200510049797 A CN200510049797 A CN 200510049797A CN 1693317 A CN1693317 A CN 1693317A
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- water
- dimethacrylate
- initiating
- methyl
- soluble
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 20
- 230000000977 initiatory effect Effects 0.000 title claims description 32
- 239000003795 chemical substances by application Substances 0.000 title claims description 19
- 238000007720 emulsion polymerization reaction Methods 0.000 title claims description 18
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 239000000243 solution Substances 0.000 claims abstract description 43
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 24
- -1 phenmethyl Chemical group 0.000 claims description 23
- 239000012782 phase change material Substances 0.000 claims description 18
- 238000007599 discharging Methods 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000012986 chain transfer agent Substances 0.000 claims description 8
- 239000004159 Potassium persulphate Substances 0.000 claims description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 7
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 7
- 239000003995 emulsifying agent Substances 0.000 claims description 7
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 7
- 235000019394 potassium persulphate Nutrition 0.000 claims description 7
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 claims description 6
- 239000007858 starting material Substances 0.000 claims description 6
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000004160 Ammonium persulphate Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 claims description 3
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims 4
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims 4
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 claims 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims 3
- 229940059574 pentaerithrityl Drugs 0.000 claims 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 3
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 claims 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims 3
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims 2
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims 2
- 101150065749 Churc1 gene Proteins 0.000 claims 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 2
- 102100038239 Protein Churchill Human genes 0.000 claims 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 2
- 101100054666 Streptomyces halstedii sch3 gene Proteins 0.000 claims 2
- 230000002378 acidificating effect Effects 0.000 claims 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 2
- 230000005669 field effect Effects 0.000 claims 2
- 230000005484 gravity Effects 0.000 claims 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims 2
- 239000011159 matrix material Substances 0.000 claims 2
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims 2
- 229920000136 polysorbate Polymers 0.000 claims 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 2
- 238000010008 shearing Methods 0.000 claims 2
- 239000002689 soil Substances 0.000 claims 2
- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 claims 1
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 230000000379 polymerizing effect Effects 0.000 abstract description 4
- 239000000839 emulsion Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 230000001804 emulsifying effect Effects 0.000 abstract 1
- 230000001960 triggered effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 239000012071 phase Substances 0.000 description 21
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 239000008346 aqueous phase Substances 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- 238000006392 deoxygenation reaction Methods 0.000 description 8
- 238000010907 mechanical stirring Methods 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000001993 wax Substances 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- 208000030208 low-grade fever Diseases 0.000 description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 150000007970 thio esters Chemical class 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 4
- 239000002088 nanocapsule Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000010550 living polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 206010011732 Cyst Diseases 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical class CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 208000031513 cyst Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
Abstract
A process for preparing microcapsule by fine emulsion polymerizing include such steps as mixing phase-transition material with one or more vinyl or polyvinyl monomers, adding amphiphilic chain transfer to become oil solution, dispersing it in alkaline aqueous solution, pre-emulsifying, stearing to become fnie emulsion, adding water-soluble trigger, and triggered polymerizing.
Description
Technical field
The present invention relates to letex polymerization, relate in particular to a kind of method of preparing microcapsule by initiating active fine emulsion polymerization of water-soluble initiating agent.
Background technology
Phase change material is a kind of material that the transformation of solid, liquid, gas phase can take place, and it has huge latent heat of phase change, can absorb, store or discharge a large amount of heats under substantially invariable temperature (being phase transition temperature).Phase change material mainly is divided into solid-solid phase change, solid-liquid phase change, liquid-gas phase change, solid-the gas phase change energy-storage material according to phase deformation type, phase transition process; Can be divided into high, medium and low temperature phase change material according to the transformation temperature scope; Can be divided into inorganic, organic (polymer) phase change material again according to its composition.In recent years, the applied research of phase change material has expanded to aspects such as intelligent automatic air-conditioning and construction thing, wrapping material, pipe container, electrical and electronic component, insulation clothes, energy storage cooker.Organic paraffin class alkane has different fusing points and ctystallizing point, changes in the phase change material the not blending ratio of alkane of the same race, can obtain different transformation temperature scopes.And this phase-change wax nontoxicity, do not corrode, non-hygroscopic, it is stable that its thermal characteristics keeps in life-time service, and latent heat of phase change reaches 100～300J/g, and raw materials cost is very low, is a kind of phase change material that is most widely used now.Because solid-liquid phase transition material liquid state occurs in the phase transition process, in case phase change material leaks, phase change material just can't recycle so, and the while may cause problem of environmental pollution.Therefore, generally be to take the method for micro encapsulation that phase change material is wrapped up with the organic or inorganic thing.The method of existing micro encapsulation generally can obtain micron to millimetre-sized capsule, because particle is too big, it is stable that its dispersion system is difficult to keep, and therefore needs the composite again in use latex that is dispersed into, not only technology is loaded down with trivial details, energy consumption is very big, and cyst wall prescription modulability is very poor.Therefore, on using, Nano capsule has been widened Application Areas greatly than micron-sized product.Particularly in the capsular research of medicament nano, scientists finds that also it has good target and slow releasing function.
Reversible addition-chain rupture chain transfer activity polymerization (Reversible Addition-Fragmentationtrain Transfer Polymerization) is called for short the RAFT technology, is a kind of living radical polymerization technique that is considered to have most industrial prospect now.The used chain-transfer agent of this technology kind is called RAFT reagent.He can control the monomeric polymerization degree and sequential structure very effectively, and the realization polymer is cut out.By selecting certain monomers and oil-soluble substance, utilize the mini-emulsion polymerization method can prepare the nucleocapsid structure latex particle of size in 50～500 nanometers.If two kinds of technology combinations then not only can realize the breakthrough on the microcapsule size, and can pass through formulating of recipe, obtain accurately controlled product of wall thickness, size of particles.
Summary of the invention
The method that the purpose of this invention is to provide a kind of preparing microcapsule by initiating active fine emulsion polymerization of water-soluble initiating agent.
A kind of method steps of preparing microcapsule by initiating active fine emulsion polymerization of water-soluble initiating agent is as follows:
1) with the phase change materials of 10～50 parts of weight, 10～200 parts of one or more vinyl monomers or multi-vinyl monomer, 0.1 part～5 parts the chain-transfer agent of parental type, forms oil solution;
2) with 0.01～10 part alkaline matter, be dissolved in 50～400 parts of water, form the aqueous solution;
3) aqueous solution and oil solution is mixed, pulverize 2～30 minutes formation miniemulsions through high shear field;
4) miniemulsion is moved into reactor, be warming up to 50～160 ℃, add 0.05～10 part of water soluble starter, initiated polymerization, polymerization is after 2～18 hours, slowly cools to discharging after the room temperature.
The method steps of another kind of preparing microcapsule by initiating active fine emulsion polymerization of water-soluble initiating agent is as follows:
1) with the phase change materials of 10～50 parts of weight, 10～200 parts of one or more vinyl monomers or multi-vinyl monomer, 0.1 part～5 parts the chain-transfer agent of parental type, forms oil solution;
2) with 0.01～10 part emulsifying agent, 0.01～10 part alkaline matter is dissolved in 50～400 parts of water, forms the aqueous solution;
3) aqueous solution and oil solution is mixed, pulverize 2～30 minutes formation miniemulsions through high shear field;
4) miniemulsion is moved into reactor, be warming up to 50～160 ℃, add 0.05～10 part of water soluble starter, initiated polymerization;
5) reach 52～90% when polymerisation conversion, add 0.01～5 part of linking agent.After the polymerization 1～18 hour, slowly cool to discharging after the room temperature.
The present invention is a core substance with phase-change wax (18～25 alkane), utilizes the miniemulsion technology, in conjunction with reversible addition-chain rupture chain transfer (being called for short the RAFT technology) living radical technology, prepares accurately controlled Nano capsule particle of structure.One big innovation of this patent is synthetic and has used the RAFT reagent of a kind of parental type (having the hydrophilic and oleophilic segment), this RAFT reagent not only has fabulous control action kou to monomer polymerization, and, can reduce or remit the consumption of emulsifying agent because it is distributed in the outside surface of drop.So behind initiated polymerization, living polymerization is limited on the interface of miniemulsion particle and carries out, polymkeric substance increases from outside to inside; By this active free radical polymerization can controlling polymers molecular weight size or sequential structure, thereby can obtain that form is regular, wall thickness is even, the accurate controlled Nano capsule particle of structure.The advantage of mini-emulsion polymerization also has: (1) system stability is high, helps industrial enforcement; (2) particle diameter of product latex reaches 50～500 nanometers; (3) polymerization efficiency height is produced and is easy to control etc.; (4) be dispersion medium with water, heat-transfer effect is good, and is environmentally friendly.Innovative point of the present invention is not only with mini-emulsion polymerization and the advantages RAFT living polymerization, but also has quoted the thinking of interfacial polymerization, for the further industrialization of microcapsule, especially Nano capsule product has proposed a kind of novelty, high-efficiency method.If use technology such as vacuum extraction, particle can also be made the material that hollow capsules recharges required parcel, thus the special product innovation of development function.
Embodiment
Used RAFT reagent is a kind of pair of monothioester among the present invention, and its chemical structure of general formula is
According to the variation of Z group and R group combination multiple structure can be arranged, parents' oligopolymer RAFT reagent that can prepare different chain lengths by above RAFT reagent and certain monomer and initiator for reaction.(hereinafter to be referred as M-RAFT) R group of the oligomer chain transfer agent of parental type comprise the structural unit number be n be that oleophylic segment and structural unit number are that m is a hydrophilic segment.
Oligopolymer RAFT chemical structure skeleton symbol used in the embodiment of the invention mainly contains following 5 kinds:
Oligopolymer RAFT (1) is obtained by the two thioesters of styrene and maleic anhydride grafting styroyl-1-phenylethyl alcohol, and wherein the styrene and maleic anhydride unit has 5 pairs, and the vinylbenzene homopolymerization section polymerization degree is 2.
Oligopolymer RAFT (2) is obtained by styrene and maleic anhydride and the two thioesters of styrene homopolymers grafting styroyl-1-phenylethyl alcohol, and wherein the styrene and maleic anhydride polymerization degree is about 5, and the vinylbenzene homopolymerization section polymerization degree is 10.
Oligopolymer RAFT (3) is obtained by styrene and maleic anhydride and the two thioesters of styrene homopolymers grafting styroyl-1-phenylethyl alcohol, and wherein the styrene and maleic anhydride polymerization degree is 4, and the vinylbenzene homopolymerization section polymerization degree is 8.
Oligopolymer RAFT (4) is by the two thioesters of the phenyl formic acid-itrile group isopropylcarbinol of methacrylic acid/methacrylic acid lauryl alcohol ester copolymer and vinylformic acid lauryl alcohol ester ground homopolymer.Wherein, the polymerization degree of methacrylic acid homo section is 4, and dodecyl methyl polymerizing acrylic acid degree is 2.
Oligopolymer RAFT (5) is by the two thioesters of the phenyl formic acid-itrile group isopropylcarbinol of methacrylic acid/methacrylic acid lauryl alcohol ester copolymer and vinylformic acid lauryl alcohol ester ground homopolymer.Wherein, the polymerization degree of methacrylic acid homo section is 5, and dodecyl methyl polymerizing acrylic acid degree is 4.
The adding of M-RAFT reagent, realized carrying out controllable free-radical polymerisation at the miniemulsion particle surface, prepare the polymer molecule of specific modality structure, in order to strengthen the intensity of microcapsule shell, the present invention comprises that simultaneously a kind of cross-linking monomer that adds makes shell-crosslinked method.Because the singularity of M-RAFT, cross-linking monomer can add at the beginning in reaction, also can add in the reaction middle and later periods.
Embodiment 1:
1) 22 ℃ of phase change materials of 4 grams, 0.5 gram oligopolymer RAFT (1) and 16 gram vinylbenzene are mixed, under magnetic agitation, form oil-phase solution;
2) 0.5 gram ammonia soln (5% quality) is joined in the 75 gram water, form aqueous phase solution;
3) above-mentioned oil-phase solution and aqueous phase solution is mixed, 60 ℃ of lower magnetic forces stirred 30 minutes, gave birth to KS-600 ultrasonic grinding 15 minutes (70% output rating) with Ningbo section then;
4) miniemulsion is moved into the reactor that mechanical stirring condensation reflux unit and nitrogen inlet, charging opening are housed, logical nitrogen deoxygenation is after 30 minutes, add 68 ℃ of water-baths, the aqueous solution (0.16 gram the is dissolved in 5 gram water) initiated polymerization that adds Potassium Persulphate simultaneously, after polymerization is finished, slowly cool to discharging after the room temperature.
Embodiment 2:
1) the oligopolymer RAFT (2) with 26 ℃ of phase-change wax of 4 grams and 0.7 gram joins in 16 gram hydroxyethyl methylacrylates, the mixed liquid of 0.2 gram Ethylene glycol dimethacrylate, and is evenly mixed under the magnetic agitation, forms oil-phase solution;
2) 0.1 gram sodium lauryl sulphate and 0.5 gram ammonia soln are joined in the 75 gram water, low-grade fever stirs into uniform aqueous phase solution;
3) above-mentioned oil-phase solution and aqueous phase solution is mixed, 60 ℃ of lower magnetic forces stirred 30 minutes, gave birth to KS-600 ultrasonic grinding 15 minutes (70% output rating) with Ningbo section then;
4) miniemulsion is moved into the reactor that mechanical stirring condensation reflux unit and nitrogen inlet, charging opening are housed, logical nitrogen deoxygenation is after 30 minutes, add 68 ℃ of water-baths, the aqueous solution (0.16 gram the is dissolved in 5 gram water) initiated polymerization that adds Potassium Persulphate simultaneously, after polymerization is finished, slowly cool to discharging after the room temperature.
Embodiment 3:
1) the oligopolymer RAFT (3) with 26 ℃ of phase-change wax of 10 grams and 1.2 grams joins in the mixed monomer of 6 gram vinylbenzene and 4 gram methyl methacrylates, and is evenly mixed under the magnetic agitation, forms uniform oil solution;
2) 0.2 gram sodium lauryl sulphate and 0.8 gram ammonia soln (5%) are joined in the 75 gram water, low-grade fever stirs into uniform aqueous phase solution;
3) above-mentioned oil-phase solution and aqueous phase solution is mixed, 60 ℃ of lower magnetic forces stirred 30 minutes, gave birth to KS-600 ultrasonic grinding 15 minutes (70% output rating) with Ningbo section then;
4) miniemulsion is moved into the reactor that mechanical stirring condensation reflux unit and nitrogen inlet, charging opening are housed, logical nitrogen deoxygenation is after 30 minutes, add 68 ℃ of water-baths, the aqueous solution (0.18 gram the is dissolved in 5 gram water) initiated polymerization that adds ammonium persulphate simultaneously, after polymerization is finished, slowly cool to discharging after the room temperature.
Embodiment 4
1) 32 ℃ of phase change materials of 12 grams, 0.5 gram oligopolymer RAFT (4) and 10 gram vinylbenzene are mixed, magnetic agitation forms oil-phase solution;
2) 0.2 gram sodium hydroxide is joined in the 75 gram water, form aqueous phase solution;
3) above-mentioned oil-phase solution and aqueous phase solution is mixed, 60 ℃ of lower magnetic forces stirred 30 minutes, gave birth to KS-600 ultrasonic grinding 15 minutes (70% output rating) with Ningbo section then;
4) miniemulsion is moved into the reactor that mechanical stirring condensation reflux unit and nitrogen inlet, charging opening are housed, logical nitrogen deoxygenation is after 30 minutes, add 68 ℃ of water-baths, the aqueous solution (0.16 gram the is dissolved in 5 gram water) initiated polymerization that adds Potassium Persulphate simultaneously, after polymerization is finished, slowly cool to discharging after the room temperature.
Embodiment 5:
1) the oligopolymer RAFT (4) with 26 ℃ of phase-change wax of 10 grams and 0.8 gram joins in the miscellany of 6 gram dodecylacrylate, 4 gram methyl methacrylates, 0.6 gram Vinylstyrene, and is evenly mixed under the magnetic agitation, forms oil solution;
2) with 0.2 gram Sodium dodecylbenzene sulfonate, 0.4 gram assistant for emulsifying agent OP-10,1 gram yellow soda ash joins in the 75 gram water, and low-grade fever stirs into aqueous phase solution;
3) above-mentioned oil-phase solution and aqueous phase solution is mixed, 60 ℃ of lower magnetic forces stirred 30 minutes, gave birth to KS-600 ultrasonic grinding 15 minutes (70% output rating) with Ningbo section then;
4) miniemulsion is moved into the reactor that mechanical stirring condensation reflux unit and nitrogen inlet, charging opening are housed, logical nitrogen deoxygenation added 68 ℃ of water-baths after 30 minutes, added the aqueous solution (0.12 gram is dissolved in 5 and the restrains water) initiated polymerization of ammonium persulphate simultaneously;
5) being polymerized to transformation efficiency is 90% o'clock, adds 0.1 gram monomer Ethylene glycol dimethacrylate altogether, behind the polyase 13 hour, slowly cools to discharging after the room temperature.
Embodiment 6:
1) the oligopolymer RAFT (2) with 32 ℃ of phase-change wax of 12 grams and 0.7 gram joins in the 10 gram methyl methacrylates, and is evenly mixed under the magnetic agitation, forms oil solution;
2) 0.1 gram sodium lauryl sulphate and 0.8 gram ammoniacal liquor (5%) solution are joined in the 75 gram water, low-grade fever stirs into aqueous phase solution;
3) above-mentioned oil-phase solution and aqueous phase solution is mixed, 60 ℃ of lower magnetic forces stirred 30 minutes, gave birth to KS-600 ultrasonic grinding 15 minutes (70% output rating) with Ningbo section then;
4) miniemulsion is moved into the reactor that mechanical stirring condensation reflux unit and nitrogen inlet, charging opening are housed, logical nitrogen deoxygenation added 68 ℃ of water-baths after 30 minutes, added the aqueous solution (0.16 gram is dissolved in 5 and the restrains water) initiated polymerization of Potassium Persulphate simultaneously;
5) being polymerized to transformation efficiency is 85% o'clock, adds 0.1 gram monomer hexanodioic acid dimethacrylate altogether, behind the polyase 13 hour, slowly cools to discharging after the room temperature.
Embodiment 7:
1) 36 ℃ of phase-change wax of 10 grams and 0.8 gram oligopolymer RAFT (5), 0.6 gram methacrylic acid glycol ester are joined in the miscellany of 5 gram t-butyl styrene, 5 gram Vinyl toluenes, evenly mixed under the magnetic agitation, form oil solution;
2) 0.3 gram sodium lauryl sulphate, 0.8 gram ammoniacal liquor (5%) solution are joined in the 75 gram water, low-grade fever stirs into aqueous phase solution;
3) above-mentioned oil-phase solution and aqueous phase solution is mixed, 60 ℃ of lower magnetic forces stirred 30 minutes, gave birth to KS-600 ultrasonic grinding 15 minutes (70% output rating) with Ningbo section then;
4) miniemulsion is moved into the reactor that mechanical stirring condensation reflux unit and nitrogen inlet, charging opening are housed, logical nitrogen deoxygenation is after 30 minutes, add 68 ℃ of water-baths, the aqueous solution (0.2 gram the is dissolved in 5 gram water) initiated polymerization that adds Potassium Persulphate simultaneously, after polymerization is finished, slowly cool to discharging after the room temperature.
Embodiment 8:
1) the oligopolymer RAFT (3) with 36 ℃ of phase-change wax of 20 grams and 0.3 gram joins in the miscellany of 6 gram butyl methacrylate, 4 gram methyl methacrylates, and is evenly mixed under the magnetic agitation, forms oil solution;
2) 0.1 gram sodium lauryl sulphate, 1 gram ammoniacal liquor (5%) solution are joined in the 75 gram water, low-grade fever stirs into uniform oil phase;
3) above-mentioned oil-phase solution and aqueous phase solution is mixed, 60 ℃ of lower magnetic forces stirred 30 minutes, gave birth to KS-600 ultrasonic grinding 15 minutes (70% output rating) with Ningbo section then;
4) miniemulsion is moved into the reactor that mechanical stirring condensation reflux unit and nitrogen inlet, charging opening are housed, logical nitrogen deoxygenation added 68 ℃ of water-baths, initiated polymerization after 30 minutes.
5) being polymerized to transformation efficiency is 90% o'clock, adds 0.4 gram monomer methacrylic acid glycol ester altogether, continue polyase 13 hour after, slowly cool to discharging after the room temperature.
Emulsion property
| Embodiment | Median size (nm) | Morphological structure | Storage stability |
| 1 | ?191.5 | Nucleocapsid | Good |
| 2 | ?144.0 | Nucleocapsid | Good |
| 3 | ?108.9 | Nucleocapsid | Good |
| 4 | ?110.8 | Nucleocapsid | Good |
| 5 | ?103.2 | Nucleocapsid | Good |
| 6 | ?124.5 | Nucleocapsid | Good |
| 7 | ?80.6 | Nucleocapsid | Good |
| 8 | ?186.4 | Nucleocapsid | Good |
Nucleocapsid structure is by transmission electron microscope observing, storage stability: GB6753.3-86.
Claims (10)
1. the method for a preparing microcapsule by initiating active fine emulsion polymerization of water-soluble initiating agent is characterized in that, the step of method is as follows:
1) with the phase change materials of 10～50 parts of weight, 10～200 parts of one or more vinyl monomers or multi-vinyl monomer, 0.1 part～5 parts the chain-transfer agent of parental type, forms oil solution;
2) with 0.01～10 part alkaline matter, be dissolved in 50～400 parts of water, form the aqueous solution;
3) aqueous solution and oil solution is mixed, pulverize 2～30 minutes formation miniemulsions through high shear field;
4) miniemulsion is moved into reactor, be warming up to 50～160 ℃, add 0.05～10 part of water soluble starter, initiated polymerization, polymerization is after 2～18 hours, slowly cools to discharging after the room temperature.
2. the method for a kind of preparing microcapsule by initiating active fine emulsion polymerization of water-soluble initiating agent according to claim 1 is characterized in that, described step 2) in be added with 0.01～10 part emulsifying agent.
3. the method for a kind of preparing microcapsule by initiating active fine emulsion polymerization of water-soluble initiating agent according to claim 1 is characterized in that described chain-transfer agent chemical structure of general formula is:
Wherein the Z group is: phenyl, phenmethyl, methyl, ethyl, propyl group, sec.-propyl, butyl and isomer thereof, amyl group and isomer thereof, oxyethyl group, methoxyl group mercaptan (SCH3), second sulfydryl (SCH
2CH
3), third sulfydryl (S (CH
2)
2CH
3), different third sulfydryl (SCH (CH
3)
2), fourth sulfydryl (S (CH
2)
3CH
3), 2-methyl-prop sulfydryl (SCH
2CH (CH
3)
2); The R group is: 1-methylbenzene methyl (CHCH
3(C
6H
6)), 1,1-dimethyl benzene methyl (C (CH
3)
2(C
6H
6)), 2-isobutyl itrile group (C (CH
3)
2CN), 2-y isobutyl acidic group (C (CH
3)
2COOH), 3-benzoyloxy ((C
6H
6) COOH), molecular weight is 200～50000 parental type (having the hydrophilic and oleophilic segment) oligopolymer; Described vinyl monomer is: vinylformic acid, methacrylic acid, methyl acrylate, ethyl propenoate, n-butyl acrylate, the special butyl ester of vinylformic acid, methyl methacrylate, butyl methacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, vinylformic acid lauryl alcohol ester, vinylbenzene, Vinyl toluene, t-butyl styrene or vinyl pyrrolidone, N hydroxymethyl acrylamide; Described multi-vinyl monomer is meant and contains two or more carbon-carbon double bond compounds in the molecule, be Vinylstyrene, Ethylene glycol dimethacrylate, allyl methyl vinylformic acid, ethylene glycol diacrylate, the diacrylate butanediol ester, tetramethylene dimethacrylate, the dimethacrylate DOPCP, the hexanodioic acid dimethacrylate, the dimethacrylate triglycol, the dimethacrylate Tetraglycol 99, TriMethylolPropane(TMP), tetramethylolmethane tetramethyl-vinylformic acid, Vinylstyrene.
4. the method for a kind of preparing microcapsule by initiating active fine emulsion polymerization of water-soluble initiating agent according to claim 1 is characterized in that described phase change materials is: C
8～C
28Alkane or its mixture; Described water soluble starter is persulphate (Potassium Persulphate, ammonium persulphate), hydrogen peroxide and derivative thereof, NP-02, N, N, N, N-Tetramethyl Ethylene Diamine.Described high shear field effect is provided by strong shearing liquid-liquid dispersing apparatus, i.e. ultrasonic grinding instrument, high-pressure homogenizer, super gravity field generating unit.
5. the method for a kind of preparing microcapsule by initiating active fine emulsion polymerization of water-soluble initiating agent according to claim 2, it is characterized in that described emulsifying agent is: sodium lauryl sulphate, cetyl trimethylammonium bromide, the soil matrix phenol polyethenoxy ether, OP series, MS-1, Span, tween, Sodium dodecylbenzene sulfonate, described alkaline matter is: sodium hydroxide, yellow soda ash, sodium bicarbonate, ammoniacal liquor, aniline.
6. the method for a preparing microcapsule by initiating active fine emulsion polymerization of water-soluble initiating agent is characterized in that, the step of method is as follows:
1) with the phase change materials of 10～50 parts of weight, 10～200 parts of one or more vinyl monomers or multi-vinyl monomer, 0.1 part～5 parts the chain-transfer agent of parental type, forms oil solution;
2) with 0.01～10 part emulsifying agent, 0.01～10 part alkaline matter is dissolved in 50～400 parts of water, forms the aqueous solution;
3) aqueous solution and oil solution is mixed, pulverize 2～30 minutes formation miniemulsions through high shear field;
4) miniemulsion is moved into reactor, be warming up to 50～160 ℃, add 0.05～10 part of water soluble starter, initiated polymerization;
5) reach 52～90% when polymerisation conversion, add 0.01～5 part of linking agent.After the polymerization 1～18 hour, slowly cool to discharging after the room temperature.
7. the method for a kind of preparing microcapsule by initiating active fine emulsion polymerization of water-soluble initiating agent according to claim 6 is characterized in that described chain-transfer agent chemical structure of general formula is:
Wherein the Z group is: phenyl, phenmethyl, methyl, ethyl, propyl group, sec.-propyl, butyl and isomer thereof, amyl group and isomer thereof, oxyethyl group, methoxyl group mercaptan (SCH3), second sulfydryl (SCH
2CH
3), third sulfydryl (S (CH
2)
2CH
3), different third sulfydryl (SCH (CH
3)
2), fourth sulfydryl (S (CH
2)
3CH
3), 2-methyl-prop sulfydryl (SCH
2CH (CH
3)
2); The R group is: 1-methylbenzene methyl (CHCH
3(C
6H
6)), 1,1-dimethyl benzene methyl (C (CH
3)
2(C
6H
6)), 2-isobutyl itrile group (C (CH
3)
2CN), 2-y isobutyl acidic group (C (CH
3)
2COOH), 3-benzoyloxy ((C
6H
6) COOH), molecular weight is 200～50000 parental type (having the hydrophilic and oleophilic segment) oligopolymer; Described vinyl monomer is: vinylformic acid, methacrylic acid, methyl acrylate, ethyl propenoate, n-butyl acrylate, the special butyl ester of vinylformic acid, methyl methacrylate, butyl methacrylate, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, vinylformic acid lauryl alcohol ester, vinylbenzene, Vinyl toluene, t-butyl styrene or vinyl pyrrolidone, N hydroxymethyl acrylamide; Described multi-vinyl monomer is meant and contains two or more carbon-carbon double bond compounds in the molecule, be Vinylstyrene, Ethylene glycol dimethacrylate, allyl methyl vinylformic acid, ethylene glycol diacrylate, the diacrylate butanediol ester, tetramethylene dimethacrylate, the dimethacrylate DOPCP, the hexanodioic acid dimethacrylate, the dimethacrylate triglycol, the dimethacrylate Tetraglycol 99, TriMethylolPropane(TMP), tetramethylolmethane tetramethyl-vinylformic acid, Vinylstyrene.
8. the method for a kind of preparing microcapsule by initiating active fine emulsion polymerization of water-soluble initiating agent according to claim 6 is characterized in that described phase change materials is C
8～C
28Alkane or its mixture; Described water soluble starter is persulphate (Potassium Persulphate, ammonium persulphate), hydrogen peroxide and derivative thereof, NP-02, N, N, N, N-Tetramethyl Ethylene Diamine; Described high shear field effect is provided by strong shearing liquid-liquid dispersing apparatus, i.e. ultrasonic grinding instrument, high-pressure homogenizer, super gravity field generating unit.
9. the method for a kind of preparing microcapsule by initiating active fine emulsion polymerization of water-soluble initiating agent according to claim 6, it is characterized in that described emulsifying agent is: sodium lauryl sulphate, cetyl trimethylammonium bromide, soil matrix phenol polyethenoxy ether, OP series, MS-1, Span, tween, Sodium dodecylbenzene sulfonate, used alkaline matter is sodium hydroxide, yellow soda ash, sodium bicarbonate, ammoniacal liquor, aniline.
10. the method for a kind of preparing microcapsule by initiating active fine emulsion polymerization of water-soluble initiating agent according to claim 6, it is characterized in that described linking agent is an allyl methyl vinylformic acid, ethylene glycol dimethacrylate, glycol diacrylate, butylene glycol diacrylate, butylene glycol dimethacrylate, neopentylglycol dimethacrylate, the hexanodioic acid dimethacrylate, the triglycol dimethacrylate, the Tetraglycol 99 dimethacrylate, TriMethylolPropane(TMP), tetramethylolmethane tetramethyl-vinylformic acid, Vinylstyrene.
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| DE102006062439A1 (en) * | 2006-12-27 | 2008-07-03 | Byk-Chemie Gmbh | Comb polymers made by reacting styrene-maleic anhydride copolymer with prim. amino-terminated polyalkylene oxide, used as wetting agents and dispersants, e.g. for production of pigment paste |
| CN102941046A (en) * | 2012-11-26 | 2013-02-27 | 天津工业大学 | Preparation method for micro/nano-capsule with metal ion complex capsule wall |
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| CN1280377C (en) * | 2003-08-21 | 2006-10-18 | 河北工业大学 | Microcapsule coated phase change material and its preparation method |
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| DE102006062439A1 (en) * | 2006-12-27 | 2008-07-03 | Byk-Chemie Gmbh | Comb polymers made by reacting styrene-maleic anhydride copolymer with prim. amino-terminated polyalkylene oxide, used as wetting agents and dispersants, e.g. for production of pigment paste |
| US8153731B2 (en) | 2006-12-27 | 2012-04-10 | BYK=Chemie GmbH | Comb (block) copolymers |
| CN102941046A (en) * | 2012-11-26 | 2013-02-27 | 天津工业大学 | Preparation method for micro/nano-capsule with metal ion complex capsule wall |
| CN103642462A (en) * | 2013-12-02 | 2014-03-19 | 上海应用技术学院 | Millimeter temperature-control slow-release aromatic gel capsule and preparation method thereof |
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| CN114621380A (en) * | 2022-03-10 | 2022-06-14 | 北京化工大学 | Method for preparing poly (styrene-maleic anhydride) special-shaped functional microspheres by miniemulsion polymerization |
| CN115322511A (en) * | 2022-09-14 | 2022-11-11 | 英创新材料(绍兴)有限公司 | Phase-change heat storage material elastic film and preparation method thereof |
| CN115322511B (en) * | 2022-09-14 | 2024-04-02 | 英创新材料(绍兴)有限公司 | Elastic film of phase-change heat storage material and preparation method thereof |
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