CN1544499A - Acrylic ester organic silicon composite modified polyether polyurethane aqueous dispersion and preparation method thereof - Google Patents
Acrylic ester organic silicon composite modified polyether polyurethane aqueous dispersion and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an acrylic ester organosilicon composite modified polyether polyurethane water dispersion and process of preparation, wherein the water dispersion is volatilized from dry film forming with 25-35% of solid portion, and 65-75% of water, the solid portion comprises 5-20% of acrylic ester monomers, 70-80% of polyether polyurethane prepolymer, 0.1-1.0% of unsaturated double bond containing organosilicon monomer, 0.1-1.0% of chain-transferring agent and 0.50-2.5% of oil soluble initiating agent emulsion through copolymerization.
Description
Technical field
The present invention relates to composite modified polyether-polyurethane water dispersion of a kind of acrylate organosilicon and preparation thereof.
Background technology
Urethane resin is widely used in every field owing to performances such as having excellent abrasive, snappiness and chemicals-resistant.But along with determining and the enhancing of environmental consciousness of various countries' environmental regulation, in traditional solvent borne polyurethane system, the toxicity of the discharging of volatile organic compounds (VOC) and isocyanic ester middle reaches divorce cyanate radical, its application is restricted, and aqueous polyurethane dispersion receives publicity just day by day because of its difficult combustion, nontoxic, pollution-free, easy storing, easy to use.Aqueous polyurethane dispersion is during as film-forming resin, and the water tolerance after its film forming is an important techniques index, and it directly influences this resinoid application.Invented acrylate modified polyurethane aqueous dispersion body in the related volatility system in the past, for example among CN1407014 and the CN1320669, adopt internal emulsification and outer emulsification composite methods, owing to introduced micromolecular emulsifying agent, made that the water tolerance after the polyurethane aqueous dispersion body film forming descends significantly.Among CN1407014, CN1089956 and the US6166127, adopt water-soluble peroxide class initiator during polymerization,, and be significantly reduced to the water tolerance behind the film also because of introducing hydrophilic radical.In EP072239A1, though adopt the oil-soluble initiator initiated polymerization, avoided adopting the defective of water soluble starter, but because the consumption of initiator is low excessively, one-step polymerization causes molecular weight too small (less than 10000) after the copolymerization, can only improve performance after the film forming by other introduction linking agent, this bicomponent system brings a lot of inconvenience to use.
Summary of the invention
The objective of the invention is to, composite modified polyether-polyurethane water dispersion of a kind of acrylate organosilicon and preparation thereof are provided, this water dispersion can be used as the film-forming resin of volatile-type single component from dry system, and paint film has excellent water tolerance and mechanical property after the film forming.
Realize the technical scheme of the object of the invention: the composite modified polyether-polyurethane water dispersion of a kind of acrylate organosilicon, this water dispersion volatilization is from doing film forming, solid part accounts for 25～35%, water accounts for 65～75%, wherein solid part is formed by acrylic ester monomer 5～20%, polyether polyurethane prepolymer 70～80%, the organosilane monomer 0.1～1.0% that contains unsaturated double-bond, chain-transfer agent 0.1～1.0% and oil-soluble initiator 0.50～2.5% emulsion copolymerization, above percentage ratio is weight percentage, polyether polyurethane prepolymer wherein has simultaneously-COOH and-COON
+HR
3Both sexes functional group, be to be 1.2～2.0 polyisocyanates, carboxylic polyvalent alcohol and polyether glycol heating copolymerization by-NCO/-OH equivalence ratio, again with crylic acid hydroxy ester class end-blocking to-NCO is zero, reduce to room temperature after, it is 65%～95% that part is neutralized to degree of neutralization, adds emulsifying water and forms.
Polyether polyurethane prepolymer in the above-mentioned water dispersion, its hydroxyl equivalent of the polyether glycol that is adopted during preparation is 50～100mgKOH/g, molecular weight 2000～3000, for example polyethers N330 etc.; The used carboxyl polyvalent alcohol that contains accounts for 4.5～5.5% of this prepolymer total amount, is lower than 4.5% emulsifying capacity deficiency, is higher than 5.5% and can causes that water tolerance descends behind the emulsion film forming, can adopt dimethylol propionic acid (DMPA) etc. as carboxylic polyvalent alcohol; Used polyisocyanates is aromatic diisocyanate or aliphatic diisocyanate, can select wherein one or more mixture for use, for example, tolylene diisocyanate (TDI), '-diphenylmethane diisocyanate, dimethylene diisocyanate, isophorone diisocyanate etc.; Used crylic acid hydroxy ester class is hydroxyethyl methylacrylate (HEMA), Propylene glycol monoacrylate (HAP) etc.; Used neutralizing agent is an organic amine, for example triethylamine (TEA) etc.
The organosilane monomer that contains unsaturated double-bond in above-mentioned water dispersion be meant in molecular structure, contain unsaturated link(age)-Si-O-R compounds, for example vinyltriethoxysilane, methyl-prop acyloxy Trimethoxy silane etc.
Chain-transfer agent in above-mentioned water dispersion is C
6～C
18Alkyl sulfhydryl, lauryl mercaptan etc. for example.
The oil-soluble initiator that above-mentioned water dispersion adopted is the oil soluble azo-compound, for example Diisopropyl azodicarboxylate (AIBN) etc., or oil soluble superoxide, for example benzoyl peroxide (BPO) etc.
In the above-mentioned water dispersion, described acrylic ester monomer is to contain in the compound with esters of acrylic acid polymerization feature of unsaturated double-bond one or more.For example hydroxyethyl methylacrylate, methyl methacrylate, vinylbenzene, Propylene glycol monoacrylate etc.
Realize that another object of the present invention promptly prepares the technical scheme of above-mentioned water dispersion: with acrylic ester monomer, polyether polyurethane prepolymer, the organosilane monomer and the chain-transfer agent that contain unsaturated double-bond, stirring heating, emulsion copolymerization in the presence of initiator, described initiator divided for three steps added, the first step adds 10～25% of initiator amount, 65～75 ℃ of copolymerization temperatures, second step added 50～75% of initiator amount, copolymerization temperature is 80～86 ℃, the 3rd step added 10～15% of initiator amount, 88～95 ℃ of copolymerization temperatures, stirring velocity 30～60rpm during the emulsion copolymerization.
The water dispersion that adopts technical solution of the present invention to make, after the film forming, paint film property can reach following index:
Sticking power, level 1～2; Snappiness, mm 1～2;
Hardness 0.45～0.55; 60 ° of gloss, % 〉=85;
Dryness: surface drying, h≤1;
Do solid work h≤6;
Water tolerance, day 〉=10.
Technique effect of the present invention: composite modified polyether-polyurethane water dispersion of acrylate organosilicon that technical solution of the present invention provided and preparation method thereof, has excellent water tolerance after making gained water dispersion film forming, this is because the used polyether polyurethane prepolymer of emulsion copolymerization, adopted the carboxylic polyvalent alcohol of appropriate quantity, by introducing this monomer that contains bifunctional (hydroxyl and carboxyl), need not add small-molecular emulsifier and both can realize self-emulsifying, guarantee to have excellent water tolerance after the water dispersion film forming again, overcome and add small-molecular emulsifier in the prior art and cause the shortcoming that water tolerance reduces after the film forming.During used polyether polyurethane prepolymer, adopt the part neutralization in preparation, like this, reduce system viscosity on the one hand, in and system stable reaction during salify, avoid occurring gel, help guaranteeing water-tolerant after the water dispersion film forming on the other hand.Because it is 65%～95% that degree of neutralization is lower than 1, therefore, exist on the molecular chain of polyether polyurethane prepolymer some amount-the COOH group, when this prepolymer and the organosilane monomer, the acrylic ester monomer that contain unsaturated double-bond carry out water dispersion film forming that emulsion copolymerization generated, in the presence of-COOH group and water in air, siloxanes Si-O-R in the organosilane monomer is easy to take place hydrolytic condensation, produce partial cross-linked, formed-the Si-O-Si-segment, the intensity that had both improved film forming matter has also improved its water tolerance.Adopt oil-soluble initiator fully, avoided the hydrophilic radical brought into because of initiator in the prior art to the water dispersion film forming after water-proof influence.The proportioning of acrylic ester monomer, polyether polyurethane prepolymer and the double bond containing organosilane monomer of in technical solution of the present invention, determining, effectively raise the water tolerance after the dispersion film forming, the reaction of emulsion copolymerization simultaneously can be stablized and be carried out, the emulsion particle of dispersion is suitable, and package stability and film-forming properties all improve.
In addition, when polyether polyurethane prepolymer prepared, before crylic acid hydroxy ester class end-blocking, control-NCO/-OH equivalence ratio and behind end-blocking-NCO content was zero.Gel takes place in the time of can preventing the prepolymer polymerization like this, nor need to introduce in addition monohydroxy-alcohol end-blocking (for example CN1407014) again, thereby avoided because the monohydroxy-alcohol of being introduced does not dewater, make it to take place disproportionation reaction, the film forming mechanical property of influence, also avoided using anhydrous monohydroxy-alcohol end-blocking, the production cost that the dewatering process that is increased causes increases.
Three steps of determining in the technical solution of the present invention of branch add initiator and carry out the method that emulsion copolymerization prepares water dispersion, the added a small amount of initiator of the first step mainly produces the pre-polymerization effect, the 3rd step, added a small amount of initiator mainly was the transformation efficiency that improves acrylic ester monomer, reduce the content of free Acrylic Acid Monomer, second step added 50～75% initiator of total amount, and polymer chain is increased fast.Like this, guarantee that polymericular weight is even, reduce micromolecular existence, significantly improve the water tolerance after the water dispersion film forming, also help film forming improved performance.Overcome the unfavorable situation that the existence of a large amount of micromolecular compounds causes water tolerance in the copolymer emulsion in the prior art.
Embodiment
1～6 couple of the present invention is further described in detail below in conjunction with example, but is not limited to this.Numeral unless otherwise indicated is weight part in the table 1 and 2.
One, the preparation of polyether polyurethane prepolymer
1, prescription: see Table 1
Table 1
| Material name | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Polyether glycol N330 N210 | ??72.36 ??- | ??33.5 ??- | ??72.36 ??- | ??72.36 ??- | ??72.36 ??- | ??- ??39.41 |
| Carboxylic polyvalent alcohol DMPA | ??7.00 | ??3.80 | ??7.00 | ??7.00 | ??7.00 | ??4.20 |
| Polyisocyanates TDI | ??20.00 | ??14.25 | ??20.00 | ??20.00 | ??20.00 | ??24.00 |
| Crylic acid hydroxy ester class HEMA HPA | ??6.89 ??- | ??9.55 ??- | ??6.89 ??- | ??6.89 ??- | ??- ??6.89 | ??14.77 ??- |
| Neutralizing agent TEA | ??4.48 | ??2.43 | ??4.48 | ??4.48 | ??4.48 | ??2.57 |
| Solvent NMP | ??32.00 | ??17.60 | ??32.00 | ??32.00 | ??32.00 | ??11.60 |
| -NCO/-OH equivalence ratio | ??1.30 | ??1.82 | ??1.30 | ??1.30 | ??1.30 | ??1.95 |
| Degree of neutralization, % | ??85 | ??85 | ??85 | ??85 | ??85 | ??81.18 |
In the table 1: DMPA is a dimethylol propionic acid, and Shandong Dongying City Sai Meike company limited produces;
TDI is a tolylene diisocyanate, and Mitsui Co., Ltd. produces;
HEMA is a hydroxyethyl methylacrylate, and is produced from the Dongfang Chemical Plant, Beijing, The East Chemical Plant,Beijing;
HPA is a Propylene glycol monoacrylate, and is produced from the Dongfang Chemical Plant, Beijing, The East Chemical Plant,Beijing;
TEM is a triethylamine, and reagent one factory in Shanghai produces;
NMP is a N-Methyl pyrrolidone, and high-end Chemicals limited liability company of Beijing Top produces;
N330 is a trihydroxy-polyoxygenated propyl ether, and Nanjing, Nanjing petrochemical industry is produced;
N210 is a dihydroxyl polyoxygenated propyl ether, and Nanjing, Nanjing petrochemical industry is produced.
2, preparation technology
Press table 1 given quantity, polyether glycol, carboxylic polyvalent alcohol, polyisocyanates and solvent NMP are dropped in the there-necked flask of belt stirrer, thermometer, stirring is warming up to 80 ℃ and be incubated 2 hours, add vinylformic acid hydroxyl ester class then and stirred end-blocking 2 hours at 85 ℃, be cooled to 25 ℃, the adding neutralizing agent neutralizes, and stirs and add emulsifying water to form the polyether-polyurethane performed polymer.
Two, the preparation of the composite modified polyether-polyurethane water dispersion of acrylate organosilicon
1, prescription: see Table 2
Table 2
| Material name | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Polyether polyurethane prepolymer | ??110.69 ??(82.03) | ??63.44 ??(88.05) | ??110.69 ??(82.03) | ??110.73 ??(82.07) | ??110.69 ??(82.03) | ??84.45 ??(91.02) |
| Acrylic ester monomer MMA | ??22.40 ??(16.60) | ??8.00 ??(11.10) | ??11.20 ??(8.30) | ??22.40 ??(16.60) | ??22.40 ??(16.60) | ??7.58 ??(8.17) |
| ??St | ??- | ??- | ??11.20 ??(8.30) | ??- | ??- | ??- |
| The organosilane monomer KH570 A151 that contains unsaturated double-bond | ??0.23 ??(0.17) | ???- ??0.10 ??(0.14) | ??0.23 ??(0.17) | ??0.23 ??(0.17) | ??0.23 ??(0.17) | ??0.23 ??(0.25) |
| Oil-soluble initiator AIBN BPO | ??0.96 ??(0.71) | ??0.11 ??(0.15) | ??0.96 ??(0.71) | ??- ??0.91 ??(0.67) | ??0.96 ??(0.71) | ??0.04 ??(0.04) |
| The chain-transfer agent lauryl mercaptan | ??0.66 ??(0.49) | ??0.40 ??(0.56) | ??0.66 ??(0.49) | ??0.66 ??(0.49) | ??0.66 ??(0.49) | ??0.48 ??(0.52) |
| Water | ??272.26 | ??146.00 | ??272.26 | ??272.26 | ??272.26 | ??192.18 |
| The shared percentage ratio of water in water dispersion, % | ??66.86 | ??66.96 | ??66.86 | ??66.85 | ??66.86 | ??67.44 |
| The shared percentage ratio of solid part in water dispersion, % | ??33.14 | ??33.04 | ??33.14 | ??33.15 | ??33.14 | ??32.56 |
MMA is a methyl methacrylate in the table 2, and is produced from the Dongfang Chemical Plant, Beijing, The East Chemical Plant,Beijing;
St is a vinylbenzene, and is produced from the Dongfang Chemical Plant, Beijing, The East Chemical Plant,Beijing;
KH570 is a methyl-prop acyloxy Trimethoxy silane, and produce in dawn chemical plant, Nanjing;
A151 is a vinyltriethoxysilane, and produce in dawn chemical plant, Nanjing;
BPO is a benzoyl peroxide, and the Jiao Xi factory that orientalizes in Wujin produces;
AIBN is a Diisopropyl azodicarboxylate, and produce in Changzhou Chen Xiang chemical plant;
Making concentration with the NMP dissolving when wherein initiator (BPO or AIBN) uses is 10% solution;
Numeral is this component shared weight percentage in water dispersion solid part of the present invention in table 2 bracket;
Polyether polyurethane prepolymer is taken from the prepolymer by table 1 corresponding instance formulation in the table 2.
2, preparation technology
Press in the table 2 given quantity, in the there-necked flask of belt stirrer, thermometer etc., add polyether polyurethane prepolymer, warming while stirring to 70 ℃, 15% of slow dropwise addition of acrylic acid esters monomer, organosilane monomer, chain-transfer agent and oil-soluble initiator consumption, be incubated 2 hours then, add 75% of initiator amount again, be warming up to 85 ℃ and continue insulation 2 hours again, add 10% of initiator amount once more, be warming up to 93 ℃ of insulations after 1 hour, cooling adds water and adjusts solids constituent, discharging.Stirring velocity is controlled in 30～60rpm scope in whole emulsion copolymerization reaction process.
Three, the water dispersion service check of example 1～6
1, the method for inspection
Prepare paint film by spraying method in the general preparation method of GB/T1727-1992 paint film with the water dispersion of the present invention that example 1～6 makes;
Measure above-mentioned paint film surface drying and do solid work the time by GB/T1728-1979 (89) first method;
Measure above-mentioned paint film adhesion by GB/T1720-1979 (89);
Measure above-mentioned hardness of paint film by GB/T1730-1993B;
Measure above-mentioned paint film flexibility by GB/T1731;
Measure above-mentioned paint film water tolerance by GB/T1733;
Measure 60 ° of gloss of above-mentioned paint film by GB/T9754;
Above-mentioned detected result sees Table 3.
Table 3
| Test item | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 |
| Time of drying surface drying, min≤do solid work, h≤ | ?32 ?4 | ?45 ?3.5 | ?48 ?4.5 | ?50 ?5.0 | ?36 ?4.5 | ?28 ?6.0 |
| Sticking power, level | ?2 | ?1 | ?1 | ?1 | ?1 | ?2 |
| Hardness | ?0.495 | ?0.489 | ?0.475 | ?0.478 | ?0.502 | ?0.546 |
| Snappiness, mm | ?1 | ?1 | ?1 | ?1 | ?1 | ?1 |
| Water tolerance, d 〉= | ?10 | ?15 | ?10 | ?10 | ?10 | ?5 |
| Gloss, 60 ° of % | ?87 | ?88 | ?90 | ?88 | ?87 | ?86 |
As can be seen from Table 3, by the composite modified polyether-polyurethane water dispersion of technical scheme synthetic acrylate organosilicon of the present invention, good gloss, mechanical property, dryness are not only arranged after the film forming, also has excellent in water resistance (shown in example 1～5), and example 6 is when selecting polyethers N210 as raw material, because molecular weight is less, the wetting ability of raw material N210 is better than N330, and hydroxy radical content is higher with respect to N330, so anti-water-break obviously descends after causing synthetic water dispersion film forming.
Claims (5)
1, the composite modified polyether-polyurethane water dispersion of a kind of acrylate organosilicon, this water dispersion volatilization is from doing film forming, it is characterized in that: solid part accounts for 25～35%, water accounts for 65～75%, wherein solid part is formed by acrylic ester monomer 5～20%, polyether polyurethane prepolymer 70～80%, the organosilane monomer 0.1～1.0% that contains unsaturated double-bond, chain-transfer agent 0.1～1.0% and oil-soluble initiator 0.50～2.5% emulsion copolymerization, above percentage ratio is weight percentage, polyether polyurethane prepolymer wherein has simultaneously-COOH and-COON
+HR
3Both sexes functional group, be to be 1.2～2.0 polyisocyanates, carboxylic polyvalent alcohol and polyether glycol heating copolymerization by-NCO/-OH equivalence ratio, again with crylic acid hydroxy ester class end-blocking to-NCO is zero, reduce to room temperature after, it is 65%～95% that part is neutralized to degree of neutralization, adds emulsifying water and forms.
2, water dispersion according to claim 1 is characterized in that: described oil-soluble initiator is oil soluble azo-compound or oil soluble superoxide.
3, water dispersion according to claim 1 is characterized in that: described chain-transfer agent is C
6～C
18Alkyl sulfhydryl.
4, water dispersion according to claim 1 is characterized in that: described acrylic ester monomer is to contain in the compound with esters of acrylic acid polymerization feature of unsaturated double-bond one or more.
5, the preparation of the composite modified polyether-polyurethane water dispersion of acrylate organosilicon of claim 1, with acrylic ester monomer, polyether polyurethane prepolymer, the organosilane monomer and the chain-transfer agent that contain unsaturated double-bond, stirring heating, emulsion copolymerization in the presence of initiator, it is characterized in that: described initiator divided for three steps added, the first step adds 10～25% of initiator amount, 65～75 ℃ of copolymerization temperatures, second step added 50～75% of initiator amount, copolymerization temperature is 80～86 ℃, the 3rd step added 10～15% of initiator amount, 88～95 ℃ of copolymerization temperatures, stirring velocity 30～60rpm during the emulsion copolymerization.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100351289C (en) * | 2005-07-13 | 2007-11-28 | 安徽大学 | Radiation polymerization method for aqueous polyurethane-siliceous acrylic resin fabric coating |
| CN102010558A (en) * | 2010-10-11 | 2011-04-13 | 中国海洋石油总公司 | Acrylic acid non-aqueous dispersoid containing amino ester bonds and siloxy groups and preparation method thereof |
| CN103467667A (en) * | 2013-09-10 | 2013-12-25 | 合肥乐凯科技产业有限公司 | Acrylate modified polyurethane emulsion and preparation method thereof |
| CN105199051A (en) * | 2015-11-02 | 2015-12-30 | 宋介珍 | Transparent organosilicon material and preparation method thereof |
-
2003
- 2003-11-13 CN CN 200310106313 patent/CN1257199C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100351289C (en) * | 2005-07-13 | 2007-11-28 | 安徽大学 | Radiation polymerization method for aqueous polyurethane-siliceous acrylic resin fabric coating |
| CN102010558A (en) * | 2010-10-11 | 2011-04-13 | 中国海洋石油总公司 | Acrylic acid non-aqueous dispersoid containing amino ester bonds and siloxy groups and preparation method thereof |
| CN102010558B (en) * | 2010-10-11 | 2012-07-04 | 中国海洋石油总公司 | Acrylic acid non-aqueous dispersoid containing amino ester bonds and siloxy groups and preparation method thereof |
| CN103467667A (en) * | 2013-09-10 | 2013-12-25 | 合肥乐凯科技产业有限公司 | Acrylate modified polyurethane emulsion and preparation method thereof |
| CN103467667B (en) * | 2013-09-10 | 2017-01-11 | 合肥乐凯科技产业有限公司 | Acrylate modified polyurethane emulsion and preparation method thereof |
| CN105199051A (en) * | 2015-11-02 | 2015-12-30 | 宋介珍 | Transparent organosilicon material and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1257199C (en) | 2006-05-24 |
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Effective date of registration: 20120910 Address after: 213016 Changzhou Zhong Road, Jiangsu Province, No. 22 Longjiang Road Patentee after: CNOOC Changzhou Paint & Coatings Industry Research Institute Address before: 213016, Jiangsu, Changzhou Province West Ring Road North intersection Patentee before: Changzhou Inst of Paint Chemical, Chinese Chemical Building Corp. |
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| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060524 Termination date: 20141113 |
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| EXPY | Termination of patent right or utility model |