CN1760224A - Method for preparing inflaming retarding type copolymerization latex of urethane acrylate - Google Patents
Method for preparing inflaming retarding type copolymerization latex of urethane acrylate Download PDFInfo
- Publication number
- CN1760224A CN1760224A CN 200510030114 CN200510030114A CN1760224A CN 1760224 A CN1760224 A CN 1760224A CN 200510030114 CN200510030114 CN 200510030114 CN 200510030114 A CN200510030114 A CN 200510030114A CN 1760224 A CN1760224 A CN 1760224A
- Authority
- CN
- China
- Prior art keywords
- acrylate
- flame retardant
- inflaming retarding
- consumption
- double key
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000007334 copolymerization reaction Methods 0.000 title claims description 35
- 239000004816 latex Substances 0.000 title claims description 35
- 229920000126 latex Polymers 0.000 title claims description 35
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 title claims description 34
- 230000000979 retarding effect Effects 0.000 title claims description 32
- 238000000034 method Methods 0.000 title description 2
- 239000000839 emulsion Substances 0.000 claims abstract description 36
- 239000004814 polyurethane Substances 0.000 claims abstract description 35
- 229920002635 polyurethane Polymers 0.000 claims abstract description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 32
- 229920001577 copolymer Polymers 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000003063 flame retardant Substances 0.000 claims description 68
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 60
- 230000000694 effects Effects 0.000 claims description 36
- 239000000178 monomer Substances 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 238000002360 preparation method Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000006185 dispersion Substances 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 24
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 24
- 229920000570 polyether Polymers 0.000 claims description 24
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 238000009413 insulation Methods 0.000 claims description 17
- -1 4,4 '-methylene Chemical group 0.000 claims description 15
- 150000002334 glycols Chemical class 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 14
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- SLKPORNFSBUSRF-UHFFFAOYSA-N [Cl].[Sb].[P] Chemical compound [Cl].[Sb].[P] SLKPORNFSBUSRF-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 150000001875 compounds Chemical group 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 claims description 6
- 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 description 6
- 239000004970 Chain extender Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 6
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- 150000003384 small molecules Chemical group 0.000 claims description 6
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 239000004159 Potassium persulphate Substances 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 4
- NUKZAGXMHTUAFE-UHFFFAOYSA-N methyl hexanoate Chemical compound CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 3
- CHUGKEQJSLOLHL-UHFFFAOYSA-N 2,2-Bis(bromomethyl)propane-1,3-diol Chemical compound OCC(CO)(CBr)CBr CHUGKEQJSLOLHL-UHFFFAOYSA-N 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- CMQUQOHNANGDOR-UHFFFAOYSA-N 2,3-dibromo-4-(2,4-dibromo-5-hydroxyphenyl)phenol Chemical compound BrC1=C(Br)C(O)=CC=C1C1=CC(O)=C(Br)C=C1Br CMQUQOHNANGDOR-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical group CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 claims description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920001083 polybutene Polymers 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 229940095064 tartrate Drugs 0.000 claims description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000011258 core-shell material Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 12
- 238000010792 warming Methods 0.000 description 12
- 238000002485 combustion reaction Methods 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000000576 coating method Methods 0.000 description 5
- 239000007859 condensation product Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 235000013336 milk Nutrition 0.000 description 5
- 239000008267 milk Substances 0.000 description 5
- 210000004080 milk Anatomy 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical group [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 2
- 229960004418 trolamine Drugs 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101001044039 Homo sapiens Lipase member N Proteins 0.000 description 1
- 102100021612 Lipase member N Human genes 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920007962 Styrene Methyl Methacrylate Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- WHLPIOPUASGRQN-UHFFFAOYSA-N butyl 2-methylprop-2-enoate;methyl 2-methylprop-2-enoate Chemical compound COC(=O)C(C)=C.CCCCOC(=O)C(C)=C WHLPIOPUASGRQN-UHFFFAOYSA-N 0.000 description 1
- NZEWVJWONYBVFL-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;styrene Chemical compound COC(=O)C(C)=C.C=CC1=CC=CC=C1.CCCCOC(=O)C=C NZEWVJWONYBVFL-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- JFVZTPIWVQKFFW-UHFFFAOYSA-N propanoate;tris(2-hydroxyethyl)azanium Chemical compound CCC([O-])=O.OCC[NH+](CCO)CCO JFVZTPIWVQKFFW-UHFFFAOYSA-N 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
A process for preparing the flame-retarding polyurethane-acrylate copolymer emulsion includes such steps as preparing the flame-retarding polyurethane seed emulsion containing double bond, core-shell copolymerizing between said seed emulsion and acrylate, and mixing it with the emulsion of meta-dishloroethene-acrylate copolymer.
Description
Technical field
The present invention relates to chemical technology field, be specifically related to a kind of preparation method of inflaming retarding type copolymerization latex of urethane acrylate.
Background technology
Along with the enhancing, particularly various countries' environmental regulation of people's environmental protection, energy consciousness strictness restriction, promoted that water-borne coatings is the development of the low-contamination type coating of representative to volatile organic matter in the coating system (VOC) content.Aqueous polyurethane (PU) emulsion and polyacrylic ester (PA) emulsion have been widely used as the base-material of coating, printing ink, tackiness agent, but its performance is difficult to match in excellence or beauty with corresponding solvent type resin usually.Yet the performance of PU and PA two class emulsions has very strong complementarity, has excellent abrasive, solvent-resisting, scratch resistance as the PU emulsion film, but aspects such as stability, solid content, gloss, cost are not fully up to expectations; The advantage of PA emulsion film is big, good with outward appearance and the relative low cost of weathering resistance of hardness, but wear resistance, chemical-resistant are relatively poor.The effective ways that improve emulsion property are with two kinds of emulsion chemistry copolymerization, and products therefrom is polyurethane/acrylate (PUA) copolymer emulsion, and its film performance combines both advantages, more and more come into one's own at present and are used widely.Along with the expansion of PUA material application surface, each industrial sector, especially furniture industry, paper industry and building industry, more and more higher to the requirement of flame retardant properties, and the preparation of inflaming retarding type copolymerization latex of urethane acrylate rarely has report simultaneously.
Find through literature search prior art, Chinese patent application number is 03113854.3 patent, this patent adopts seeded emulsion polymerization technology, the acrylate urethane copolymer emulsion that has prepared the cross linking of epoxy resin modification, its film have excellent in water resistance, solvent resistance, high rigidity and good surface appearance, but relevant fire-retardant problem is proposed.Also find in the retrieval, Chinese patent application number is 200410012458.5 patent, this patent adopts the LIPN polymerization, prepared polyurethane/polyacrylate latex interpenetrating network polymer emulsion, can be used for hide finishes, wood lacquer, automobile damping material etc., but it does not satisfy the requirement of materials such as woodenware to flame retardant properties yet.In further retrieving, find as yet and the identical or similar bibliographical information of theme of the present invention " inflaming retarding type copolymerization latex of urethane acrylate and preparation method thereof ".
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of preparation method who prepares inflaming retarding type copolymerization latex of urethane acrylate is provided.Make it pass through " particle design ",, give the PUA aqueous dispersion interior flame retardant resistance of filming, satisfying the raising to fire-retardant requirement such as furniture industry, paper industry and building industry, and enlarge the range of application of PUA flame-retardant polyurethane and acrylic ester copolymer.
The present invention is achieved by the following technical solutions, and the present invention adopts the molecular designing means, makes double bond containing flame-retardant polyurethane seed emulsion; Utilize the particle design means again, flame retardant polyurethane seed emulsion and acrylate are carried out core-shell copolymerized, promptly obtain inflaming retarding type copolymerization latex of urethane acrylate with vinylidene chloride/acrylate copolymer emulsion thorough mixing then.Method steps is as follows:
(1) earlier vulcabond, flame retardant resistance polyvalent alcohol, non-flame retardant resistance polyvalent alcohol and the compound bearing active hydrogen that has that can form hydrophilic radical are carried out the prepolymer hybrid reaction earlier, obtain flame retardant polyurethane prepolymer I;
(2) with prepolymer I and the monomer reaction that contains activity double key to-NCO content to prescribed value, add neutralizing agent and all acrylate monomer then, in and hydrophilic radical and reduce prepolymer viscosity, make the flame retardant polyurethane prepolymer II of ionic band activity double key and the mixture of acrylate monomer; (3) prepolymer II is distributed in the deionized water, adds small molecule chain extender simultaneously and carry out chain extension, make acrylate monomer swollen flame-retardant polyurethane water dispersion;
(4) with above-mentioned aqueous dispersion, heat temperature raising to 50～80 ℃ are incubated 0.5～1.5 hour; In 1～3.5 hour, initiator and remaining acrylate monomer are dropwised then, continued insulation reaction again 1～3 hour, cooling is filtered, and obtains inflaming retarding type copolymerization latex of urethane acrylate then with behind a certain amount of vinylidene chloride (VdC)/acrylate (Acrylate) copolymer emulsion thorough mixing;
Wherein the consumption of each raw material is as follows:
Described vulcabond, consumption be ionic band activity double key flame retardant polyurethane prepolymer gross weight 14%～55%;
Described flame retardant resistance polyvalent alcohol, consumption be ionic band activity double key flame retardant polyurethane prepolymer gross weight 6.5%～76%;
Described non-flame retardant resistance polyvalent alcohol, consumption be ionic band activity double key flame retardant polyurethane prepolymer gross weight 0%～54%;
The described compound bearing active hydrogen that has that forms hydrophilic radical, consumption account for according to its contained carboxyl quality ionic band activity double key flame retardant polyurethane prepolymer gross weight 1.4%～2.7%;
Described neutralizing agent, consumption be in the flame retardant polyurethane prepolymer of ionic band activity double key the carboxyl molar weight 70%～120%;
The described monomer that contains activity double key, consumption be ionic band activity double key flame retardant polyurethane prepolymer gross weight 2.5%～15%;
Described small molecule chain extender, consumption be ionic band activity double key the polyurethane prepolymer total mass 0%～12.5%;
Described vinylidene chloride/acrylate copolymer emulsion, its consumption is determined by 0%～100% of its solid part quality polyurethane prepolymer total mass that is ionic band activity double key;
Described acrylate monomer, consumption be ionic band activity double key the polyurethane prepolymer total mass 30%～150%;
Described initiator, consumption are 0.5%～1.2% of acrylate monomer total mass.
Described vulcabond is selected from tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), naphthalene-1,5-vulcabond (NDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,6-vulcabond methyl caproate (LDI), 4,4 '-methylene radical-dicyclohexyl vulcabond (H
12MDI), xylylene diisocyanate (XDI), 1,12-dodecyl vulcabond (C
12DDI) etc. a kind of in common aromatic series and the aliphatic diisocyanate.
That described flame retardant resistance polyvalent alcohol is selected from is phosphorous, the polyvalent alcohol with anti-flaming function of one or more elements in the antimony, halogen, as one or more the mixture in phosphoric acid ester polyether glycol, phosphorus antimony chlorine ternary phosphoric acid ester polyether glycol, halogenated polyether polyvalent alcohol, dibromoneopentyl glycol, the tetrabromo-bisphenol.Wherein:
Described phosphoric acid ester polyether glycol is for being phosphide with in phosphorus trichloride, phosphoric acid or five phosphorus oxide one or more, in glycerine, TriMethylolPropane(TMP), butyleneglycol, propylene glycol, sorbyl alcohol, the tetramethylolmethane one or more are polyol, ethylene oxide, propylene oxide, epoxy chloropropane, butylene oxide ring, 1,1,1-three chloro-3, one or more in the 4-butylene oxide ring are the phosphor-containing flame-proof dibasic alcohol of feedstock production gained for epoxide;
Described phosphorus antimony chlorine ternary phosphoric acid ester polyether glycol is for being phosphide with in phosphorus trichloride, phosphoric acid or five phosphorus oxide one or more, in glycerine, TriMethylolPropane(TMP), propylene glycol, sorbyl alcohol, the tetramethylolmethane one or more are polyol, ethylene oxide, propylene oxide, epoxy chloropropane, butylene oxide ring, 1-three chloro-3, in the 4-butylene oxide ring one or more are epoxide, and butter of antimony is phosphorous, the antimony of feedstock production gained, the dibasic alcohol of three kinds of ignition-proof elements of chlorine;
Described halogenated polyether polyvalent alcohol is 4,4,4-three chloro-1, and 2-butylene oxide ring or 4,4,4-three bromo-1, the 2-butylene oxide ring is a raw material, lewis' acid is a catalyzer, the various halogenated polyether dibasic alcohol that reaction makes.
Described non-flame retardant resistance polyvalent alcohol is selected from polyether Glycols commonly used, polyester diol, polycarbonate diol, polybutadiene diol, polybutene glycol, acrylate polyvalent alcohol, polycaprolactone glycol, the mixture of one or more in the PTMG.
The described compound bearing active hydrogen that has that forms hydrophilic radical is selected from dibasic alcohol such as dimethylol propionic acid, tartrate that contains carboxyl structure and one or more the mixture in the dibasic alcohol that contains the sulfonic acid structure.
Described neutralizing agent be selected from the energy and mineral alkalis such as tertiary amines organic bases, sodium hydroxide, ammoniacal liquor such as the compound of carboxylic acid and sulfonic acid such as triethylamine in one or more mixture.
The described monomer that contains activity double key be selected from contain " C=C " double bond structure band can with the monomer of-NCO reactive activity hydrogen, as one or more mixture of Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, N hydroxymethyl acrylamide.
Described small molecule chain extender is selected from micromolecular diamine, polyamine, as quadrol, hexanediamine, diethylenetriamine, hydrazine hydrate etc.
Described vinylidene chloride/acrylate copolymer emulsion is a VdC content at vinylidene chloride/acrylate copolymer emulsion of 30%～70%.
Described acrylate monomer is selected from alkyl acrylate, alkyl methacrylate or vinyl carboxylic acid, as methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, the mixture of one or more in butyl methacrylate, hexanediyl ester, decyl acrylate, lauryl methacrylate(LMA), hydroxyethyl methylacrylate, N hydroxymethyl acrylamide, vinyl cyanide, vinylbenzene, the acrylamide.
Described initiator is selected from water-soluble thermal initiator, oil soluble thermal initiators, redox initiator, a kind of as in Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate, benzoyl peroxide, t-butyl hydroperoxide/xitix, the Potassium Persulphate/sodium bisulfite.
The preparation condition and the equipment of the preparation condition of inflaming retarding type copolymerization latex of urethane acrylate of the present invention and equipment and existing copolymerization latex of urethane acrylate are basic identical.
The inflaming retarding type copolymerization latex of urethane acrylate of the present invention's preparation is compared with existing copolymerization latex of urethane acrylate has following advantage: (1) the present invention has designed the chemical structure that has anti-flaming function on polyurethane backbone, and makes it to have prepared the good PUA copolymer emulsion that has flame retarding construction of consistency with acrylic ester copolymer; (2) chemical structure of band anti-flaming function gives the inflaming retarding type copolymerization latex of urethane acrylate goods certain interior flame retardant effect, has avoided adding fire retardant to the copolymerization latex of urethane acrylate Effect on Performance.
Embodiment
Below by embodiment embodiment of the present invention are described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
Inflaming retarding type copolymerization latex of urethane acrylate prescription one:
| Raw material | Quality (g) |
| Toluene di-isocyanate(TDI) phosphorus antimony chlorine ternary phosphoric acid ester polyether Glycols (hydroxyl value 50mgKOH/g) dihydromethyl propionic acid triethylamine hydroxyethyl methacrylate methyl methacrylate butyl acrylate EMA styrene initator | 17400g 95724g 5452g 3493g 4366g 76573g 9524g 25140g 15198g 632g |
In the reactor that stirring arm, thermometer and condenser are housed, add tolylene diisocyanate, hydroxyl value is the phosphorus antimony chlorine ternary phosphoric acid ester polyether Glycols of 50mgKOH/g, dimethylol propionic acid, be warming up to 60 ℃, insulation reaction 0.5 hour is warming up to 75 ℃ of reactions to-NCO content again and reaches prescribed value.The hydroxyethyl methylacrylate that adds metering, 75 ℃ of following insulation reaction 2 hours are cooled to 30 ℃ then, obtain being with activity double key flame retardant polyurethane prepolymer.Add triethylamine and all acrylate monomer, stir the miscellany that obtained end capped flame retardant polyurethane performed polymer of anionic activity double key and acrylate monomer in 0.5 hour.Above-mentioned miscellany is added deionized water carry out emulsification in emulsify at a high speed equipment, make acrylate monomer swollen flame-retardant polyurethane water dispersion.With above-mentioned aqueous dispersion heat temperature raising to 50 ℃, be incubated 1 hour; Be warming up to 80 ℃ and in 1 hour initiator is dropwised then, continued insulation reaction again 3 hours, discharging is filtered in cooling, obtains inflaming retarding type copolymerization latex of urethane acrylate.In the prescription of the present invention, NCO/OH (mol ratio) is 1.2, and-COOH mass content is 1.4%, and neutralization ratio is 85%.The flame-retardant polyurethane water dispersion of the present invention preparation be translucent, do not have mechanical impurity, no condensation product milk sap.This emulsion has good stability to hydrolysis and storage stability, and water-resistance property of coating, solvent resistance are good.The flame-retardant polyurethane water dispersion of the present invention that takes a morsel preparation is measured according to GB GB12441-1998 " finishing fire retardant paint general technical specifications ", its anti-combustion time 〉=20min, ratio≤35 are relayed in the fire combustion, reach secondary domestic enterprise production fire resistance.
Embodiment 2
Inflaming retarding type copolymerization latex of urethane acrylate prescription two:
| Raw material | Quality (g) |
| IPDI phosphoric acid ester polyether Glycols (hydroxyl value 200mgKOH/g) dibromoneopentyl glycol tartaric acid hydroxypropyl acrylate NaOH hexamethylene diamine methyl methacrylate initator vinylidene chloride/acrylate copolymer emulsion (VdC content be 50%, solid content 45%) | 22200g 6626g 2907g 1682g 6007g 628g 5053g 12015g 120g 44500g |
In the reactor that stirring arm, thermometer and condenser are housed, add tolylene diisocyanate, hydroxyl value is the phosphoric acid ester polyether Glycols of 200mgKOH/g, dibromoneopentyl glycol, dimethylol propionic acid, be warming up to 60 ℃, insulation reaction 1 hour is warming up to 85 ℃ of reactions to-NCO content again and reaches prescribed value.The Propylene glycol monoacrylate that adds metering, 80 ℃ of following insulation reaction 1～2 hour are cooled to 45 ℃ then, obtain being with activity double key flame retardant polyurethane prepolymer.Add NaOH and whole methyl methacrylate, stir the miscellany that obtained end capped flame retardant polyurethane performed polymer of anionic activity double key and methyl methacrylate monomer in 1 hour.Said mixture is added deionized water carry out emulsification in emulsify at a high speed equipment, make methyl methacrylate monomer swollen flame-retardant polyurethane water dispersion.With above-mentioned aqueous dispersion heat temperature raising to 60 ℃, be incubated 1 hour; In 3.5 hours initiator is dropwised then, continued insulation reaction again 2 hours, discharging is filtered in cooling, and it is even to add vinylidene chloride/acrylate copolymer emulsion thorough mixing then, obtains inflaming retarding type copolymerization latex of urethane acrylate.In the prescription of the present invention, NCO/OH (mol ratio) is 3.0, and-COOH mass content is 2.5%, and neutralization ratio is 70%.The flame-retardant polyurethane water dispersion of the present invention preparation for milky white, do not have mechanical impurity, no condensation product milk sap.This emulsion has good stability to hydrolysis and storage stability, smears water tolerance, solvent resistance is good.The flame-retardant polyurethane water dispersion of the present invention that takes a morsel preparation is measured according to GB GB12441-1998 " finishing fire retardant paint general technical specifications ", its anti-combustion time 〉=10min, ratio≤55 are relayed in the fire combustion, reach three grades of domestic enterprise's production fire resistances.
Embodiment 3
Inflaming retarding type copolymerization latex of urethane acrylate prescription three:
| Raw material | Quality |
| Hexamethylene diisocyanate phosphoric acid ester polyether Glycols (hydroxyl value 200mgKOH/g) PTMG (mean molecule quantity 1000) dihydromethyl propionic acid triethanolamine N hydroxymethyl acrylamide ethylenediamine styrene methyl methacrylate initator vinylidene chloride/acrylate copolymer emulsion (VdC content be 70%, solid content 45%) | 16800g 4058g 33272g 3502g 2639g 1545g 2541g 13570g 60609g 890g 137368g |
Stirring arm is being housed, in the reactor of thermometer and condenser, add hexamethylene diisocyanate, the phosphoric acid ester polyether Glycols, PTMG (molecular-weight average 1000), dimethylol propionic acid, be warming up to 60 ℃, insulation reaction 1.5 hours, be warming up to 90 ℃ of reactions to-NCO content again and reach prescribed value, the N hydroxymethyl acrylamide that adds metering, 85 ℃ of following insulation reaction 2 hours are cooled to 35 ℃ then, add trolamine and whole methyl methacrylate and vinylbenzene, stir the miscellany that obtains end capped flame retardant polyurethane performed polymer of anionic activity double key and acrylate monomer after 1 hour.Said mixture is added deionized water carry out emulsification in emulsify at a high speed equipment, make acrylate monomer swollen flame-retardant polyurethane water dispersion.With above-mentioned aqueous dispersion heat temperature raising to 50 ℃, be incubated 1.5 hours; Be warming up to 80 ℃ then and in 2.5 hours initiator dropwised, continued insulation reaction again 2 hours, cooling is filtered, and it is even to add vinylidene chloride/acrylate copolymer emulsion thorough mixing then, obtains inflaming retarding type copolymerization latex of urethane acrylate.In the prescription of the present invention, NCO/OH (mol ratio) is 2.0, and-COOH mass content is 1.9%, and neutralization ratio is 100%.The flame-retardant polyurethane water dispersion of the present invention preparation is oyster white, do not have mechanical impurity, no condensation product milk sap.The flame-retardant polyurethane water dispersion of the present invention that takes a morsel preparation is measured according to GB GB12441-1998 " finishing fire retardant paint general technical specifications ", its anti-combustion time 〉=10min, ratio≤70 are relayed in the fire combustion, reach three grades of domestic enterprise's production fire resistances.
Embodiment 4
Inflaming retarding type copolymerization latex of urethane acrylate prescription four:
| Raw material | Quality |
| 4,4 '-methyl diphenylene diisocyanate (MDI) phosphoric acid ester polyether Glycols (hydroxyl value 150mgKOH/g) chloro polyether Glycols (hydroxyl value 100mgKOH/g) dihydromethyl propionic acid hydroxy-ethyl acrylate hydroxyethyl methacrylate triethylamine hexamethylene diamine methyl methacrylate butyl acrylate styrene | 25000g 6904g 10355g 4169g 2620g 1076g 2671g 3127g 55350g 13006g 10837g |
| Initiator vinylidene chloride/acrylate copolymer emulsion (VdC content be 30%, solid content 45%) | 792g 35196g |
Stirring arm is being housed, in the reactor of thermometer and condenser, add 4,4 '-diphenylmethanediisocyanate, the phosphoric acid ester polyether Glycols, the chloro polyether Glycols, dimethylol propionic acid, be warming up to 60 ℃, insulation reaction 1 hour is warming up to 85 ℃ of reactions to-NCO content again and reaches prescribed value, add Hydroxyethyl acrylate and hydroxyethyl methylacrylate, 90 ℃ of following insulation reaction 2 hours are cooled to 55 ℃ then, are cooled to 40 ℃, add trolamine and all acrylate monomer and vinylbenzene, stir the miscellany that obtains end capped flame retardant polyurethane performed polymer of anionic activity double key and acrylate monomer after 1 hour.Said mixture is added deionized water carry out emulsification in emulsify at a high speed equipment, and added the hexanediamine stirring reaction 30 minutes, make acrylate monomer swollen flame-retardant polyurethane water dispersion.With above-mentioned aqueous dispersion heat temperature raising to 65 ℃, be incubated 1 hour; In 2 hours initiator is dropwised then, continued insulation reaction again 3 hours, cooling is filtered, and it is even to add vinylidene chloride/acrylate copolymer emulsion thorough mixing then, obtains inflaming retarding type copolymerization latex of urethane acrylate.In the prescription of the present invention, NCO/OH (mol ratio) is 1.7, and-COOH mass content is 2.7%, and neutralization ratio is 85%.The flame-retardant polyurethane water dispersion of the present invention preparation for milky white, do not have mechanical impurity, no condensation product milk sap.The flame-retardant polyurethane water dispersion of the present invention that takes a morsel preparation is measured according to GB GB12441-1998 " finishing fire retardant paint general technical specifications ", its anti-combustion time 〉=10min, ratio≤60 are relayed in the fire combustion, reach three grades of domestic enterprise's production fire resistances.
Embodiment 5
Flame-retardant polyurethane water dispersion prescription five:
| Raw material | Quality |
| 4,4 '-methylene radical-dicyclohexyl vulcabond (H 12MDI) phosphorus antimony chlorine ternary phosphoric acid ester polyether Glycols (hydroxyl value 112mgKOH/g) polyoxypropyleneglycol (mean molecule quantity 2000) PTMG (mean molecule quantity 1000) dihydromethyl propionic acid triethylamine hydroxypropyl acrylate | 26200g 14917g 9945g 4972g 4113g 2635g 3304g |
| Hexamethylene diamine methyl methacrylate butyl methacrylate initator vinylidene chloride/acrylate copolymer emulsion (VdC content be 50%, solid content 45%) | 3681g 54312g 11774g 661g 88114g |
Stirring arm is being housed, in the reactor of thermometer and condenser, add 4,4 '-methylene radical-dicyclohexyl vulcabond, phosphorus antimony chlorine ternary phosphoric acid ester polyether Glycols, the polyoxytrimethylene dibasic alcohol, PTMG, dimethylol propionic acid is warming up to 60 ℃, insulation reaction 1.5 hours, be warming up to 90 ℃ of reactions to-NCO content again and reach prescribed value, the Propylene glycol monoacrylate that adds metering, 90 ℃ of following insulation reaction 3 hours are cooled to 40 ℃, add triethylamine and all acrylate monomer, stir the miscellany that obtains end capped flame retardant polyurethane performed polymer of anionic activity double key and acrylate monomer after 1 hour.Said mixture is added deionized water carry out emulsification in emulsify at a high speed equipment, and added the hexanediamine stirring reaction 30 minutes, make acrylate monomer swollen flame-retardant polyurethane water dispersion.With above-mentioned aqueous dispersion heat temperature raising to 65 ℃, be incubated 1 hour; In 2 hours initiator is dropwised then, continued insulation reaction again 3 hours, cooling is filtered, and it is even to add vinylidene chloride/acrylate copolymer emulsion thorough mixing then, obtains inflaming retarding type copolymerization latex of urethane acrylate.Above-mentioned performed polymer is added deionized water carry out emulsification in emulsify at a high speed equipment, promptly get the polyurethane aqueous dispersions that anionic has anti-flaming function.In the prescription of the present invention, NCO/OH (mol ratio) is 1.8, and-COOH mass content is 2.2%, and neutralization ratio is 85%.The flame-retardant polyurethane water dispersion of the present invention preparation for milky white, do not have mechanical impurity, no condensation product milk sap.The flame-retardant polyurethane water dispersion of the present invention that takes a morsel preparation is measured according to GB GB12441-1998 " finishing fire retardant paint general technical specifications ", its anti-combustion time 〉=10min, ratio≤55 are relayed in the fire combustion, reach three grades of domestic enterprise's production fire resistances.
Claims (10)
1, a kind of preparation method of inflaming retarding type copolymerization latex of urethane acrylate is characterized in that, may further comprise the steps:
(1) earlier vulcabond, flame retardant resistance polyvalent alcohol, non-flame retardant resistance polyvalent alcohol and the compound bearing active hydrogen that has that can form hydrophilic radical are carried out the prepolymer hybrid reaction earlier, obtain flame retardant polyurethane prepolymer I;
(2) with prepolymer I and the monomer reaction that contains activity double key to-NCO content to prescribed value, add neutralizing agent and part or all of acrylate monomer then, in and hydrophilic radical and reduce prepolymer viscosity, make the flame retardant polyurethane prepolymer II of ionic band activity double key and the mixture of acrylate monomer;
(3) prepolymer II is distributed in the deionized water, adds small molecule chain extender simultaneously and carry out chain extension, make acrylate monomer swollen flame-retardant polyurethane water dispersion;
(4) with above-mentioned aqueous dispersion heat temperature raising to 50～80 ℃, be incubated 0.5～1.5 hour; In 1～3.5 hour, initiator, remaining acrylate monomer are dropwised then, continued insulation reaction again 1～3 hour, cooling is filtered, and obtains inflaming retarding type copolymerization latex of urethane acrylate then with behind vinylidene chloride/acrylate copolymer emulsion thorough mixing;
Wherein the consumption of each raw material is as follows:
Described vulcabond, consumption be ionic band activity double key flame retardant polyurethane prepolymer gross weight 14%～55%;
Described flame retardant resistance polyvalent alcohol, consumption be ionic band activity double key flame retardant polyurethane prepolymer gross weight 6.5%～76%;
Described non-flame retardant resistance polyvalent alcohol, consumption be ionic band activity double key flame retardant polyurethane prepolymer gross weight 0%～54%;
The described compound bearing active hydrogen that has that forms hydrophilic radical, consumption account for according to its contained carboxyl quality ionic band activity double key flame retardant polyurethane prepolymer gross weight 1.4%～2.7%;
Described neutralizing agent, consumption be in the flame retardant polyurethane prepolymer of ionic band activity double key the carboxyl molar weight 70%～120%;
The described monomer that contains activity double key, consumption be ionic band activity double key flame retardant polyurethane prepolymer gross weight 2.5%～15%;
Described small molecule chain extender, consumption be ionic band activity double key the polyurethane prepolymer total mass 0%～12.5%;
Described vinylidene chloride/acrylate copolymer emulsion, its consumption are that 0%～100% of ionic polyurethanes prepolymer total mass is determined by its solid part quality;
Described acrylate monomer, consumption be ionic band activity double key the polyurethane prepolymer total mass 30%～150%;
Described initiator, consumption are 0.5%～1.2% of acrylate monomer total mass.
2, the preparation method of inflaming retarding type copolymerization latex of urethane acrylate according to claim 1, it is characterized in that, in the step (1), described vulcabond is selected from tolylene diisocyanate TDI, diphenylmethanediisocyanate MDI, naphthalene-1,5-vulcabond NDI, hexamethylene diisocyanate HDI, isophorone diisocyanate IPDI, 2,6-vulcabond methyl caproate LDI, 4,4 '-methylene radical-dicyclohexyl vulcabond H
12MDI, xylylene diisocyanate XDI, 1,12-dodecyl vulcabond C
12A kind of among the DDI.
3, according to the preparation method of claim 1 or 2 described inflaming retarding type copolymerization latex of urethane acrylate, it is characterized in that, in the step (1), described flame retardant resistance polyvalent alcohol is selected from one or more the mixture in phosphoric acid ester polyether glycol, phosphorus antimony chlorine ternary phosphoric acid ester polyether glycol, halogenated polyether polyvalent alcohol, dibromoneopentyl glycol, the tetrabromo-bisphenol.
4, according to the preparation method of claim 1 or 2 described inflaming retarding type copolymerization latex of urethane acrylate, it is characterized in that, in the step (1), described non-flame retardant resistance polyvalent alcohol is selected from polyether Glycols commonly used, polyester diol, polycarbonate diol, polybutadiene diol, polybutene glycol, acrylate polyvalent alcohol, polycaprolactone glycol, the mixture of one or more in the PTMG.
5, according to the preparation method of claim 1 or 2 described inflaming retarding type copolymerization latex of urethane acrylate, it is characterized in that, in the step (1), the described compound bearing active hydrogen that has that forms hydrophilic radical is selected from the dibasic alcohol that contains carboxyl structure, is one or more the mixture in dimethylol propionic acid, tartrate and the dibasic alcohol that contains the sulfonic acid structure.
6, the preparation method of inflaming retarding type copolymerization latex of urethane acrylate according to claim 1, it is characterized in that, in the step (2), described neutralizing agent is selected from the energy and the basic cpd of carboxylic acid and sulfonic acid, is one or more the mixture in triethylamine, tri-n-butylamine, sodium hydroxide, the ammoniacal liquor.
7, according to the preparation method of claim 1 or 6 described inflaming retarding type copolymerization latex of urethane acrylate, it is characterized in that, in the step (2), the described monomer that contains activity double key be selected from contain " C==C " double bond structure band can with the monomer of-NCO reactive activity hydrogen, be one or more mixture of Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, N hydroxymethyl acrylamide.
8, the preparation method of inflaming retarding type copolymerization latex of urethane acrylate according to claim 1 is characterized in that, in the step (3), described small molecule chain extender is selected from quadrol, hexanediamine, diethylenetriamine, hydrazine hydrate.
9, the preparation method of inflaming retarding type copolymerization latex of urethane acrylate according to claim 1, it is characterized in that, in the step (4), described initiator is selected from a kind of in Potassium Persulphate, ammonium persulphate, Diisopropyl azodicarboxylate, benzoyl peroxide, t-butyl hydroperoxide/xitix, the Potassium Persulphate/sodium bisulfite; Described vinylidene chloride/acrylate copolymer emulsion is a vinylidene chloride content at vinylidene chloride/acrylate copolymer emulsion of 30%～70%.
10, the preparation method of inflaming retarding type copolymerization latex of urethane acrylate according to claim 1, it is characterized in that, described acrylate monomer is selected from methyl acrylate, methyl methacrylate, ethyl propenoate, Jia Jibingxisuanyizhi, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, the mixture of one or more in butyl methacrylate, hexanediyl ester, decyl acrylate, lauryl methacrylate(LMA), hydroxyethyl methylacrylate, N hydroxymethyl acrylamide, vinyl cyanide, vinylbenzene, the acrylamide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100301141A CN100413901C (en) | 2005-09-29 | 2005-09-29 | Method for preparing inflaming retarding type copolymerization latex of urethane acrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100301141A CN100413901C (en) | 2005-09-29 | 2005-09-29 | Method for preparing inflaming retarding type copolymerization latex of urethane acrylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1760224A true CN1760224A (en) | 2006-04-19 |
| CN100413901C CN100413901C (en) | 2008-08-27 |
Family
ID=36706467
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100301141A Expired - Fee Related CN100413901C (en) | 2005-09-29 | 2005-09-29 | Method for preparing inflaming retarding type copolymerization latex of urethane acrylate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100413901C (en) |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102418276A (en) * | 2011-11-01 | 2012-04-18 | 吴江市北厍盛源纺织品助剂厂 | Preparation method of flame-retardant waterborne polyurethane |
| CN102585140A (en) * | 2011-01-13 | 2012-07-18 | 嘉纳尔科技（北京）有限公司 | Flame retardant polyurethane composition, flame retardant polyurethane foam material and method for preparing same |
| CN102858844A (en) * | 2010-03-29 | 2013-01-02 | 宇部兴产株式会社 | Process for production of polycarbonate diol diacrylate and high-purity polycarbonate diol diacrylate |
| CN101429270B (en) * | 2007-10-02 | 2013-04-10 | 香港科技大学 | Method for preparing aqueous polyacrylate modified polyurethane dispersions |
| CN103554466A (en) * | 2013-10-31 | 2014-02-05 | 淄博德信联邦化学工业有限公司 | Preparation method of flame-retardant polyether polyol containing phosphorus, chlorine and antimony |
| CN103709333A (en) * | 2013-12-17 | 2014-04-09 | 武汉海源九天新材料有限公司 | Self-phosphating waterborne polyurethane acrylate resin for axle and preparation method thereof |
| CN104292449A (en) * | 2014-09-29 | 2015-01-21 | 句容宁武新材料发展有限公司 | Preparation method and application of flame-retardant polyether |
| US20160280807A1 (en) * | 2015-03-24 | 2016-09-29 | Mark D. Soucek | Preparation of non-isocyanate urethane (meth) acrylates for urethane functional latex |
| CN106589297A (en) * | 2016-11-01 | 2017-04-26 | 北京理工大学 | High-efficient essence type aqueous polyurethane with flame retardation |
| CN106986979A (en) * | 2017-04-13 | 2017-07-28 | 合肥科天水性科技有限责任公司 | A kind of synchronous chain extension preparation technology of cationic aromatic aqueous polyurethane |
| CN107286306A (en) * | 2017-07-25 | 2017-10-24 | 东莞长联新材料科技股份有限公司 | A kind of aqueous polyurethane acrylate copolymer emulsion and preparation method thereof |
| CN107652762A (en) * | 2017-10-24 | 2018-02-02 | 惠州市舜丰印材科技有限公司 | A kind of PET film printing water ink and preparation method thereof |
| CN108231301A (en) * | 2017-12-30 | 2018-06-29 | 江苏华友装饰工程有限公司 | Preparation method of high-temperature-resistant high-thermal-conductivity mica tape |
| TWI629286B (en) * | 2017-06-13 | 2018-07-11 | 和友紡織股份有限公司 | Method for preparing super soft waterborne polyacrylate urethane core-core copolymer by solventless process |
| CN110684459A (en) * | 2019-11-01 | 2020-01-14 | 深圳纽沃新材料有限公司 | Flame-retardant UV-moisture dual-curing polyurethane acrylate three-proofing paint |
| CN113423748A (en) * | 2019-02-15 | 2021-09-21 | 日信化学工业株式会社 | Vinyl chloride resin emulsion, aqueous ink, and recording paper |
| CN115024189A (en) * | 2022-05-07 | 2022-09-09 | 大连地拓环境科技有限公司 | Multifunctional three-dimensional greening sponge matrix and preparation method thereof |
| CN115368521A (en) * | 2022-09-22 | 2022-11-22 | 清华大学 | Phosphorus-containing copolymer emulsion and preparation method and application thereof |
| CN117165140A (en) * | 2023-09-26 | 2023-12-05 | 北京蓝彬尚科建筑工程有限公司 | Coating with heat insulation and fireproof functions and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5128387A (en) * | 1987-07-28 | 1992-07-07 | Borden, Inc. | Extensible and pasteurizable radiation curable coating for metal |
| CN1176129C (en) * | 2001-04-23 | 2004-11-17 | 中国科学技术大学 | Phosphorus contained ultra-branched polyurethane acrylate as fire retarding agent solidified by radiation and its preparing process |
| CN100338111C (en) * | 2002-06-12 | 2007-09-19 | 中国科学院成都有机化学研究所 | Double-phobia polyurethane-polyacrylic ester microemulsion and preparation process thereof |
-
2005
- 2005-09-29 CN CNB2005100301141A patent/CN100413901C/en not_active Expired - Fee Related
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429270B (en) * | 2007-10-02 | 2013-04-10 | 香港科技大学 | Method for preparing aqueous polyacrylate modified polyurethane dispersions |
| CN102858844A (en) * | 2010-03-29 | 2013-01-02 | 宇部兴产株式会社 | Process for production of polycarbonate diol diacrylate and high-purity polycarbonate diol diacrylate |
| CN102858844B (en) * | 2010-03-29 | 2015-01-21 | 宇部兴产株式会社 | Process for production of polycarbonate diol diacrylate and high-purity polycarbonate diol diacrylate |
| CN102585140A (en) * | 2011-01-13 | 2012-07-18 | 嘉纳尔科技（北京）有限公司 | Flame retardant polyurethane composition, flame retardant polyurethane foam material and method for preparing same |
| CN102418276A (en) * | 2011-11-01 | 2012-04-18 | 吴江市北厍盛源纺织品助剂厂 | Preparation method of flame-retardant waterborne polyurethane |
| CN103554466A (en) * | 2013-10-31 | 2014-02-05 | 淄博德信联邦化学工业有限公司 | Preparation method of flame-retardant polyether polyol containing phosphorus, chlorine and antimony |
| CN103709333A (en) * | 2013-12-17 | 2014-04-09 | 武汉海源九天新材料有限公司 | Self-phosphating waterborne polyurethane acrylate resin for axle and preparation method thereof |
| CN103709333B (en) * | 2013-12-17 | 2016-05-25 | 武汉海源九天新材料有限公司 | A kind of vehicle bridge is used from phosphatization aqueous polyurethane acrylate resin and preparation method thereof |
| CN104292449A (en) * | 2014-09-29 | 2015-01-21 | 句容宁武新材料发展有限公司 | Preparation method and application of flame-retardant polyether |
| CN104292449B (en) * | 2014-09-29 | 2016-09-28 | 句容宁武新材料发展有限公司 | The preparation method of a kind of flame retarding polyether and the application of prepared product |
| US20160280807A1 (en) * | 2015-03-24 | 2016-09-29 | Mark D. Soucek | Preparation of non-isocyanate urethane (meth) acrylates for urethane functional latex |
| CN106589297A (en) * | 2016-11-01 | 2017-04-26 | 北京理工大学 | High-efficient essence type aqueous polyurethane with flame retardation |
| CN106986979A (en) * | 2017-04-13 | 2017-07-28 | 合肥科天水性科技有限责任公司 | A kind of synchronous chain extension preparation technology of cationic aromatic aqueous polyurethane |
| TWI629286B (en) * | 2017-06-13 | 2018-07-11 | 和友紡織股份有限公司 | Method for preparing super soft waterborne polyacrylate urethane core-core copolymer by solventless process |
| CN107286306A (en) * | 2017-07-25 | 2017-10-24 | 东莞长联新材料科技股份有限公司 | A kind of aqueous polyurethane acrylate copolymer emulsion and preparation method thereof |
| CN107652762A (en) * | 2017-10-24 | 2018-02-02 | 惠州市舜丰印材科技有限公司 | A kind of PET film printing water ink and preparation method thereof |
| CN108231301A (en) * | 2017-12-30 | 2018-06-29 | 江苏华友装饰工程有限公司 | Preparation method of high-temperature-resistant high-thermal-conductivity mica tape |
| CN113423748A (en) * | 2019-02-15 | 2021-09-21 | 日信化学工业株式会社 | Vinyl chloride resin emulsion, aqueous ink, and recording paper |
| CN113423748B (en) * | 2019-02-15 | 2024-05-10 | 日信化学工业株式会社 | Vinyl chloride resin emulsion, aqueous ink and recording paper |
| CN110684459A (en) * | 2019-11-01 | 2020-01-14 | 深圳纽沃新材料有限公司 | Flame-retardant UV-moisture dual-curing polyurethane acrylate three-proofing paint |
| CN110684459B (en) * | 2019-11-01 | 2021-07-13 | 深圳纽沃新材料有限公司 | Flame-retardant UV-moisture dual-curing polyurethane acrylate three-proofing paint |
| CN115024189A (en) * | 2022-05-07 | 2022-09-09 | 大连地拓环境科技有限公司 | Multifunctional three-dimensional greening sponge matrix and preparation method thereof |
| CN115368521A (en) * | 2022-09-22 | 2022-11-22 | 清华大学 | Phosphorus-containing copolymer emulsion and preparation method and application thereof |
| CN117165140A (en) * | 2023-09-26 | 2023-12-05 | 北京蓝彬尚科建筑工程有限公司 | Coating with heat insulation and fireproof functions and preparation method thereof |
| CN117165140B (en) * | 2023-09-26 | 2024-04-26 | 北京蓝彬尚科建筑工程有限公司 | Coating with heat insulation and fireproof functions and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100413901C (en) | 2008-08-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100413901C (en) | Method for preparing inflaming retarding type copolymerization latex of urethane acrylate | |
| CN100335522C (en) | Flame-retardant polyurethane water dispersion and its preparing method | |
| CN101225226B (en) | Method for preparing water-dispersion montmorillonite/organic block polyurethane nano composite material and uses thereof | |
| CN103130977B (en) | Polyurethane polyol dispersion of a kind of aqueous wood lacquer with double components and preparation method thereof | |
| CN101638464A (en) | Method for preparing polyurethane-polyacrylic ester microemulsion | |
| CN107698731B (en) | A kind of high rigidity acrylic acid-polyurethane emulsion that POSS/B is modified | |
| EP2834283A1 (en) | Polyurethane/acrylic hybrid dispersions for roof coatings and their preparation | |
| CN1880374A (en) | Acrylate polyurethane water-dispersed resin and its making method | |
| CN1926165A (en) | Hydrophobic low viscosity polyols | |
| CN1556145A (en) | Polyurethane-acrylate water dispersion resin and its preparation | |
| CN114573775B (en) | Phosphorus-containing flame-retardant copolymerized aqueous polyurethane and preparation method thereof | |
| CN111925642B (en) | Preparation method of self-repairing carbon nano tube-cationic waterborne polyurethane electromagnetic shielding composite material | |
| CN102702450A (en) | Preparation method of waterborne polyurethane-acrylate emulsion | |
| CN105778029A (en) | Preparation method of hyperbranched poly(isocyanurate-ester) type waterborne polyurethane | |
| JP5578406B2 (en) | One-part moisture curable sealant composition for improving antibacterial and antifungal properties of outer wall joint top coating film, and method for improving antibacterial and antifungal properties of outer wall joint top coating film using the same | |
| CN111171702B (en) | Dual-curing polyurethane aqueous dispersion and aqueous UV coating | |
| CN112778888B (en) | Process for producing polyurethane coating film and coating composition | |
| CN102356197B (en) | Paper coating composition | |
| KR100969247B1 (en) | Method for processing aqueous polyurethane dispersed solution with excellent suncream and abrasion resistance containing hydroxy group, and soft coating composition containing the same | |
| KR102053023B1 (en) | The reactive floor coating material composition and preparation method thereof | |
| CN104356020B (en) | A kind of amide groups ester and synthetic method, application | |
| CN104262575A (en) | Phosphate ester based epoxy modified waterborne polyurethane and preparation method thereof | |
| KR101009998B1 (en) | A process for preparing water-soluble polyurethane acrylate | |
| CN110511350B (en) | Polycarbon type waterborne polyurethane and preparation method thereof | |
| CN115926570B (en) | Water-based carbon dioxide-based polyurethane-acrylic acid interior wall coating and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20090814 Address after: Qingpu District of Shanghai City, Zhilu No. 1889 zip code: 201708 Co-patentee after: ALLIGATOR COATINGS (SHANGHAI) CO.,LTD. Patentee after: SHANGHAI SHENZHEN ENTERPRISE DEVELOPMENT Co.,Ltd. Address before: Qingpu District of Shanghai City, Zhilu No. 1889 zip code: 201708 Patentee before: SHANGHAI SHENZHEN ENTERPRISE DEVELOPMENT Co.,Ltd. |
|
| ASS | Succession or assignment of patent right |
Free format text: FORMER OWNER: ALLIGATOR COATINGS (SHANGHAI) CO., LTD. Effective date: 20111231 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20111231 Address after: Huaxin Town, Qingpu District 201708 of Shanghai City, No. 1889 Zhilu Patentee after: SHANGHAI SHENZHEN ENTERPRISE DEVELOPMENT Co.,Ltd. Address before: Qingpu District of Shanghai City, No. 1889 Zhilu 201708 Co-patentee before: ALLIGATOR COATINGS (SHANGHAI) CO.,LTD. Patentee before: SHANGHAI SHENZHEN ENTERPRISE DEVELOPMENT Co.,Ltd. |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20170703 Address after: 201703, No. 3966, Shanghai Qing Ping highway, Shanghai Patentee after: ALLIGATOR COATINGS (SHANGHAI) CO.,LTD. Address before: Huaxin Town, Qingpu District 201708 of Shanghai City, No. 1889 Zhilu Patentee before: SHANGHAI SHENZHEN ENTERPRISE DEVELOPMENT Co.,Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080827 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |