CN103450416A - Preparation method of cold-resistant acrylate resin paint - Google Patents
Preparation method of cold-resistant acrylate resin paint Download PDFInfo
- Publication number
- CN103450416A CN103450416A CN201310425854XA CN201310425854A CN103450416A CN 103450416 A CN103450416 A CN 103450416A CN 201310425854X A CN201310425854X A CN 201310425854XA CN 201310425854 A CN201310425854 A CN 201310425854A CN 103450416 A CN103450416 A CN 103450416A
- Authority
- CN
- China
- Prior art keywords
- weight
- acrylic resin
- preparation
- monomer
- temperature
- 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
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003973 paint Substances 0.000 title abstract 3
- 239000000178 monomer Substances 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000002086 nanomaterial Substances 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 239000000839 emulsion Substances 0.000 claims abstract description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 5
- 239000003999 initiator Substances 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims description 28
- 238000000576 coating method Methods 0.000 claims description 28
- 229920000178 Acrylic resin Polymers 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000009413 insulation Methods 0.000 claims description 18
- 230000035484 reaction time Effects 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 6
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-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
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 238000004945 emulsification Methods 0.000 claims description 6
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 6
- -1 methyl siloxane Chemical class 0.000 claims description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 6
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 6
- KZOJQMWTKJDSQJ-UHFFFAOYSA-M sodium;2,3-dibutylnaphthalene-1-sulfonate Chemical group [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CCCC)C(CCCC)=CC2=C1 KZOJQMWTKJDSQJ-UHFFFAOYSA-M 0.000 claims description 6
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 5
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 claims description 5
- 239000004902 Softening Agent Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- CPYRNEFBPGOZKT-UHFFFAOYSA-N 1-(2-methylpropyl)-4,5-dihydroimidazole Chemical class CC(C)CN1CCN=C1 CPYRNEFBPGOZKT-UHFFFAOYSA-N 0.000 claims description 3
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 claims description 3
- IHLDEDLAZNFOJB-UHFFFAOYSA-N 6-octoxy-6-oxohexanoic acid Chemical group CCCCCCCCOC(=O)CCCCC(O)=O IHLDEDLAZNFOJB-UHFFFAOYSA-N 0.000 claims description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 3
- 101710194948 Protein phosphatase PhpP Proteins 0.000 claims description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- VNJCDDZVNHPVNM-UHFFFAOYSA-N chloro(ethyl)silane Chemical compound CC[SiH2]Cl VNJCDDZVNHPVNM-UHFFFAOYSA-N 0.000 claims description 3
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 claims description 3
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 claims description 3
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 3
- XWVQUJDBOICHGH-UHFFFAOYSA-N dioctyl nonanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCC(=O)OCCCCCCCC XWVQUJDBOICHGH-UHFFFAOYSA-N 0.000 claims description 3
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 3
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- CRGGPIWCSGOBDN-UHFFFAOYSA-N magnesium;dioxido(dioxo)chromium Chemical compound [Mg+2].[O-][Cr]([O-])(=O)=O CRGGPIWCSGOBDN-UHFFFAOYSA-N 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 3
- 235000019801 trisodium phosphate Nutrition 0.000 claims description 3
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 claims description 2
- JYELWBARXZUASV-UHFFFAOYSA-N 1-(2-methylpropanoyloxy)pentyl 2-methylpropanoate Chemical class CCCCC(OC(=O)C(C)C)OC(=O)C(C)C JYELWBARXZUASV-UHFFFAOYSA-N 0.000 claims description 2
- BSWXAWQTMPECAK-UHFFFAOYSA-N 6,6-diethyloctyl dihydrogen phosphate Chemical compound CCC(CC)(CC)CCCCCOP(O)(O)=O BSWXAWQTMPECAK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 2
- 150000001409 amidines Chemical class 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 239000007859 condensation product Substances 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 239000004014 plasticizer Substances 0.000 abstract 1
- 150000003377 silicon compounds Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 206010016590 Fibrin deposition on lens postoperative Diseases 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
Abstract
The invention discloses a preparation method of cold-resistant acrylate resin paint. The preparation method comprises the following steps: adding de-ionized water, an emulsifier and acrylic acid; increasing the reaction temperature to 45 DEG C; stirring and reacting for 30 minutes; adding acrylate monomer to emulsify for 40-60 minutes; dropwise adding 0.3-0.5 percent by weight of ammonium persulfate for 1-4 hours at the temperature of 80 DEG C; preserving the temperature and reacting for 2-3hours; dropwise adding 2-8 percent by weight of organic silicon compound to react for 2-4 hours so as to obtain nuclear layer emulsion; simultaneously dropwise adding the acrylate monomer and 0.4-0.5 percent by weight of initiator into the nuclear layer emulsion for 2-3 hours; preserving the temperature at 80-90 DEG C and reacting for 1.5 hours; adding 6-9 percent of plasticizer and 5-15 percent of nanomaterial dispersion dropwise; preserving the temperature and reacting for 1-3 hours; cooling to 50 DEG C; adding 0.3 percent of OS-15 into the reaction system to react for 30 minutes; adding ammonia water to adjust the pH (potential of Hydrogen) value to be 7-8 so as to obtain the cold-resistant acrylate resin paint. The obtained acrylate resin can improve the defect of cold shortness of the conventional acrylate resin.
Description
Technical field
The present invention relates to a kind of preparation method of acrylic resin coating, particularly the preparation method of winter hardiness acrylic resin coating.
Background technology
Acrylic resin is a class coating of current widespread use, be widely used in the fields such as aviation, shipbuilding, vehicle, machinery, electronic industry, building, process hides, there is the advantages such as film forming is pliable and tough, high resilience, and coating is fast light, ageing-resistant, the wet-rub resistance energy is excellent, with low cost.But the acrylic resin coating of linear structure belongs to thermoplastic material, easily produce " hot sticky cold crisp " phenomenon, the normal core-shell emulsion polymerization method that adopts is improved at present.
The core-shell emulsion polymerization method can reduce the second-order transition temperature of acrylic resin preferably, improves the winter hardiness of coating, but the material used for fields such as external wall, process hides coating, machineries uses at lower temperature, and there is certain defect in this method.
Summary of the invention
The present invention has adopted following technical scheme.
(1) add deionized water weight 40 ~ 55%, emulsifying agent weight 0.4 ~ 1.7%, vinylformic acid weight 0.2 ~ 4.0% in reaction vessel, temperature of reaction is risen to 45 ℃, stir 30min, add the A monomer, emulsification times 40 ~ 60min.Logical recirculation water when temperature is raised to 70 ℃, start to drip ammonium persulphate weight 0.3 ~ 0.5% during to 80 ℃ of temperature, time for adding 1 ~ 4h, and insulation reaction 2 ~ 3h, dropping silicoorganic compound weight 2 ~ 8%, reaction times 2 ~ 4h, obtain the stratum nucleare emulsion;
A monomer and consumption thereof: the A monomer is mixed and is formed by Hydroxyethyl acrylate weight 5 ~ 8%, pentaerythritol triacrylate weight 4 ~ 6%, Propylene glycol monoacrylate weight 2.5 ~ 3.5%, 2-phenoxyethyl acrylate weight 0 ~ 3%;
(2) add nano material, dispersion agent weight 5 ~ 15%, cellulose 2 ~ 5% that weight is 2 ~ 3% in the deionized water that is 50 ~ 60% to weight, temperature is 30 ℃, shear agitation speed 700 ~ 2500rpm, regulation system pH7 ~ 8, churning time 20min, obtain the nano material dispersion liquid standby;
(3) drip B monomer and initiator weight 0.4 ~ 0.5% in the stratum nucleare emulsion simultaneously, time for adding 2 ~ 3h, 80 ~ 90 ℃ of insulation reaction time 1.5h, drip the nano material dispersion liquid 5 ~ 15% of softening agent 6 ~ 9% and above-mentioned (2), insulation reaction 1 ~ 3h, cool to 50 ℃, OS-15 weight 0.3% is added in reaction system, reaction times 30min, add ammoniacal liquor adjust pH 7 ~ 8, obtains winter hardiness acrylic resin coating;
B monomer and consumption thereof: the B monomer is mixed and is formed by vinylformic acid hydroxy butyl ester weight 3 ~ 5%, methyl methacrylate weight 0.5 ~ 3.5%, ethyl propenoate weight 3.5 ~ 6.5%, dodecyl acrylate weight 2 ~ 3.5%.
Emulsifying agent is sodium dibutyl naphthalene sulfonate and the OS-15 mixture by weight 3:1; Silicoorganic compound are any one in ethyl chlorosilane, dichloromethyl phenylsilane, a phenyl-trichloro-silicane, diphenyl dichlorosilane, α ﹒ ω hydroxyl-terminated injecting two methyl siloxane; Nano material is any one in nano-calcium carbonate, Nanoscale Chromic Oxides, nanometer magnesium chromate; Dispersion agent is any one in tripoly phosphate sodium STPP, Sodium hexametaphosphate 99, trisodium phosphate, triethyl hexyl phosphoric acid, naphthene sulfonic acid-formaldehyde condensation products; Mierocrystalline cellulose is any one in methylcellulose gum, Natvosol, hydroxypropylcellulose, Vltra tears, carboxymethyl cellulose; Initiator is any one in azo diisobutyl amidine hydrochloride, azo two isobutyl imidazoline salt hydrochlorates, azo dicyano valeric acid, azo di-isopropyl tetrahydroglyoxaline; Softening agent is Octyl adipate, diisodecyl adipate, dioctyl azelate, dioctyl sebacate, 2,2, any one of 4 one trimethylammonium one 1,3 one pentanediol diisobutyrates, butyl stearate, LHAT acid one glycol ether one two one 2 one ethyl acid esters, HMPA.
The present invention has following characteristics:
(1) prepared winter hardiness acrylic resin coating consistency is good, can obviously improve the cold short defect of conventional acrylic resinoid;
(2) softening agent, nano material, organosilicon, Mierocrystalline cellulose synergistic improve the winter hardiness of acrylic resin;
(3) hydroxy acrylate, vinylformic acid and organosilicon, fibrin reaction, improved kindliness and the winter hardiness of acrylic resin.
embodimentfurther illustrate the present invention below in conjunction with example.
example one
(1) add deionized water weight 40g, sodium dibutyl naphthalene sulfonate 0.3g, OS weight 0.1g, vinylformic acid weight 0.2g in the 250ml there-necked flask, temperature of reaction is risen to 45 ℃, stirring reaction 30min, add the A monomer, emulsification times 40min.Logical recirculation water when temperature is raised to 70 ℃, start to drip during to 80 ℃ of temperature and distill water-soluble ammonium persulfate solution weight 5.3g with 5g, time for adding 1h, and insulation reaction 2h, dropping ethyl chlorosilane 2g, reaction times 2h, obtain the stratum nucleare emulsion;
A monomer and consumption thereof: the A monomer is mixed and is formed by Hydroxyethyl acrylate weight 5g, pentaerythritol triacrylate weight 4g, Propylene glycol monoacrylate weight 2.5g;
(2) to the deionized water, nano-calcium carbonate 2g, tripoly phosphate sodium STPP 5g and the methylcellulose gum 2g that add 50g in the 200ml beaker, temperature is 30 ℃, shear agitation speed 700rpm, and regulation system pH7 ~ 8, churning time 20min, obtain the nano material dispersion liquid standby;
(3) to drip the B monomer in the stratum nucleare emulsion and with the water-soluble azo diisobutyl of 5g amidine hydrochloride solution weight 5.4g simultaneously, time for adding 2h, 80 ℃ of insulation reaction time 1.5h, drip Octyl adipate 6g and above-mentioned nano material dispersion liquid 5g, insulation reaction 1h, cool to 50 ℃, OS-15 weight 0.3g is added in there-necked flask, reaction times 30min, add ammoniacal liquor adjust pH 7 ~ 8, obtains winter hardiness acrylic resin coating;
B monomer and consumption thereof: the B monomer is mixed and is formed by vinylformic acid hydroxy butyl ester weight 3g, methyl methacrylate weight 0.5g, ethyl propenoate weight 3.5g, dodecyl acrylate weight 2g.
example two
(1) add deionized water weight 55g, sodium dibutyl naphthalene sulfonate 1.3g, OS weight 0.4g in the 250ml there-necked flask, vinylformic acid weight 4.0g, rise to 45 ℃ by temperature of reaction, and stirring reaction 30min, add the A monomer, emulsification times 60min.Logical recirculation water when temperature is raised to 70 ℃ of left and right, start to drip the ammonium persulfate solution weight 5.5g of use 5g deionized water dissolving, time for adding 4h during to 80 ℃ of temperature, insulation reaction 3h, drip dichloromethyl phenylsilane weight 8g, reaction times 4h, obtain the stratum nucleare emulsion;
A monomer and consumption thereof: the A monomer is mixed and is formed by Hydroxyethyl acrylate weight 8g, pentaerythritol triacrylate weight 6g, Propylene glycol monoacrylate weight 3.5g, 2-phenoxyethyl acrylate 3g;
(2) to adding the deionized water of 60g in the 200ml beaker, to weight, be 60g, Nanoscale Chromic Oxides 3g, Sodium hexametaphosphate 99 15g and Natvosol 5g, temperature is 30 ℃, shear agitation speed 2500rpm, regulation system pH7 ~ 8, churning time 20min, obtain the nano material dispersion liquid standby;
(3) to drip the B monomer in the stratum nucleare emulsion and with the water-soluble azo two isobutyl imidazoline salt acid salt solution weight 5.5g of 5g simultaneously, time for adding 3h, 90 ℃ of insulation reaction time 1.5h, drip diisodecyl adipate 9g and above-mentioned nano material dispersion liquid 15g, insulation reaction 3h, cool to 50 ℃, OS-15 weight 0.3g is added in there-necked flask, reaction times 30min, add ammoniacal liquor adjust pH 7 ~ 8, obtains winter hardiness acrylic resin coating;
B monomer and consumption thereof: the B monomer is mixed and is formed by vinylformic acid hydroxy butyl ester weight 5g, methyl methacrylate weight 3.5g, ethyl propenoate weight 6.5g, dodecyl acrylate weight 3.5g;
example three
(1) add deionized water weight 48g, sodium dibutyl naphthalene sulfonate 0.75g, OS weight 0.25g, vinylformic acid weight 2.1g in the 250ml there-necked flask, temperature of reaction is risen to 45 ℃, stir 30min, add the A monomer, emulsification times 50min.Logical recirculation water when temperature is raised to 70 ℃, start dropping during to 80 ℃ of temperature and distill water-soluble ammonium persulfate solution weight 5.4g with 5g, time for adding 2.5h, and insulation reaction 2.5h, drip a phenyl-trichloro-silicane weight 5g, and reaction times 3h, obtain the stratum nucleare emulsion;
A monomer and consumption thereof: the A monomer is mixed and is formed by Hydroxyethyl acrylate weight 6.5g, pentaerythritol triacrylate weight 5g, Propylene glycol monoacrylate weight 3g, 2-phenoxyethyl acrylate 1.5g;
(2) to the deionized water, Nanoscale Chromic Oxides 2.5g, trisodium phosphate 10g and the hydroxypropylcellulose 3.5g that add 55g in the 200ml beaker, temperature is 30 ℃, shear agitation speed 1600rpm, regulation system pH7 ~ 8, churning time 20min, obtain the nano material dispersion liquid standby;
(3) to drip the B monomer in the stratum nucleare emulsion and with the water-soluble azo dicyano of 5g valeric acid solution weight 5.5g simultaneously, time for adding 2.5h, 85 ℃ of insulation reaction time 1.5h, drip dioctyl azelate 7.5g and above-mentioned nano material dispersion liquid 10g, insulation reaction 2h, cool to 50 ℃, OS-15 weight 0.3g is added in reaction system, reaction times 30min, add ammoniacal liquor adjust pH 7 ~ 8, obtains winter hardiness acrylic resin coating;
B monomer and consumption thereof: the B monomer is mixed and is formed by vinylformic acid hydroxy butyl ester weight 4g, methyl methacrylate weight 2g, ethyl propenoate weight 5g, dodecyl acrylate weight 3g;
example four
(1) add deionized water weight 48g, sodium dibutyl naphthalene sulfonate 0.75g, OS weight 0.25g, vinylformic acid weight 2.1g in the 250ml there-necked flask, temperature of reaction is risen to 45 ℃, stir 30min, add the A monomer, emulsification times 50min.Logical recirculation water when temperature is raised to 70 ℃, start to drip during to 80 ℃ of temperature and distill water-soluble ammonium persulfate solution weight 5.4g with 5g, time for adding 2.5h, and insulation reaction 2.5h, dropping diphenyl dichlorosilane weight 5g, reaction times 3h, obtain the stratum nucleare emulsion;
A monomer and consumption thereof: the A monomer is mixed and is formed by Hydroxyethyl acrylate weight 6.5g, pentaerythritol triacrylate weight 5g, Propylene glycol monoacrylate weight 3g, 2-phenoxyethyl acrylate 1.5g;
(2) to the deionized water, nanometer magnesium chromate 2.5g, triethyl hexyl phosphatase 11 5g and the Vltra tears 4g that add 55g in the 200ml beaker, temperature is 30 ℃, shear agitation speed 1600rpm, regulation system pH7 ~ 8, churning time 20min, obtain the nano material dispersion liquid standby;
(3) to drip the B monomer in the stratum nucleare emulsion and with the water-soluble azo di-isopropyl of 5g imidazoline solutions weight 5.5g simultaneously, time for adding 2.5h, 85 ℃ of insulation reaction time 1.5h, drip the above-mentioned nano material dispersion liquid of dioctyl sebacate 7.5g 10g, insulation reaction 2h, cool to 50 ℃, OS-15 weight 0.3g is added in there-necked flask, reaction times 30min, add ammoniacal liquor adjust pH 7 ~ 8, obtains winter hardiness acrylic resin coating;
B monomer and consumption thereof: the B monomer is mixed and is formed by vinylformic acid hydroxy butyl ester weight 4g, methyl methacrylate weight 2g, ethyl propenoate weight 5g, dodecyl acrylate weight 3g;
Table one and table two are winter hardiness temperature of the prepared winter hardiness acrylic resin coating of example one, two, three, four of the present invention, are designated as D, E, F, G, and CL277 is reasonable winter hardiness acrylate resin on market.
The cold-resistant temperature of table one winter hardiness acrylic resin coating institute film forming
| Title | CL277 | D | E | F | G |
| Cold-resistant temperature/℃ | -15 | -35 | -22 | -26 | -27 |
As shown in Table 1, after having used winter hardiness acrylic resin coating of the present invention institute film forming, cold-resistant temperature significantly reduces.
Table two winter hardiness acrylic resin coating institute film forming the flexibility of subzero 20 ℃
| Title | CL277 | D | E | F | G |
| Flexibility | Firmly | Soft | Softer | Soft | Soft |
The flexibility of institute's film forming is divided into firmly, more soft soft, coating flexibility prepared by the present invention is all relatively good.
Claims (8)
1. the preparation method of a winter hardiness acrylic resin coating is characterized in that:
(1) add deionized water weight 40 ~ 55%, emulsifying agent weight 0.4 ~ 1.7%, vinylformic acid weight 0.2 ~ 4.0% in reaction vessel, temperature of reaction is risen to 45 ℃, stir 30min, add the A monomer, emulsification times 40 ~ 60min; Logical recirculation water when temperature is raised to 70 ℃, start to drip ammonium persulphate weight 0.3 ~ 0.5% during to 80 ℃ of temperature, time for adding 1 ~ 4h, and insulation reaction 2 ~ 3h, dropping silicoorganic compound weight 2 ~ 8%, reaction times 2 ~ 4h, obtain the stratum nucleare emulsion;
A monomer and consumption thereof: the A monomer is mixed and is formed by Hydroxyethyl acrylate weight 5 ~ 8%, pentaerythritol triacrylate weight 4 ~ 6%, Propylene glycol monoacrylate weight 2.5 ~ 3.5%, 2-phenoxyethyl acrylate weight 0 ~ 3%;
(2) add nano material, dispersion agent weight 5 ~ 15%, cellulose 2 ~ 5% that weight is 2 ~ 3% in the deionized water that is 50 ~ 60% to weight, temperature is 30 ℃, shear agitation speed 700 ~ 2500rpm, regulation system pH7 ~ 8, churning time 20min, obtain the nano material dispersion liquid standby;
(3) drip B monomer and initiator weight 0.4 ~ 0.5% in the stratum nucleare emulsion simultaneously, time for adding 2 ~ 3h, 80 ~ 90 ℃ of insulation reaction time 1.5h, drip the nano material dispersion liquid 5 ~ 15% of softening agent 6 ~ 9% and above-mentioned (2), insulation reaction 1 ~ 3h, cool to 50 ℃, OS-15 weight 0.3% is added in reaction system, reaction times 30min, add ammoniacal liquor adjust pH 7 ~ 8, obtains winter hardiness acrylic resin coating;
B monomer and consumption thereof: the B monomer is mixed and is formed by vinylformic acid hydroxy butyl ester weight 3 ~ 5%, methyl methacrylate weight 0.5 ~ 3.5%, ethyl propenoate weight 3.5 ~ 6.5%, dodecyl acrylate weight 2 ~ 3.5%.
2. the preparation method of a kind of winter hardiness acrylic resin coating as claimed in claim 1 is characterized in that: emulsifying agent is sodium dibutyl naphthalene sulfonate and the OS-15 mixture by weight 3:1.
3. the preparation method of a kind of winter hardiness acrylic resin coating as claimed in claim 1, it is characterized in that: silicoorganic compound are any one in ethyl chlorosilane, dichloromethyl phenylsilane, a phenyl-trichloro-silicane, diphenyl dichlorosilane, α ﹒ ω hydroxyl-terminated injecting two methyl siloxane.
4. the preparation method of a kind of winter hardiness acrylic resin coating as claimed in claim 1, it is characterized in that: nano material is any one in nano-calcium carbonate, Nanoscale Chromic Oxides, nanometer magnesium chromate.
5. the preparation method of a kind of winter hardiness acrylic resin coating as claimed in claim 1, it is characterized in that: dispersion agent is any one in tripoly phosphate sodium STPP, Sodium hexametaphosphate 99, trisodium phosphate, triethyl hexyl phosphoric acid, naphthene sulfonic acid-formaldehyde condensation products.
6. the preparation method of a kind of winter hardiness acrylic resin coating as claimed in claim 1, it is characterized in that: Mierocrystalline cellulose is any one in methylcellulose gum, Natvosol, hydroxypropylcellulose, Vltra tears, carboxymethyl cellulose.
7. the preparation method of a kind of winter hardiness acrylic resin coating as claimed in claim 1, it is characterized in that: initiator is any one in azo diisobutyl amidine hydrochloride, azo two isobutyl imidazoline salt hydrochlorates, azo dicyano valeric acid, azo di-isopropyl tetrahydroglyoxaline.
8. the preparation method of a kind of winter hardiness acrylic resin coating as claimed in claim 1, it is characterized in that: softening agent is Octyl adipate, diisodecyl adipate, dioctyl azelate, dioctyl sebacate, 2,2, any one of 4 one trimethylammonium one 1,3 one pentanediol diisobutyrates, butyl stearate, LHAT acid one glycol ether one two one 2 one ethyl acid esters, HMPA.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310425854.XA CN103450416B (en) | 2013-09-18 | 2013-09-18 | Preparation method of cold-resistant acrylate resin paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310425854.XA CN103450416B (en) | 2013-09-18 | 2013-09-18 | Preparation method of cold-resistant acrylate resin paint |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103450416A true CN103450416A (en) | 2013-12-18 |
| CN103450416B CN103450416B (en) | 2015-05-13 |
Family
ID=49733281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310425854.XA Active CN103450416B (en) | 2013-09-18 | 2013-09-18 | Preparation method of cold-resistant acrylate resin paint |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103450416B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819992A (en) * | 2014-03-24 | 2014-05-28 | 段宝荣 | Preparation method of light resistance coating |
| CN103937364A (en) * | 2014-05-04 | 2014-07-23 | 段小宁 | Preparation method of light-resistant and waterproof paint |
| CN104087106A (en) * | 2014-08-06 | 2014-10-08 | 段宝荣 | Preparation method of light-resistant water-based paint and adhesive |
| CN105111876A (en) * | 2014-07-27 | 2015-12-02 | 朱蕾 | Preparation method of core-shell type water-based acrylic resin paint for building and furniture |
| CN105778686A (en) * | 2016-03-16 | 2016-07-20 | 郑州航空工业管理学院 | Preparation method for aircraft leather cushion finishing agent and building external wall coating |
| CN107903553A (en) * | 2017-12-04 | 2018-04-13 | 青岛岩康塑料机械有限公司 | Preparation method with toughness, the acrylic resin of hardness under a kind of low temperature |
| CN109360682A (en) * | 2018-09-25 | 2019-02-19 | 青岛长城巨龙电缆有限公司 | Super low-temperature resistant environmental protection flexible cable and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086246A (en) * | 2010-11-29 | 2011-06-08 | 江苏足迹涂料有限公司 | Method for preparing nano silica-fluorine-containing acrylic resin through in-situ solution polymerization |
-
2013
- 2013-09-18 CN CN201310425854.XA patent/CN103450416B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086246A (en) * | 2010-11-29 | 2011-06-08 | 江苏足迹涂料有限公司 | Method for preparing nano silica-fluorine-containing acrylic resin through in-situ solution polymerization |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103819992A (en) * | 2014-03-24 | 2014-05-28 | 段宝荣 | Preparation method of light resistance coating |
| CN103937364A (en) * | 2014-05-04 | 2014-07-23 | 段小宁 | Preparation method of light-resistant and waterproof paint |
| CN103937364B (en) * | 2014-05-04 | 2016-01-20 | 佛山市顺德区合胜化工实业有限公司 | A kind of fast light preparation method with preventing water coating |
| CN105111876A (en) * | 2014-07-27 | 2015-12-02 | 朱蕾 | Preparation method of core-shell type water-based acrylic resin paint for building and furniture |
| CN105111876B (en) * | 2014-07-27 | 2017-06-13 | 河北晨阳工贸集团有限公司 | Building, the preparation method of the core-shell type aqueous acrylic resin coating of furniture |
| CN104087106A (en) * | 2014-08-06 | 2014-10-08 | 段宝荣 | Preparation method of light-resistant water-based paint and adhesive |
| CN105778686A (en) * | 2016-03-16 | 2016-07-20 | 郑州航空工业管理学院 | Preparation method for aircraft leather cushion finishing agent and building external wall coating |
| CN107903553A (en) * | 2017-12-04 | 2018-04-13 | 青岛岩康塑料机械有限公司 | Preparation method with toughness, the acrylic resin of hardness under a kind of low temperature |
| CN109360682A (en) * | 2018-09-25 | 2019-02-19 | 青岛长城巨龙电缆有限公司 | Super low-temperature resistant environmental protection flexible cable and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103450416B (en) | 2015-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103450416B (en) | Preparation method of cold-resistant acrylate resin paint | |
| CN103864982B (en) | Preparation method of fluorinated acrylate emulsion | |
| CN101429267B (en) | Preparation and uses of epoxy/acrylic acid hybridisation emulsion | |
| CN107266626A (en) | A kind of multiple self-crosslinking core-shell type emulsion of room temperature and its preparation method and application | |
| CN105859936B (en) | Acrylate copolymer emulsion and using it as the aqueous industrial anti-decaying paint of film forming matter | |
| CN106832106A (en) | A kind of water polyacrylic acid emulsion and preparation method thereof | |
| CN102993355A (en) | Preparation method of acrylate microemulsion with high solid content | |
| CN103059681B (en) | Water-based quick-drying external crosslinking functional paint and preparation method thereof | |
| CN104877089A (en) | Preparation method of modified fluorine-containing acrylic superhydrophobic resin emulsion | |
| CN102167946A (en) | Waterborne anti-corrosive primer and preparation method thereof | |
| CN101638541A (en) | Waterborne rusted paint and preparation method thereof | |
| CN103130943A (en) | Preparation method of water-borne acrylic resin emulsion for wood paint | |
| CN106118365A (en) | A kind of shock resistance Cold resistant paint based on graphene powder and preparation method thereof | |
| CN105175615A (en) | Water-based environment-friendly film-forming material applied in steel fastener surface, and preparation method and application thereof | |
| CN108517173A (en) | A kind of preparation method of ultra-hydrophobic property polyaniline composite anticorrosion coating | |
| CN105820719A (en) | Base coat used for air conditioner foil and preparation method thereof | |
| CN103833888A (en) | Preparation method of aqueous fluorine-modified phosphorus-containing acrylate emulsion | |
| CN103755890A (en) | Method for preparing special epoxy modified polyacrylate emulsion for waterborne industrial paints | |
| CN104761676A (en) | Preparation method of super-stable water-based polyacrylate emulsion | |
| JP2012087283A (en) | Polymerization method for acrylic latex without emulisifier | |
| CN103694403A (en) | Preparation method of self-crosslinking polyester film primer acrylic ester emulsion | |
| CN102533018B (en) | Antirust paint emulsion and its preparation method | |
| CN107417850A (en) | Pure-acrylic emulsion and preparation method thereof and metal Roof waterproof antirusting paint | |
| CN105693944B (en) | A kind of preparation method of heat resist modification styrene-acrylic emulsion | |
| CN105085779B (en) | With the high-solid-content and low-viscosity high stability polyacrylate dispersion and method of the preparation of double polymerisable emulsifiers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent of invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Yang Xiaofang Inventor after: Peng Yun Inventor after: Lu Jianguo Inventor after: Sun Hengji Inventor after: Li Cheng Inventor after: Zou Zhonghua Inventor before: Duan Baorong Inventor before: Gao Long Inventor before: Song Yu |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: DUAN BAORONG GAO LONG SONG YU TO: YANG XIAOFANG PENG YUN LU JIANGUO SUN HENGJI LI CHENG ZOU ZHONGHUA |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: ZHONGSHAN BOHAI FINE CHEMICALS CO., LTD. Free format text: FORMER OWNER: DUAN BAORONG Effective date: 20150508 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 264005 YANTAI, SHANDONG PROVINCE TO: 528447 ZHONGSHAN, GUANGDONG PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20150508 Address after: Wood River port town in Guangdong province Zhongshan City West Jing 528447 No. 5 Patentee after: ZHONGSHAN BOHAI FINE CHEMICAL CO.,LTD. Address before: 264005 Shandong Province, Yantai city Laishan District Road No. 30 spring Patentee before: Duan Baorong |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20161017 Address after: 526000 Guangdong city of Zhaoqing Province Gaoyao District Gaoyao Jinli Gaoyao Avenue and Han industrial base room 211 Patentee after: GUANGDONG BOHAI CHEMICAL TECHNOLOGY Co.,Ltd. Address before: Wood River port town in Guangdong province Zhongshan City West Jing 528447 No. 5 Patentee before: ZHONGSHAN BOHAI FINE CHEMICAL CO.,LTD. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170605 Address after: Wood River port town in Guangdong province Zhongshan City West Jing 528400 No. 5 Patentee after: ZHONGSHAN BOHAI FINE CHEMICAL CO.,LTD. Address before: 526000 Guangdong city of Zhaoqing Province Gaoyao District Gaoyao Jinli Gaoyao Avenue and Han industrial base room 211 Patentee before: GUANGDONG BOHAI CHEMICAL TECHNOLOGY Co.,Ltd. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Preparation method of cold-resistant acrylate resin paint Effective date of registration: 20170920 Granted publication date: 20150513 Pledgee: Postal Savings Bank of China Limited by Share Ltd. Zhongshan branch Pledgor: ZHONGSHAN BOHAI FINE CHEMICAL CO.,LTD. Registration number: 2017440000088 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20220803 Granted publication date: 20150513 Pledgee: Postal Savings Bank of China Limited by Share Ltd. Zhongshan branch Pledgor: ZHONGSHAN BOHAI FINE CHEMICAL CO.,LTD. Registration number: 2017440000088 |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221019 Address after: 526000 room 211, Hanhe Gaoyao industrial base, Jinli Avenue, Jinli Town, Gaoyao District, Zhaoqing City, Guangdong Province Patentee after: GUANGDONG BOHAI CHEMICAL TECHNOLOGY Co.,Ltd. Address before: 528400 No. 5 Muhe Lingxi Port Town, Zhongshan City, Guangdong Province Patentee before: ZHONGSHAN BOHAI FINE CHEMICAL CO.,LTD. |