CN103265704A - Organic silicon modified acrylic ultraviolet curable water-based resin and preparation method thereof - Google Patents
Organic silicon modified acrylic ultraviolet curable water-based resin and preparation method thereof Download PDFInfo
- Publication number
- CN103265704A CN103265704A CN2013102078877A CN201310207887A CN103265704A CN 103265704 A CN103265704 A CN 103265704A CN 2013102078877 A CN2013102078877 A CN 2013102078877A CN 201310207887 A CN201310207887 A CN 201310207887A CN 103265704 A CN103265704 A CN 103265704A
- Authority
- CN
- China
- Prior art keywords
- acid
- reaction
- catalyzer
- silicone oil
- organosilicon
- 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
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 21
- 239000010703 silicon Substances 0.000 title claims abstract description 21
- 239000011347 resin Substances 0.000 title abstract description 8
- 229920005989 resin Polymers 0.000 title abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 7
- 238000002360 preparation method Methods 0.000 title abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229920002545 silicone oil Polymers 0.000 claims abstract description 49
- 239000001257 hydrogen Substances 0.000 claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 40
- 239000000178 monomer Substances 0.000 claims abstract description 36
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims abstract description 35
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 10
- 238000012986 modification Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 67
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 66
- 239000002253 acid Substances 0.000 claims description 62
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 60
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 54
- 239000000203 mixture Substances 0.000 claims description 49
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 36
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 36
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 32
- 229920000642 polymer Polymers 0.000 claims description 31
- 239000004593 Epoxy Substances 0.000 claims description 28
- 229920000647 polyepoxide Polymers 0.000 claims description 28
- 239000013035 waterborne resin Substances 0.000 claims description 25
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 17
- 238000010792 warming Methods 0.000 claims description 17
- 150000002431 hydrogen Chemical class 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 11
- 150000002924 oxiranes Chemical group 0.000 claims description 11
- 238000001556 precipitation Methods 0.000 claims description 11
- 230000003252 repetitive effect Effects 0.000 claims description 11
- 238000005201 scrubbing Methods 0.000 claims description 11
- 238000001291 vacuum drying Methods 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000000839 emulsion Substances 0.000 abstract description 2
- 239000010985 leather Substances 0.000 abstract description 2
- 238000009988 textile finishing Methods 0.000 abstract description 2
- 238000007865 diluting Methods 0.000 abstract 1
- 238000006459 hydrosilylation reaction Methods 0.000 abstract 1
- 238000009835 boiling Methods 0.000 description 10
- 238000000016 photochemical curing Methods 0.000 description 7
- 238000009413 insulation Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001723 curing Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002650 habitual effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 231100000652 hormesis Toxicity 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Landscapes
- Silicon Polymers (AREA)
Abstract
The invention relates to a preparation method of an organic silicon modified acrylic ultraviolet curable water-based resin. The method comprises the following steps of: carrying out a hydrosilylation reaction between a hydrogen-containing silicone oil and glycidyl methacrylate so as to synthesize silicone oil containing a side epoxy group; then reacting the silicone oil containing the side epoxy group with an acrylic monomer to obtain a low-viscosity organic silicon acrylic prepolymer; and finally, performing grafting modification on the low-viscosity organic silicon acrylic prepolymer by using tetra-hydrophthalic anhydride and introducing a hydrophilic group to the molecular chain, thus obtaining the organic silicon modified acrylic ultraviolet curable water-based resin; besides, diluting the organic silicon modified acrylic ultraviolet curable water-based resin by adding water for efficient dispersion, thereby obtaining an ultraviolet curable organic silicon modified acrylic water-based emulsion. The product prepared by the method can be applied to technical fields of textile finishing, exterior wall coating, leather finishing and the like.
Description
Technical field
The present invention relates to a kind of organosilicon-modified acrylic UV-curable water-borne resin and preparation method thereof.
Background technology
UV-curing technology and coating thereof have obtained developing rapidly and using in recent years, but habitual esters of acrylic acid reactive thinner has stronger hormesis to people's skin and eyes in traditional oiliness curing system, influences the healthy of operator; Many reactive thinners are difficult to complete reaction in the ultraviolet light irradiation process in addition, and residual monomer directly has influence on the long-term behaviour of cured film, and have limited its application in the food sanitation industry.And aqueous solidified coating combines the advantage of traditional curing technology and water-borne coatings technology, and particularly environmentally safe does not have influence to HUMAN HEALTH, nonflammable, security is good, is developed fast over past ten years, and has become a main direction of coating development.
Acrylic resin itself has that look shallow, transparency is high, protects light, light is plentiful, absorb characteristics such as little at infrared region, and has advantage such as excellent erosion resistance, strong adhesion and monomer are numerous, synthetic easily, low price and be used widely.
The singularity of organosilicon polymer structure has been given its many excellent properties: ventilation property, snappiness, weathering resistance, water-repellancy and good physiology inertia, photocuring technology has fast setting, less energy-consumption, high-level efficiency, advantage such as pollution-free, the photocuring organosilicon material is extremely people's favor owing to the advantage that has both concurrently, and is used widely.
The photocuring organosilicon not only can be used as auxiliary agent and joins in the photocuring system, improves wettability, scratch resistance and the flow leveling of material, can also add photocuring system as reactive monomer, improves surface property, thermostability and the mechanical property of material.
In the prior art, adopt silicon hydrogen additive process to prepare organosilicon-modified acrylic, concrete grammar is: adopt the acrylic resin that contains organosilane or the organo-siloxane of reactive hydrogen and have a unsaturated link(age) to carry out the addition of silicon hydrogen and the organosilicon chain is incorporated in the acrylic resin.But existing organosilicon-modified acrylic adopts addition reaction of silicon with hydrogen, and the modified resin that is synthesized is a hydrophilic resin, has but lost the performance of ultraviolet light polymerization, and this severe reaction conditions, and productive rate is low, the cost height.
Summary of the invention
One of purpose of the present invention is to provide a kind of method of organosilicon-modified acrylic UV-curable water-borne resin, described method reaction conditions gentleness, the productive rate height, cost is low, and the photocuring water-base resin for preparing is both hydrophilic, simultaneously can ultraviolet light polymerization, have excellent surface property, thermostability and mechanical property.
In order to achieve the above object, the present invention has adopted following technical scheme:
A kind of method of organosilicon-modified acrylic UV-curable water-borne resin, described method comprises the steps:
(1) will contain pendant epoxies base silicone oil and stopper and add in the reaction vessel, under nitrogen protection, slowly dropwise addition of acrylic acid monomer and catalyzer in the reaction vessel, reaction, when pH in the reaction system was 7.0, stopped reaction obtained the acid-organosilicon crylic acid performed polymer;
(2) drip the mixing solutions of tetrahydrophthalic anhydride, stopper and catalyzer in the acid-organosilicon crylic acid performed polymer that obtains to step (1), 60～70 ℃ of reactions, when acid number reaches theoretical value, be cooled to room temperature, obtain organosilicon-modified acrylic UV-curable water-borne resin.
Preferably, under nitrogen protection, stir be warming up to 80～90 ℃ after, slowly dropwise addition of acrylic acid monomer and catalyzer in the reaction vessel, the preferred stirring is warming up to 82～88 ℃, further preferred 83～87 ℃.Described intensification temperature for example is 81 ℃, 81.5 ℃, 82.5 ℃, 83.5 ℃, 84 ℃, 85 ℃, 86 ℃, 87.5 ℃, 88.5 ℃, 89.5 ℃.
Preferably, the dropping time of Acrylic Acid Monomer and catalyzer is 1～1.5 hour, for example 1.05 hours, 1.1 hours, 1.15 hours, 1.2 hours, 1.25 hours, 1.3 hours, 1.35 hours, 1.4 hours, 1.45 hours, preferred 1.06～1.47 hours, further preferred 1.12～1.42 hours.
Preferably, the described temperature of reaction of step (1) is 90～100 ℃, for example 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, and preferred 91.5～98.5 ℃, further preferred 92.5～97.5 ℃.
Preferably, the described reaction times of step (1) is 2～6 hours, for example 2.2 hours, 2.4 hours, 2.7 hours, 3.2 hours, 3.6 hours, 4 hours, 4.4 hours, 4.8 hours, 5.2 hours, 5.6 hours, preferred 2.5～5.5 hours, further preferred 3～5.5 hours.
In reaction process, the pH value of assaying reaction system at any time, when pH in the reaction system was 7.0, stopped reaction obtained the acid-organosilicon crylic acid performed polymer.
Preferably, the carboxyl molar mass of described Acrylic Acid Monomer is 1:1 with the ratio of the epoxy group(ing) molar mass that contains pendant epoxies base silicone oil, so that react completely.
Preferably, described stopper is selected from the mixture of any one or at least two kinds in MEHQ, p methoxy phenol, Resorcinol or the 2,6 ditertiary butyl p cresol.Described mixture for example 2, the mixture of 6-ditertbutylparacresol and Resorcinol, the mixture of Resorcinol and p methoxy phenol, the mixture of p methoxy phenol and MEHQ, 2, the mixture of 6-ditertbutylparacresol and p methoxy phenol, the mixture of Resorcinol and MEHQ, 2, the mixture of 6-ditertbutylparacresol, Resorcinol and p methoxy phenol, the mixture of Resorcinol, p methoxy phenol, MEHQ and 2,6 ditertiary butyl p cresol.
Preferably, the mass percent that the quality of the described stopper of step (1) accounts for the total mass of all raw materials of step (1) is 0.2～1.2wt%, for example 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, preferred 0.25～1.15wt%, further preferred 0.35～1.05wt%.All raw materials are namely: contain pendant epoxies base silicone oil, stopper, Acrylic Acid Monomer and catalyzer.
Preferably, described catalyzer is selected from triethylamine, Tetramethylammonium hydroxide, tetraethylammonium bromide or N, the mixture of any one in the N-dimethylbenzyl ammonium or at least two kinds.Described mixture is N for example, the mixture of N-dimethylbenzyl ammonium and tetraethylammonium bromide, the mixture of tetraethylammonium bromide and Tetramethylammonium hydroxide, the mixture of Tetramethylammonium hydroxide and triethylamine, N, the mixture of N-dimethylbenzyl ammonium and Tetramethylammonium hydroxide, the mixture of tetraethylammonium bromide and triethylamine, N, the mixture of N-dimethylbenzyl ammonium, tetraethylammonium bromide and Tetramethylammonium hydroxide, Tetramethylammonium hydroxide, triethylamine, N, the mixture of N-dimethylbenzyl ammonium and tetraethylammonium bromide.
Preferably, the mass percent that the quality of the described catalyzer of step (1) accounts for the total mass of all raw materials of step (1) is 0.4～1.5wt%, for example 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, preferred 0.45～1.45wt%, further preferred 0.55～1.35wt%.All raw materials are namely: contain pendant epoxies base silicone oil, stopper, Acrylic Acid Monomer and catalyzer.
Preferably, drip the mixing solutions of tetrahydrophthalic anhydride, stopper and catalyzer during the acid-organosilicon crylic acid performed polymer that step (2) obtains step (1) is cooled to after 60～70 ℃, preferably be cooled to 61～69 ℃, further preferably be cooled to 62～68 ℃.Described cooling temperature for example is 60.5 ℃, 61.5 ℃, 62.5 ℃, 63 ℃, 64 ℃, 65 ℃, 66 ℃, 67 ℃, 68.5 ℃, 69.5 ℃.
In reaction process, acid number in the detection reaction system when acid number reaches theoretical value, is cooled to room temperature, and the side chain that obtains the tetrahydrophthalic anhydride modification has the organosilicon-modified acrylic UV-curable water-borne resin of hydrophilic radical carboxyl.Described theoretical value can obtain by following principle: in theory, the tetrahydrophthalic anhydride that adds 1 mole generates 1 mole carboxyl, according to the amount of the tetrahydrophthalic anhydride that adds, calculates the growing amount of theoretical carboxyl, and then determines theoretical acid number amount.
Preferably, described stopper is selected from the mixture of any one or at least two kinds in MEHQ, p methoxy phenol, Resorcinol or the 2,6 ditertiary butyl p cresol.Described mixture for example 2, the mixture of 6-ditertbutylparacresol and Resorcinol, the mixture of Resorcinol and p methoxy phenol, the mixture of p methoxy phenol and MEHQ, 2, the mixture of 6-ditertbutylparacresol and p methoxy phenol, the mixture of Resorcinol and MEHQ, 2, the mixture of 6-ditertbutylparacresol, Resorcinol and p methoxy phenol, the mixture of Resorcinol, p methoxy phenol, MEHQ and 2,6 ditertiary butyl p cresol.
Preferably, the mass percent that the quality of the described stopper of step (2) accounts for the total mass of all raw materials of step (2) is 0.2～1.2wt%, for example 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, preferred 0.25～1.15wt%, further preferred 0.35～1.05wt%.All raw materials are namely: acid-organosilicon crylic acid performed polymer, tetrahydrophthalic anhydride, stopper and catalyzer.
Preferably, described catalyzer is selected from triethylamine, Tetramethylammonium hydroxide, tetraethylammonium bromide or N, the mixture of any one in the N-dimethylbenzyl ammonium or at least two kinds.Described mixture is N for example, the mixture of N-dimethylbenzyl ammonium and tetraethylammonium bromide, the mixture of tetraethylammonium bromide and Tetramethylammonium hydroxide, the mixture of Tetramethylammonium hydroxide and triethylamine, N, the mixture of N-dimethylbenzyl ammonium and Tetramethylammonium hydroxide, the mixture of tetraethylammonium bromide and triethylamine, N, the mixture of N-dimethylbenzyl ammonium, tetraethylammonium bromide and Tetramethylammonium hydroxide, Tetramethylammonium hydroxide, triethylamine, N, the mixture of N-dimethylbenzyl ammonium and tetraethylammonium bromide.
Preferably, the mass percent that the quality of the described catalyzer of step (2) accounts for the total mass of all raw materials of step (2) is 0.4～1.5wt%, for example 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, preferred 0.45～1.45wt%, further preferred 0.55～1.35wt%.All raw materials are namely: acid-organosilicon crylic acid performed polymer, tetrahydrophthalic anhydride, stopper and catalyzer.
Preferably, the molar mass of described tetrahydrophthalic anhydride is 1:1 with the ratio of the molar mass of acid-organosilicon crylic acid performed polymer hydroxyl.
Preferably, the described pendant epoxies base silicone oil that contains is prepared by following method:
Add 100 parts of containing hydrogen silicone oils, 10～20 parts of glycidyl methacrylate, 0.1～5 part of isopropyl alcohol solution of chloroplatinic acid and 30～100 parts of solvents in container, 90～110 ℃ by silicon hydrogen addition isothermal reaction discharging in 6～12 hours; Do precipitation agent with methyl alcohol reaction product be precipitated out, and with methyl alcohol repetitive scrubbing throw out, removing unreacted monomer and catalyzer Platinic chloride, after the vacuum-drying faint yellow transparent side base band epoxide group arranged contain pendant epoxies base silicone oil.
Described temperature of reaction is 90～110 ℃, and for example 92 ℃, 94 ℃, 96 ℃, 98 ℃, 102 ℃, 104 ℃, 106 ℃, 108 ℃, the described reaction times is 6～12 hours, for example 7 hours, 8 hours, 9 hours, 10 hours, 11 hours.
The massfraction of the reactive hydrogen of described containing hydrogen silicone oil is 0.06～0.2wt%, for example 0.08wt%, 0.1wt%, 0.12wt%, 0.14wt%, 0.16wt%, 0.18wt%, 0.19wt%, preferred 0.07～0.17wt%, further preferred 0.08～0.15wt%.
The massfraction of Platinic chloride is 1～3wt% in the described isopropyl alcohol solution of chloroplatinic acid, for example 1.2wt%, 1.4wt%, 1.6wt%, 1.8wt%, 2.1wt%, 2.3wt%, 2.5wt%, 2.7wt%, 2.9wt%, preferred 1.1～2.8wt%, further preferred 1.3～2.6wt%.
Described solvent is selected from the mixture of any one or at least two kinds in toluene, dimethylbenzene, ethyl glycollate, ethyl acetate, acetone, butanone, diacetylmethane, Virahol, butanols, diacetone alcohol, ether, sherwood oil, glycerine or the aromatic alcohol.Described mixture is the mixture of toluene and dimethylbenzene for example, the mixture of ethyl acetate and acetone, the mixture of butanone and diacetylmethane, the mixture of Virahol and butanols, the mixture of diacetone alcohol and ether, the mixture of sherwood oil and aromatic alcohol.
A kind of method of organosilicon-modified acrylic UV-curable water-borne resin, described method comprises the steps:
(1 ') adds 100 parts of containing hydrogen silicone oils, 10～20 parts of glycidyl methacrylate, 0.1～5 part of isopropyl alcohol solution of chloroplatinic acid and 30～100 parts of solvents in container, 90～110 ℃ by silicon hydrogen addition isothermal reaction discharging in 6～12 hours; Do precipitation agent with methyl alcohol reaction product be precipitated out, and with methyl alcohol repetitive scrubbing throw out, removing unreacted monomer and catalyzer Platinic chloride, after the vacuum-drying faint yellow transparent side base band epoxide group arranged contain pendant epoxies base silicone oil;
(1) will contain pendant epoxies base silicone oil and stopper and add in the reaction vessel, under nitrogen protection, slowly dropwise addition of acrylic acid monomer and catalyzer in the reaction vessel, reaction, when pH in the reaction system was 7.0, stopped reaction obtained the acid-organosilicon crylic acid performed polymer;
(2) drip the mixing solutions of tetrahydrophthalic anhydride, stopper and catalyzer in the acid-organosilicon crylic acid performed polymer that obtains to step (1), reaction is cooled to room temperature when acid number reaches theoretical value, obtain organosilicon-modified acrylic UV-curable water-borne resin.
A kind of method of organosilicon-modified acrylic UV-curable water-borne resin, described method comprises the steps:
(1 ' ') in container, add 100 parts of containing hydrogen silicone oils, 10～20 parts of glycidyl methacrylate, 0.1～5 parts of isopropyl alcohol solution of chloroplatinic acid and 30～100 parts of solvents, wherein, the massfraction of this containing hydrogen silicone oil reactive hydrogen is 0.06～0.2wt%, the Platinic chloride massfraction of isopropyl alcohol solution of chloroplatinic acid is 2wt%, 90～110 ℃ by silicon hydrogen addition isothermal reaction discharging in 6～12 hours, doing precipitation agent with methyl alcohol is precipitated out reaction product, and with methyl alcohol repetitive scrubbing throw out, removing unreacted monomer and catalyzer Platinic chloride, after the vacuum-drying faint yellow transparent side base band epoxide group arranged contain pendant epoxies base silicone oil;
(2 ' ') with above-mentioned make contain pendant epoxies base silicone oil, stopper adds in the container, N
2Protection is stirred and is warming up to 80～90 ℃ down, and slowly dropwise addition of acrylic acid monomer and catalyzer dripped off in 1～1.5 hour, be warming up to 90～100 ℃ subsequently, reacted 2～6 hours, at any time the assaying reaction system pH, when the pH value equaled 7.0, stopped reaction obtained the acid-organosilicon crylic acid performed polymer;
(3 ' ') above-mentioned acid-organosilicon crylic acid performed polymer is cooled to 60～70 ℃, drip the mixing solutions of tetrahydrophthalic anhydride, stopper and catalyzer in the system, after dropwising, insulation reaction, when reaching theoretical value, acid number is cooled to room temperature,, the side chain that obtains the tetrahydrophthalic anhydride modification has the organosilicon-modified acrylic UV-curable water-borne resin of hydrophilic radical carboxyl.
Exemplary reaction principle of the present invention is as follows:
Two of purpose of the present invention is to provide a kind of organosilicon-modified acrylic UV-curable water-borne resin, and described organosilicon-modified acrylic UV-curable water-borne resin is prepared by method as mentioned above.The organosilicon-modified acrylic UV-curable water-borne resin that adopts the method for the invention to obtain is both hydrophilic, and having simultaneously can ultraviolet light polymerization, has excellent surface property, thermostability and mechanical property.
With organosilicon-modified acrylic UV-curable water-borne resin, thin up, obtain uV curable organosilicon-modified acrylic water-based emulsion efficient the dispersion, can be applicable to technical fields such as textile finishing, exterior coating, leather finish.
Compared with prior art, the present invention has following beneficial effect: reaction conditions gentleness, productive rate height, cost is low, and the photocuring water-base resin for preparing is both hydrophilic, and having simultaneously can ultraviolet light polymerization, has excellent surface property, thermostability and mechanical property.
Embodiment
For the present invention is described better, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1
(1) add 100g containing hydrogen silicone oil (the reactive hydrogen massfraction is 0.1%), 14g glycidyl methacrylate, 0.2g isopropyl alcohol solution of chloroplatinic acid and 30g solvent in the 250ml four-hole boiling flask, 90 ℃ by silicon hydrogen addition isothermal reaction discharging in 6 hours.Do precipitation agent with methyl alcohol reaction product is precipitated out, and with methyl alcohol repetitive scrubbing throw out for several times, to remove unreacted monomer and catalyzer Platinic chloride.After the vacuum-drying faint yellow transparent side base band epoxide group arranged contain pendant epoxies base silicone oil.
(2) add above-mentioned gained in the 250ml four-hole boiling flask and contain pendant epoxies base silicone oil, 0.4g MEHQ, logical N
2Protection; stirring is warming up to 80 ℃; slowly drip an amount of Acrylic Acid Monomer 8g and catalyst of triethylamine 0.5g according to the silicone oil oxirane value; dripped off in 1～1.5 hour, and be warming up to 90 ℃ subsequently, reacted 2～6 hours; at any time measure system pH; when the pH value equaled 7.0, stopped reaction obtained the acid-organosilicon crylic acid performed polymer.
(3) above-mentioned acid-organosilicon crylic acid performed polymer is cooled to 60 ℃, drip the mixing solutions of 15g tetrahydrophthalic anhydride, 0.4g MEHQ and 0.5g triethylamine, after dropwising, insulation reaction, be cooled to room temperature until detecting when acid number reaches theoretical value (1 mole of tetrahydrophthalic anhydride produces 1 mole of carboxyl in theory), the side chain that obtains the tetrahydrophthalic anhydride modification has the organosilicon-modified acrylic UV-curable water-borne resin of hydrophilic radical carboxyl.
Embodiment 2
(1) add 100g containing hydrogen silicone oil (the reactive hydrogen massfraction is 0.1%), 17g glycidyl methacrylate, 0.4g isopropyl alcohol solution of chloroplatinic acid and 30g solvent in the 500ml four-hole boiling flask, 100 ℃ by silicon hydrogen addition isothermal reaction discharging in 10 hours.Do precipitation agent with methyl alcohol reaction product is precipitated out, and with methyl alcohol repetitive scrubbing throw out for several times, to remove unreacted monomer and catalyzer Platinic chloride.After the vacuum-drying faint yellow transparent side base band epoxide group arranged contain pendant epoxies base silicone oil.
(2) in four-hole boiling flask, add the 0.7g MEHQ, logical N
2Protection; stirring is warming up to 85 ℃; slowly drip an amount of Acrylic Acid Monomer 8g and catalyst of triethylamine 0.8g according to the silicone oil oxirane value; dripped off in 1～1.5 hour, and be warming up to 95 ℃ subsequently, reacted 2～6 hours; at any time measure system pH; when the pH value equaled 7.0, stopped reaction obtained the acid-organosilicon crylic acid performed polymer.
(3) above-mentioned acid-organosilicon crylic acid performed polymer is cooled to 60 ℃, drip the mixing solutions of 15g tetrahydrophthalic anhydride, 0.7g MEHQ and 0.8g triethylamine, after dropwising, insulation reaction, be cooled to room temperature until detecting when acid number reaches theoretical value (1 mole of tetrahydrophthalic anhydride produces 1 mole of carboxyl in theory), the side chain that obtains the tetrahydrophthalic anhydride modification has the organosilicon-modified acrylic UV-curable water-borne resin of hydrophilic radical carboxyl.
Embodiment 3
(1) add 100g containing hydrogen silicone oil (the reactive hydrogen massfraction is 0.1%), 20g glycidyl methacrylate, 0.8g isopropyl alcohol solution of chloroplatinic acid and 60g solvent in the 250ml four-hole boiling flask, 110 ℃ by silicon hydrogen addition isothermal reaction discharging in 12 hours.Do precipitation agent with methyl alcohol reaction product is precipitated out, and with methyl alcohol repetitive scrubbing throw out for several times, to remove unreacted monomer and catalyzer Platinic chloride.After the vacuum-drying faint yellow transparent side base band epoxide group arranged contain pendant epoxies base silicone oil.
(2) in four-hole boiling flask, add the 1g MEHQ, logical N
2Protection; stirring is warming up to 90 ℃; slowly drip an amount of Acrylic Acid Monomer 8g and catalyst of triethylamine 1g according to the silicone oil oxirane value; dripped off in 1～1.5 hour, and be warming up to 100 ℃ subsequently, reacted 2～6 hours; at any time measure system pH; when the pH value equaled 7.0, stopped reaction obtained the acid-organosilicon crylic acid performed polymer.
(3) above-mentioned acid-organosilicon crylic acid performed polymer is cooled to 70 ℃, drip the mixing solutions of 15g tetrahydrophthalic anhydride, 1g MEHQ and 1g triethylamine, after dropwising, insulation reaction, be cooled to room temperature until detecting when acid number reaches theoretical value (1 mole of tetrahydrophthalic anhydride produces 1 mole of carboxyl in theory), the side chain that obtains the tetrahydrophthalic anhydride modification has the organosilicon-modified acrylic UV-curable water-borne resin of hydrophilic radical carboxyl.
Embodiment 4
(1) in the 250ml four-hole boiling flask, adds 100g containing hydrogen silicone oil (the reactive hydrogen massfraction is 0.06wt%), 10g glycidyl methacrylate, 0.1g isopropyl alcohol solution of chloroplatinic acid and 30g solvent toluene, the massfraction of Platinic chloride is 1wt% in the described isopropyl alcohol solution of chloroplatinic acid, and 90 ℃ by silicon hydrogen addition isothermal reaction discharging in 12 hours.Do precipitation agent with methyl alcohol reaction product is precipitated out, and with methyl alcohol repetitive scrubbing throw out for several times, to remove unreacted monomer and catalyzer Platinic chloride.After the vacuum-drying faint yellow transparent side base band epoxide group arranged contain pendant epoxies base silicone oil.
(2) add above-mentioned gained in the 250ml four-hole boiling flask and contain pendant epoxies base silicone oil, Resorcinol, logical N
2Protection; stirring is warming up to 90 ℃; slow dropwise addition of acrylic acid monomer and catalyzer Tetramethylammonium hydroxide; dripped off in 1～1.5 hour; the mass percent that the quality of described Resorcinol accounts for the total mass of all raw materials in this step (2) is 0.2wt%; the mass percent that the quality of described Tetramethylammonium hydroxide accounts for the total mass of all raw materials in this step (2) is 0.4wt%; the carboxyl molar mass of described Acrylic Acid Monomer is 1:1 with the ratio of the epoxy group(ing) molar mass that contains pendant epoxies base silicone oil; be warming up to 100 ℃ subsequently; reacted 2～6 hours, and measured system pH at any time, when the pH value equals 7.0; stopped reaction obtains the acid-organosilicon crylic acid performed polymer.
(3) above-mentioned acid-organosilicon crylic acid performed polymer is cooled to 70 ℃, drip tetrahydrophthalic anhydride, the mixing solutions of MEHQ and triethylamine, the mass percent that the quality of described MEHQ accounts for the total mass of all raw materials in this step (3) is 0.2wt%, the mass percent that the quality of described triethylamine accounts for the total mass of all raw materials in this step (3) is 0.4wt%, the molar mass of described tetrahydrophthalic anhydride is 1:1 with the ratio of the molar mass of acid-organosilicon crylic acid performed polymer hydroxyl, insulation reaction, be cooled to room temperature until detecting when acid number reaches theoretical value (1 mole of tetrahydrophthalic anhydride produces 1 mole of carboxyl in theory), the side chain that obtains the tetrahydrophthalic anhydride modification has the organosilicon-modified acrylic UV-curable water-borne resin of hydrophilic radical carboxyl.
Embodiment 5
(1) in the 500ml four-hole boiling flask, adds 100g containing hydrogen silicone oil (the reactive hydrogen massfraction is 0.2wt%), 20g glycidyl methacrylate, 5g isopropyl alcohol solution of chloroplatinic acid and 100g solvent butanone, the massfraction of Platinic chloride is 3wt% in the described isopropyl alcohol solution of chloroplatinic acid, and 110 ℃ by silicon hydrogen addition isothermal reaction discharging in 6 hours.Do precipitation agent with methyl alcohol reaction product is precipitated out, and with methyl alcohol repetitive scrubbing throw out for several times, to remove unreacted monomer and catalyzer Platinic chloride.After the vacuum-drying faint yellow transparent side base band epoxide group arranged contain pendant epoxies base silicone oil.
(2) add above-mentioned gained in the 250ml four-hole boiling flask and contain pendant epoxies base silicone oil, p methoxy phenol, slow dropwise addition of acrylic acid monomer and catalyzer Tetramethylammonium hydroxide, dripped off in 1～1.5 hour, the mass percent that the quality of described p methoxy phenol accounts for the total mass of all raw materials of this step (2) is 1.2wt%, the mass percent that the quality of Tetramethylammonium hydroxide accounts for the total mass of all raw materials of this step (2) is 1.5wt%, the carboxyl molar mass of Acrylic Acid Monomer is 1:1 with the ratio of the epoxy group(ing) molar mass that contains pendant epoxies base silicone oil, be warming up to 95 ℃ subsequently, reacted 2～6 hours, at any time measure system pH, when the pH value equals 7.0, stopped reaction obtains the acid-organosilicon crylic acid performed polymer.
(3) above-mentioned acid-organosilicon crylic acid performed polymer is cooled to 60 ℃, drip tetrahydrophthalic anhydride, the mixing solutions of MEHQ and triethylamine, the mass percent that the quality of described MEHQ accounts for the total mass of all raw materials in this step (3) is 1.2wt%, the mass percent that the quality of described triethylamine accounts for the total mass of all raw materials in this step (3) is 1.5wt%, the molar mass of described tetrahydrophthalic anhydride is 1:1 with the ratio of the molar mass of acid-organosilicon crylic acid performed polymer hydroxyl, after dropwising, insulation reaction, be cooled to room temperature until detecting when acid number reaches theoretical value (1 mole of tetrahydrophthalic anhydride produces 1 mole of carboxyl in theory), the side chain that obtains the tetrahydrophthalic anhydride modification has the organosilicon-modified acrylic UV-curable water-borne resin of hydrophilic radical carboxyl.
Should be noted that and understand, under the situation that does not break away from the desired the spirit and scope of the present invention of accompanying Claim, can make various modifications and improvement to the present invention of foregoing detailed description.Therefore, the scope of claimed technical scheme is not subjected to the restriction of given any specific exemplary teachings.
Applicant's statement, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not mean that namely the present invention must rely on above-mentioned method detailed and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. the method for an organosilicon-modified acrylic UV-curable water-borne resin is characterized in that, described method comprises the steps:
(1) will contain pendant epoxies base silicone oil and stopper and add in the reaction vessel, under nitrogen protection, slowly dropwise addition of acrylic acid monomer and catalyzer in the reaction vessel, reaction, when pH in the reaction system was 7.0, stopped reaction obtained the acid-organosilicon crylic acid performed polymer;
(2) drip the mixing solutions of tetrahydrophthalic anhydride, stopper and catalyzer in the acid-organosilicon crylic acid performed polymer that obtains to step (1), 60～70 ℃ of reactions, when acid number reaches theoretical value, be cooled to room temperature, obtain organosilicon-modified acrylic UV-curable water-borne resin.
2. the method for claim 1 is characterized in that, under nitrogen protection, stir be warming up to 80～90 ℃ after, slowly dropwise addition of acrylic acid monomer and catalyzer in the reaction vessel, the preferred stirring is warming up to 82～88 ℃, further preferred 83～87 ℃;
Preferably, the dropping time of Acrylic Acid Monomer and catalyzer is 1～1.5 hour, preferred 1.06～1.47 hours, and further preferred 1.12～1.42 hours;
Preferably, the described temperature of reaction of step (1) is 90～100 ℃, preferred 91.5～98.5 ℃, and further preferred 92.5～97.5 ℃.
3. method as claimed in claim 1 or 2 is characterized in that, the described reaction times of step (1) is 2～6 hours, preferred 2.5～5.5 hours, and further preferred 3～5.5 hours;
Preferably, the carboxyl molar mass of described Acrylic Acid Monomer is 1:1 with the ratio of the epoxy group(ing) molar mass that contains pendant epoxies base silicone oil;
Preferably, the described stopper of step (1) is selected from the mixture of any one or at least two kinds in MEHQ, p methoxy phenol, Resorcinol or the 2,6 ditertiary butyl p cresol.
4. as the described method of one of claim 1-3, it is characterized in that, the mass percent that the quality of the described stopper of step (1) accounts for the total mass of all raw materials of step (1) is 0.2～1.2wt%, preferred 0.25～1.15wt%, further preferred 0.35～1.05wt%;
Preferably, the described catalyzer of step (1) is selected from triethylamine, Tetramethylammonium hydroxide, tetraethylammonium bromide or N, the mixture of any one in the N-dimethylbenzyl ammonium or at least two kinds;
Preferably, the mass percent that the quality of the described catalyzer of step (1) accounts for the total mass of all raw materials of step (1) is 0.4～1.5wt%, preferred 0.45～1.45wt%, further preferred 0.55～1.35wt%.
5. as the described method of one of claim 1-4, it is characterized in that, during being cooled to after 60～70 ℃, the acid-organosilicon crylic acid performed polymer that step (2) obtains step (1) drips the mixing solutions of tetrahydrophthalic anhydride, stopper and catalyzer, preferably be cooled to 61～69 ℃, further preferably be cooled to 62～68 ℃;
Preferably, the described stopper of step (2) is selected from the mixture of any one or at least two kinds in MEHQ, p methoxy phenol, Resorcinol or the 2,6 ditertiary butyl p cresol.
6. as the described method of one of claim 1-5, it is characterized in that, the mass percent that the quality of the described stopper of step (2) accounts for the total mass of all raw materials of step (2) is 0.2～1.2wt%, preferred 0.25～1.15wt%, further preferred 0.35～1.05wt%;
Preferably, the described catalyzer of step (2) is selected from triethylamine, Tetramethylammonium hydroxide, tetraethylammonium bromide or N, the mixture of any one in the N-dimethylbenzyl ammonium or at least two kinds;
Preferably, the mass percent that the quality of the described catalyzer of step (2) accounts for the total mass of all raw materials of step (2) is 0.4～1.5wt%, preferred 0.45～1.45wt%, further preferred 0.55～1.35wt%.
7. as the described method of one of claim 1-6, it is characterized in that the molar mass of described tetrahydrophthalic anhydride is 1:1 with the ratio of the molar mass of acid-organosilicon crylic acid performed polymer hydroxyl;
Preferably, the described pendant epoxies base silicone oil that contains is prepared by following method:
Add 100 parts of containing hydrogen silicone oils, 10～20 parts of glycidyl methacrylate, 0.1～5 part of isopropyl alcohol solution of chloroplatinic acid and 30～100 parts of solvents in container, 90～110 ℃ by silicon hydrogen addition isothermal reaction discharging in 6～12 hours; Do precipitation agent with methyl alcohol reaction product be precipitated out, and with methyl alcohol repetitive scrubbing throw out, removing unreacted monomer and catalyzer Platinic chloride, after the vacuum-drying faint yellow transparent side base band epoxide group arranged contain pendant epoxies base silicone oil.
8. method as claimed in claim 7 is characterized in that, the massfraction of the reactive hydrogen of described containing hydrogen silicone oil is 0.06～0.2wt%, preferred 0.07～0.17wt%, further preferred 0.08～0.15wt%;
Preferably, the massfraction of Platinic chloride is 1～3wt% in the described isopropyl alcohol solution of chloroplatinic acid, preferred 1.1～2.8wt%, further preferred 1.3～2.6wt%;
Described solvent is selected from the mixture of any one or at least two kinds in toluene, dimethylbenzene, ethyl glycollate, ethyl acetate, acetone, butanone, diacetylmethane, Virahol, butanols, diacetone alcohol, ether, sherwood oil, glycerine or the aromatic alcohol.
9. as the described method of one of claim 1-8, it is characterized in that described method comprises the steps:
(1 ') adds 100 parts of containing hydrogen silicone oils, 10～20 parts of glycidyl methacrylate, 0.1～5 part of isopropyl alcohol solution of chloroplatinic acid and 30～100 parts of solvents in container, 90～110 ℃ by silicon hydrogen addition isothermal reaction discharging in 6～12 hours; Do precipitation agent with methyl alcohol reaction product be precipitated out, and with methyl alcohol repetitive scrubbing throw out, removing unreacted monomer and catalyzer Platinic chloride, after the vacuum-drying faint yellow transparent side base band epoxide group arranged contain pendant epoxies base silicone oil;
(1) will contain pendant epoxies base silicone oil and stopper and add in the reaction vessel, under nitrogen protection, slowly dropwise addition of acrylic acid monomer and catalyzer in the reaction vessel, reaction, when pH in the reaction system was 7.0, stopped reaction obtained the acid-organosilicon crylic acid performed polymer;
(2) drip the mixing solutions of tetrahydrophthalic anhydride, stopper and catalyzer in the acid-organosilicon crylic acid performed polymer that obtains to step (1), reaction is cooled to room temperature when acid number reaches theoretical value, obtain organosilicon-modified acrylic UV-curable water-borne resin;
Preferably, described method comprises the steps:
(1 ' ') in container, add 100 parts of containing hydrogen silicone oils, 10～20 parts of glycidyl methacrylate, 0.1～5 parts of isopropyl alcohol solution of chloroplatinic acid and 30～100 parts of solvents, wherein, the massfraction of this containing hydrogen silicone oil reactive hydrogen is 0.06～0.2wt%, the Platinic chloride massfraction of isopropyl alcohol solution of chloroplatinic acid is 2wt%, 90～110 ℃ by silicon hydrogen addition isothermal reaction discharging in 6～12 hours, doing precipitation agent with methyl alcohol is precipitated out reaction product, and with methyl alcohol repetitive scrubbing throw out, removing unreacted monomer and catalyzer Platinic chloride, after the vacuum-drying faint yellow transparent side base band epoxide group arranged contain pendant epoxies base silicone oil;
(2 ' ') with above-mentioned make contain pendant epoxies base silicone oil, stopper adds in the container, N
2Protection is stirred and is warming up to 80～90 ℃ down, and slowly dropwise addition of acrylic acid monomer and catalyzer dripped off in 1～1.5 hour, be warming up to 90～100 ℃ subsequently, reacted 2～6 hours, at any time the assaying reaction system pH, when the pH value equaled 7.0, stopped reaction obtained the acid-organosilicon crylic acid performed polymer;
(3 ' ') above-mentioned acid-organosilicon crylic acid performed polymer is cooled to 60～70 ℃, drip the mixing solutions of tetrahydrophthalic anhydride, stopper and catalyzer, after dropwising, reaction, be cooled to room temperature when acid number reaches theoretical value, the side chain that obtains the tetrahydrophthalic anhydride modification has the organosilicon-modified acrylic UV-curable water-borne resin of hydrophilic radical carboxyl.
10. an organosilicon-modified acrylic UV-curable water-borne resin is characterized in that, described organosilicon-modified acrylic UV-curable water-borne resin is prepared by the described method of one of claim 1-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310207887.7A CN103265704B (en) | 2013-05-28 | 2013-05-28 | A kind of organosilicon-modified acrylic UV-Curing Waterborne Resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310207887.7A CN103265704B (en) | 2013-05-28 | 2013-05-28 | A kind of organosilicon-modified acrylic UV-Curing Waterborne Resin and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103265704A true CN103265704A (en) | 2013-08-28 |
| CN103265704B CN103265704B (en) | 2015-12-23 |
Family
ID=49009375
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310207887.7A Expired - Fee Related CN103265704B (en) | 2013-05-28 | 2013-05-28 | A kind of organosilicon-modified acrylic UV-Curing Waterborne Resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103265704B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109517177A (en) * | 2018-11-26 | 2019-03-26 | 衡阳思迈科科技有限公司 | The preparation method of the carboxy-modified conductive silver glue lotion of hydrocarbon |
| CN110183664A (en) * | 2019-04-30 | 2019-08-30 | 常州大学 | A kind of preparation method and application of ultraviolet curing type silicone oil containing methacrylate |
| CN110698911A (en) * | 2019-11-24 | 2020-01-17 | 邵美忠 | Double-curing glass printing ink and preparation method thereof |
| CN110760260A (en) * | 2019-11-24 | 2020-02-07 | 邵美忠 | Dual-curing vacuum coating primer and preparation method thereof |
| CN110790936A (en) * | 2019-11-24 | 2020-02-14 | 邵美忠 | Dual-curing organic silicon resin and preparation method thereof |
| CN112574418A (en) * | 2020-12-07 | 2021-03-30 | 万华化学集团股份有限公司 | Organic silicon compound containing epoxy group and preparation method thereof, epoxy resin composition and preparation method thereof |
| CN117843885A (en) * | 2023-12-15 | 2024-04-09 | 广州海豚新材料有限公司 | A kind of organic silicon hand feeling additive and its preparation method and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4908274A (en) * | 1987-02-06 | 1990-03-13 | Th. Goldschmidt Ag | Polysiloxanes with (meth) acrylate ester groups linked through sic groups and their use as radiation-curable coating materials for flat carriers |
| US7172809B2 (en) * | 2000-07-31 | 2007-02-06 | Ppg Industries Ohio, Inc. | Coating compositions comprising silyl blocked components, coatings, coated substrates and methods related thereto |
| CN101048460A (en) * | 2004-10-25 | 2007-10-03 | 陶氏康宁公司 | Moldable compositions containing carbinol functional silicone reisins or anhydride functional silicone resins |
| CN103030810A (en) * | 2011-09-29 | 2013-04-10 | 信越化学工业株式会社 | (Meth)acrylic-modified organopolysiloxane, radiation-curable silicone composition, silicone release liner, and making methods |
-
2013
- 2013-05-28 CN CN201310207887.7A patent/CN103265704B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4908274A (en) * | 1987-02-06 | 1990-03-13 | Th. Goldschmidt Ag | Polysiloxanes with (meth) acrylate ester groups linked through sic groups and their use as radiation-curable coating materials for flat carriers |
| US7172809B2 (en) * | 2000-07-31 | 2007-02-06 | Ppg Industries Ohio, Inc. | Coating compositions comprising silyl blocked components, coatings, coated substrates and methods related thereto |
| CN101048460A (en) * | 2004-10-25 | 2007-10-03 | 陶氏康宁公司 | Moldable compositions containing carbinol functional silicone reisins or anhydride functional silicone resins |
| CN103030810A (en) * | 2011-09-29 | 2013-04-10 | 信越化学工业株式会社 | (Meth)acrylic-modified organopolysiloxane, radiation-curable silicone composition, silicone release liner, and making methods |
Non-Patent Citations (1)
| Title |
|---|
| 吴建伟等: "甲基四氢苯酐中温固化低粘环氧树脂体系研究", 《化学与粘合》, no. 4, 31 December 2001 (2001-12-31) * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109517177A (en) * | 2018-11-26 | 2019-03-26 | 衡阳思迈科科技有限公司 | The preparation method of the carboxy-modified conductive silver glue lotion of hydrocarbon |
| CN110183664A (en) * | 2019-04-30 | 2019-08-30 | 常州大学 | A kind of preparation method and application of ultraviolet curing type silicone oil containing methacrylate |
| CN110183664B (en) * | 2019-04-30 | 2021-09-28 | 常州大学 | Preparation method and application of ultraviolet-curing methacrylate-containing silicone oil |
| CN110698911A (en) * | 2019-11-24 | 2020-01-17 | 邵美忠 | Double-curing glass printing ink and preparation method thereof |
| CN110760260A (en) * | 2019-11-24 | 2020-02-07 | 邵美忠 | Dual-curing vacuum coating primer and preparation method thereof |
| CN110790936A (en) * | 2019-11-24 | 2020-02-14 | 邵美忠 | Dual-curing organic silicon resin and preparation method thereof |
| CN112574418A (en) * | 2020-12-07 | 2021-03-30 | 万华化学集团股份有限公司 | Organic silicon compound containing epoxy group and preparation method thereof, epoxy resin composition and preparation method thereof |
| CN117843885A (en) * | 2023-12-15 | 2024-04-09 | 广州海豚新材料有限公司 | A kind of organic silicon hand feeling additive and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103265704B (en) | 2015-12-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103265704B (en) | A kind of organosilicon-modified acrylic UV-Curing Waterborne Resin and preparation method thereof | |
| CN101880360B (en) | Preparation method of water dispersed modified acrylic ester resin for automobile finish varnish | |
| CN104744644B (en) | A kind of organo-mineral complexing modified aqueous acrylic acid epoxy ester resin and preparation method thereof | |
| EP3241875B1 (en) | Resin composition for hard coating, and hard-coating film comprising cured form of same as coating layer | |
| KR20190105127A (en) | Hollow particles and use thereof | |
| CN109312059B (en) | Thermosetting epoxy resin composition and method for producing same | |
| CN103154074A (en) | Cationic polymerization initiator and thermosetting epoxy resin composition | |
| CN104812854B (en) | Superhydrophilic antireflection coating composition comprising silicone compounds utilizes its Superhydrophilic antireflection film and preparation method thereof | |
| CN101735379A (en) | Self-drying low aliphatic chain oxosilane modified water-borne acrylic resin and preparation method thereof | |
| CN114249878B (en) | High-temperature-resistant low-yellowing resin for UV (ultraviolet) ink as well as preparation method and application thereof | |
| JP2017061664A (en) | Organic-inorganic hybrid hollow particles and uses thereof | |
| WO2013053328A1 (en) | Gel time controllable two part epoxy adhesive | |
| CN106243988A (en) | High-solid-content water-based ultraviolet-curing transparent heat-insulating coating and preparation method thereof | |
| CN109796917A (en) | A kind of preparation method of UV cured polyurethane acrylate adhesive | |
| CN103146297B (en) | The preparation method of hydrolysis fibroin coating | |
| JP6994562B2 (en) | A coating film containing a coating resin composition and a cured product thereof as a coating layer. | |
| CN102731558A (en) | Organosilicone oligomer and preparation method thereof, and bi-component system and application thereof | |
| CN108546485A (en) | A kind of organic-inorganic hybrid resin of high solids content and preparation method thereof | |
| CN103881031A (en) | Special organic silicon resin for photocureable coating and preparation process of organic silicon resin | |
| JP6912601B2 (en) | A coating film containing a coating resin composition and a cured product thereof as a coating layer. | |
| CN109053952A (en) | A kind of water-based acrylic resin and its application | |
| CN104031591A (en) | Ultraviolet-curing composition for LED packaging | |
| CN104718231A (en) | Glycidyl ether compound, liquid crystal sealant, and method for producing glycidyl ether compound | |
| KR101666052B1 (en) | Organic-inorganic composite coating composition for hard coating and method for producing the same | |
| KR102246756B1 (en) | Photocurable coating material compositions of vinyl-silicon compounds |
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: 20160630 Address after: 226017 Jiangsu city of Nantong Province Economic and Technological Development Zone Road, No. 31. Patentee after: Shengda Technology (Nantong) Co., Ltd. Address before: Wuxi District of Jiangsu city of Wuxi province Qingyuan Road 214135 No. 18 Pacific Park University Science Park 530 building A908 Patentee before: Lu Ru |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20151223 Termination date: 20210528 |