CN103012726A - Preparation method of polyurethane urea cross-linking agent and modified acrylic ester elastic emulsion thereof - Google Patents
Preparation method of polyurethane urea cross-linking agent and modified acrylic ester elastic emulsion thereof Download PDFInfo
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- CN103012726A CN103012726A CN2011102898608A CN201110289860A CN103012726A CN 103012726 A CN103012726 A CN 103012726A CN 2011102898608 A CN2011102898608 A CN 2011102898608A CN 201110289860 A CN201110289860 A CN 201110289860A CN 103012726 A CN103012726 A CN 103012726A
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Abstract
The invention discloses a preparation method of a polyurethane urea cross-linking agent containing end double bonds. The preparation method is carried out by the following steps: mixing micromolecule dihydric alcohol and diamine, and subsequently carrying out a pre-polymerization reaction with excessive diisocyanate, and then carrying out an end-capping reaction with crylic acid beta-hydroxyethyl ester to obtain the polyurethane urea cross-linking agent containing end double bonds. An aqueous acrylic ester elastic emulsion is synthesized by using the polyurethane urea cross-linking agent as a micro cross-linking agent. The elastic emulsion has the advantages of good mechanical strength and elasticity and can be used for preparing aqueous and elastic emulsion varnish.
Description
Technical field
The present invention relates to the preparation method of the little cross-linking modified acrylic ester elastic emulsion of a kind of polyurethane-urea, this emulsion can be used for exterior wall elastic emulsion paint in the preparation high-decoration
Background technology
Have high-decoration and film-forming properties after the acrylate copolymer emulsion film forming, and urethane, polyureas and polyurethane-urea have snappiness, sticking power and water tolerance, with they compound aqueous polymer emulsions that can obtain higher comprehensive performance.A lot of people have carried out the research work of urethane or polyurethane-urea modified acrylate emulsion, but are mostly two kinds of water-based emulsions are carried out physical mixed, and the two consistency is poor, are difficult to realize perfectly compound.Yang Ning etc. have reported preparation method's (coatings industry of the little crosslinked acrylic ester elastic emulsion of a kind of polyurethane-urea, 2011,41 (4): 31-34), to be that 2000 Amino Terminated polyether(ATPE) and tolylene diisocyanate (TDI) pre-polymerization synthesize two ends with the polyurethane prepolymer of isocyanate group with molecular weight, after preparing the macromolecules cross-linking agent with the Hydroxyethyl acrylate end-blocking, obtain the little crosslinked elastic emulsion of polyurethane urea with copolymerization such as acrylate, but because the molecular weight of Amino Terminated polyether(ATPE) is very large, the molecular weight of prepared macromolecules cross-linking agent has reached 2582, only contain two ammonia ester bonds and two urea keys in the macromole, when it is participated in copolymerization as little linking agent, the massfraction of the macromolecules cross-linking agent that adds is about 2%, otherwise easy breakdown of emulsion is crosslinked or the generation gelation reaction, and make letex polymerization failed, and, at this moment, the molar fraction of linking agent only has about 0.08%, like this, ammonia ester bond and the urea key introduced in the multipolymer are just few, and the effect of modification is also not obvious.
Summary of the invention
The present invention overcomes the deficiency of the existing little cross linked acrylic elastic emulsion of polyurethane-urea technology of preparing, a kind of method that contains the macromolecules cross-linking agent of more ammonia ester bond and urea key is provided, and has synthesized the little cross linked acrylic elastic emulsion of the obvious polyurethane-urea of modified effect take it as linking agent by emulsion copolymerization.
The preparation method who contains the linking agent of ammonia ester bond and urea key is:
1, the polyurethane-urea prepolymer is synthetic
Small molecules dibasic alcohol and diamine fully mixed with vulcabond after the drying respectively by a certain percentage carried out prepolymerization reaction 2-3 hour at 60-80 ℃, mol ratio by control vulcabond and dibasic alcohol and diamine, make vulcabond excessive, the ending isocyanate prepolymer that preparation has following structure, in this structural formula-O (CN)-refer to might be Sauerstoffatom, being to be ammonia ester bond in the structural formula, also might be hydrogen bound to nitrogen, namely is the urea key in the structural formula.When the mol ratio of the total mole number of hydroxyl and amido in dibasic alcohol and the diamine and vulcabond is 2: 3, n=1; When the mol ratio of the two was 3: 4, n=2 by that analogy, can introduce a plurality of ammonia ester bonds and urea key like this in prepolymer, and control n is between 1-4 among the present invention
2, the preparation of the crosslinked large monomer of polyurethane-urea
Will be in the above prepolymer that obtains add and the equimolar propenoic acid beta-hydroxy base of isocyanate group ethyl ester, carried out end capping 3-4 hour in 70-80 ℃ according to following reaction formula, just obtained the polyurethane-urea linking agent that two keys are contained at two ends.
The preparation method of the little cross-linking modified acrylic ester elastic emulsion of polyurethane-urea:
Deionized water is placed reaction flask, the anion surfactant of adding total monomer weight 0.5%-2% and the nonionogenic tenside of 1%-4% are as compound emulsifying agent, the water-soluble persulfate initiator of total monomer weight 0.2-1%, stirring is warming up to 60-90 ℃, the synthesis of polyurethane linking agent of total monomer weight 1-4% is dissolved in the methyl methacrylate and vinylformic acid mix monomer of acrylic monomer and requirement, in 2-3 hour, be added drop-wise in the reaction flask, insulation reaction 2-3 hour again, just obtained polyurethane-modified acrylic ester elastic emulsion.
Concrete formula rate is as follows:
The said small molecules dibasic alcohol of the present invention is selected from ethylene glycol, BDO, 1, and one or several in 6-hexylene glycol, glycol ether, Triethylene glycol, pentanediol, ethohexadiol, the decanediol are dibasic alcohol that hydroxyl is contained at two ends.Diamine is quadrol, 1, one or several in 6-hexanediamine and the 1，10-diaminodecane.Dibasic alcohol and diamine mix use, and the mol ratio of the two is controlled between 1: 2 to 2: 1.
The said vulcabond of the present invention comprise 2,4 toluene diisocyanate (2,4-TDI), 2,4 toluene diisocyanate/2,6-tolylene diisocyanate mixture, mainly comprise two kinds, a kind of is commodity TDI (80/20), and a kind of is TDI (65/35).Other also comprise isofoer diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 1,5-naphthalene diisocyanate (NDI).
The said acrylic monomer of the present invention comprises methyl acrylate, ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer.
The said anion surfactant of the present invention mainly is sodium lauryl sulphate or Sodium dodecylbenzene sulfonate, and nonionogenic tenside is selected from alkylphenol polyoxyethylene.
The said water soluble starter of the present invention is selected from Potassium Persulphate, ammonium persulphate.
Embodiment
One, the preparation example of polyurethane-urea linking agent
Embodiment 1
With 18g (0.2mol) 1,4-butyleneglycol, 6g quadrol (0.1mol) are mixed in the reaction flask with 69.6g (0.4mol) commodity TDI (80/20), be warming up to 60-80 ℃ of reaction 2.5 hours, it is 2 polyurethane-urea prepolymer that cooling discharging obtains n, wherein the ratio of ammonia ester bond and urea key is 2: 1, and molecular weight is 936g/mol.
Getting the above polyurethane-urea prepolymer 93.6g that makes (isocyanate terminated basic content 0.2mol) is mixed in the reaction flask with 21.2g propenoic acid beta-hydroxy base ethyl ester, stir and to be warming up to 70-80 ℃ and to carry out end capping 3-4 hour down, just obtained the polyurethane-urea linking agent PUC-1 that pair keys are contained at two ends.The molecular weight of this linking agent is 1148g/mol, contains ammonia ester bond and urea key totally 8/mol.
Embodiment 2
With 13.5g (0.15mol) 1,4-butyleneglycol, 17.4g 1,6-hexanediamine (0.15mol) is mixed in the reaction flask with 69.6g (0.4mol) commodity TDI (80/20), be warming up to 60-80 ℃ of reaction 2.5 hours, it is 2 polyurethane-urea prepolymer that cooling discharging obtains n, wherein the ratio of ammonia ester bond and urea key is 1: 1, and molecular weight is 1005g/mol.
Getting the above polyurethane-urea prepolymer 20.1g that makes (isocyanate terminated basic content 0.04mol) is mixed in the reaction flask with 4.24g propenoic acid beta-hydroxy base ethyl ester, stir and to be warming up to 70-80 ℃ and to carry out end capping 3-4 hour down, just obtained the polyurethane-urea linking agent PUC-2 that pair keys are contained at two ends.The molecular weight of this linking agent is 1217g/mol, contains ammonia ester bond and urea key totally 8/mol.
Embodiment 3
With 10.6g (0.1mol) glycol ether, 11.6g 1,6-hexanediamine (0.1mol) is mixed in the reaction flask with 50.4g (0.3mol) HDI, be warming up to 60-80 ℃ of reaction 3 hours, it is 1 polyurethane-urea prepolymer that cooling discharging obtains n, and ammonia ester bond and urea key ratio are that the molecular weight of 1: 1 gained prepolymer is 726g/mol.
Getting the above polyurethane-urea prepolymer 72.6g that makes (isocyanate terminated basic content 0.2mol) is mixed in the reaction flask with 21.2g propenoic acid beta-hydroxy base ethyl ester, stir and to be warming up to 70-80 ℃ and to carry out end capping 3-4 hour down, just obtained the polyurethane-urea linking agent PUC-3 that pair keys are contained at two ends.The molecular weight of this linking agent is 938g/mol, contains ammonia ester bond and urea key totally 6/mol.
Embodiment 4
With 23.6g (0.2mol) 1,6-hexylene glycol, 23.2g 1,6-hexanediamine (0.2mol) with 87g (0.5mol) 2,4-TDI is mixed in the reaction flask, be warming up to 40 ℃ of reactions 1 hour, after be warming up to 80 ℃ of reactions 2 hours, it is 3 polyurethane-urea prepolymer that cooling discharging obtains n, the molecular weight of gained prepolymer is 1340g/mol, and the ratio of ammonia ester bond and urea key is 1: 1.
Getting the above polyurethane prepolymer 67g that makes (isocyanate terminated basic content 0.1mol) is mixed in the reaction flask with 10.6g propenoic acid beta-hydroxy base ethyl ester, stir and to be warming up to 70-80 ℃ and to carry out end capping 3-4 hour down, just obtained the polyurethane-urea linking agent PUC-1 that pair keys are contained at two ends.The molecular weight of this linking agent is 1546g/mol, contains ammonia ester bond and urea key totally 10/mol.
Embodiment 5
With 18.6g (0.3mol) ethylene glycol, 37.4g 1,10-decamethylene diamine (0.2mol) is mixed in the reaction flask with 133.2g (0.6mol) IPDI, be warming up to 60-80 ℃ of reaction 2 hours, it is 4 polyurethane-urea prepolymer that cooling discharging obtains n, the molecular weight of gained prepolymer is 1892g/mol, and the ratio of ammonia ester bond and urea key is 3: 2.
Getting the above polyurethane prepolymer 94.6g that makes (isocyanate terminated basic content 0.1mol) is mixed in the reaction flask with 10.6g propenoic acid beta-hydroxy base ethyl ester, stir and to be warming up to 80 ℃ and to carry out end capping 3-4 hour down, just obtained the polyurethane cross-linking agent PUC-5 that pair keys are contained at two ends.The molecular weight of this linking agent is 1998g/mol, contains ammonia ester bond and urea key totally 12/mol.
Embodiment 6
With 9g (0.1mol) 1,4-butyleneglycol, 11.6g 1,6-hexanediamine (0.1mol) is mixed in the reaction flask with 50.4g (0.3mol) HDI, be warming up to 40 ℃ of reactions 1 hour, after be warming up to 80 ℃ the reaction 2 hours, it is 1 polyurethane-urea prepolymer that cooling discharging obtains n, and the molecular weight of gained prepolymer is 710g/mol, and ammonia ester bond and urea key ratio are 1: 1.
Getting the above polyurethane prepolymer 71g that makes (isocyanate terminated basic content 0.2mol) is mixed in the reaction flask with 21.2g propenoic acid beta-hydroxy base ethyl ester, stir and to be warming up to 80 ℃ and to carry out end capping 3-4 hour down, just obtained the polyurethane-urea linking agent PUC-6 that pair keys are contained at two ends.The molecular weight of this linking agent is 922g/mol, contains ammonia ester bond and urea key totally 6/mol.
Two, the preparation of polyurethane-urea improved elastic emulsion
Embodiment 7
Add the 45ml deionized water in there-necked flask, add 0.5g sodium lauryl sulphate and 1g OP-10 as compound emulsifying agent, the 0.4g ammonium persulfate initiator stirs and is warming up to 60-90 ℃.30g butyl acrylate, 20g methyl methacrylate are mixed with 1g vinylformic acid, aforementioned PUC-1 polyurethane-urea linking agent 1.28g fully is dissolved in the above mix monomer, in 2-3 hour, be added drop-wise in the reaction flask, insulation reaction 2-3 hour again, just obtained the acrylic ester elastic emulsion PUA-1 of polyurethane-urea modification.
Embodiment 8
Add the 45ml deionized water in there-necked flask, add 0.4g Sodium dodecylbenzene sulfonate and 0.8g OP-10 as compound emulsifying agent, the 0.5g ammonium persulfate initiator stirs and is warming up to 60-90 ℃.32g butyl acrylate, 16g methyl methacrylate are mixed with 1g vinylformic acid, aforementioned PUC-1 polyurethane-urea linking agent 1.5g fully is dissolved in the above mix monomer, in 2-3 hour, be added drop-wise in the reaction flask, insulation reaction 2-3 hour again, just obtained the acrylic ester elastic emulsion PUA-2 of polyurethane-urea modification.
Embodiment 9
Add the 45ml deionized water in there-necked flask, add 0.45g sodium lauryl sulphate and 0.9g OP-10 as compound emulsifying agent, the 0.45g ammonium persulfate initiator stirs and is warming up to 60-90 ℃.32g butyl acrylate, 16g methyl methacrylate are mixed with 1.3g vinylformic acid, aforementioned PUC-2 polyurethane-urea linking agent 1.7g fully is dissolved in the above mix monomer, in 2-3 hour, be added drop-wise in the reaction flask, insulation reaction 2-3 hour again, just obtained the acrylic ester elastic emulsion PUA-3 of polyurethane-urea modification.
Embodiment 10
Add the 46ml deionized water in there-necked flask, add 0.3g sodium lauryl sulphate and 0.6g OP-10 as compound emulsifying agent, the 0.35g ammonium persulfate initiator stirs and is warming up to 60-90 ℃.30g butyl acrylate, 20g methyl methacrylate are mixed with 1.5g vinylformic acid, aforementioned PUC-2 polyurethane-urea linking agent 2g fully is dissolved in the above mix monomer, in 2-3 hour, be added drop-wise in the reaction flask, insulation reaction 2-3 hour again, just obtained the acrylic ester elastic emulsion PUA-4 of polyurethane-urea modification.
Embodiment 11
Add the 48ml deionized water in there-necked flask, add 0.45g Sodium dodecylbenzene sulfonate and 0.9g OP-10 as compound emulsifying agent, the 0.41g ammonium persulfate initiator stirs and is warming up to 60-90 ℃.31g butyl acrylate, 17g methyl methacrylate are mixed with 1.8g vinylformic acid, aforementioned PUC-3 polyurethane-urea linking agent 1g fully is dissolved in the above mix monomer, in 2-3 hour, be added drop-wise in the reaction flask, insulation reaction 2-3 hour again, just obtained the acrylic ester elastic emulsion PUA-5 of polyurethane-urea modification.
Embodiment 12
Add the 45ml deionized water in there-necked flask, add 0.4g sodium lauryl sulphate and 0.8g OP-10 as compound emulsifying agent, the 0.4g ammonium persulfate initiator stirs and is warming up to 60-90 ℃.29g butyl acrylate, 20g methyl methacrylate are mixed with 1.1g vinylformic acid, aforementioned PUC-4 polyurethane-urea linking agent 0.8g fully is dissolved in the above mix monomer, in 2-3 hour, be added drop-wise in the reaction flask, insulation reaction 2-3 hour again, just obtained the acrylic ester elastic emulsion PUA-6 of polyurethane-urea modification.
Embodiment 13
Add the 46ml deionized water in there-necked flask, add 0.43g sodium lauryl sulphate and 0.86g OP-10 as compound emulsifying agent, the 0.365g ammonium persulfate initiator stirs and is warming up to 60-90 ℃.28g butyl acrylate, 22g methyl methacrylate are mixed with 1.3g vinylformic acid, aforementioned PUC-5 polyurethane-urea linking agent 2g fully is dissolved in the above mix monomer, in 2-3 hour, be added drop-wise in the reaction flask, insulation reaction 2-3 hour again, just obtained the acrylic ester elastic emulsion PUA-7 of polyurethane-urea modification.
Embodiment 14
Add the 45ml deionized water in there-necked flask, add 0.45g sodium lauryl sulphate and 0.9g OP-10 as compound emulsifying agent, the 0.35g ammonium persulfate initiator stirs and is warming up to 60-90 ℃.28g butyl acrylate, 22g methyl methacrylate are mixed with 1.5g vinylformic acid, aforementioned PUC-6 polyurethane-urea linking agent 2g fully is dissolved in the above mix monomer, in 2-3 hour, be added drop-wise in the reaction flask, insulation reaction 2-3 hour again, just obtained the acrylic ester elastic emulsion PUA-8 of polyurethane-urea modification.
The performance of the prepared acrylic ester elastic emulsion of embodiment 7-14 is listed in table one:
Can find out that by data in the table intensity of the elastic emulsion that this is polyurethane-modified and elasticity are all fine, also section is higher than related data (coatings industry, 2011,41 (4): 31-34) of the little crosslinked acrylic ester elastic emulsion of the urethane of the report such as Yang Ning.
Claims (12)
1. the preparation method of a polyurethane-urea linking agent may further comprise the steps:
1) will the small molecules dibasic alcohol, diamine mixes through after the abundant drying, carries out prepolymerization reaction 2-3 hour the ending isocyanate prepolymer that preparation has following structure at 60-80 ℃ with excessive vulcabond.
2) will be in the polyurethane-urea prepolymer for preparing add and the equimolar propenoic acid beta-hydroxy base of isocyanate group ethyl ester, carried out end capping 3-4 hour in 70-80 ℃, just obtained the polyurethane-urea linking agent that two keys are contained at two ends.
2. according to polyurethane-urea linking agent claimed in claim 1, it is characterized in that, its polymerization degree n is between 1-4
3. according to polyurethane-urea linking agent claimed in claim 1, it is characterized in that, described small molecules dibasic alcohol is to be selected from ethylene glycol, BDO, 1, one or several in 6-hexylene glycol, glycol ether, Triethylene glycol, pentanediol, ethohexadiol, the decanediol.
4. according to polyurethane-urea linking agent claimed in claim 1, it is characterized in that, described small molecules diamine is to be selected from quadrol, 1, one or several in 6-hexanediamine, the 1，10-diaminodecane
5. according to polyurethane-urea linking agent claimed in claim 1, it is characterized in that, the mol ratio of described small molecules dibasic alcohol and diamine is between 1: 2 to 2: 1
6. according to polyurethane-urea linking agent claimed in claim 1, it is characterized in that, described vulcabond is selected from 2,4-tolylene diisocyanate (2,4-TDI), 2,4-tolylene diisocyanate/2,6-tolylene diisocyanate mixture, isofoer diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 1,5-naphthalene diisocyanate (NDI).
7. the acrylic ester elastic emulsion of a polyurethane-urea modification, it is characterized in that: the prescription of this emulsion comprises:
8. according to the polyurethane-urea improved elastic emulsion of the described prescription of claim 6, its preparation method is:
Deionized water is placed reaction flask, the anion surfactant of adding formula ratio and nonionogenic tenside are as compound emulsifying agent, water-soluble persulfate initiator, stirring is warming up to 60-90 ℃, to be dissolved in acrylic monomer and methyl methacrylate and the vinylformic acid mix monomer according to the described synthetic polyurethane-urea linking agent of claim 1, in 2-3 hour, be added drop-wise in the reaction flask, insulation reaction 2-3 hour again, just obtained the acrylic ester elastic emulsion of polyurethane-urea modification.
9. comprise methyl acrylate, ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer according to claim 7 and 8 described acrylic monomers.
10. be sodium lauryl sulphate or Sodium dodecylbenzene sulfonate according to claim 7 and 8 described anion surfactants.
11. be selected from alkylphenol polyoxyethylene according to claim 7 and 8 described nonionogenic tensides.
12. be selected from Potassium Persulphate, ammonium persulphate according to claim 7 and 8 described water soluble starters.
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| CN104311724A (en) * | 2014-10-11 | 2015-01-28 | 湖南中汉高分子材料科技有限公司 | Preparation method of volatile polyacrylate elastic resin |
| CN108707217A (en) * | 2018-05-30 | 2018-10-26 | 苏州中来光伏新材股份有限公司 | Crosslinking agent, the manufacturing method of crosslinking agent and solar cell backboard |
| CN109476816A (en) * | 2016-07-15 | 2019-03-15 | 巴斯夫涂料有限公司 | Water-borne base coat and use base coat prepare multilayer paint system |
| CN112266457A (en) * | 2020-11-06 | 2021-01-26 | 广州市嵩达新材料科技有限公司 | Photocuring hydrophilic polyurea nano particle and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104311724A (en) * | 2014-10-11 | 2015-01-28 | 湖南中汉高分子材料科技有限公司 | Preparation method of volatile polyacrylate elastic resin |
| CN109476816A (en) * | 2016-07-15 | 2019-03-15 | 巴斯夫涂料有限公司 | Water-borne base coat and use base coat prepare multilayer paint system |
| CN109476816B (en) * | 2016-07-15 | 2021-09-03 | 巴斯夫涂料有限公司 | Aqueous base coat and preparation of multicoat paint system using the base coat |
| CN108707217A (en) * | 2018-05-30 | 2018-10-26 | 苏州中来光伏新材股份有限公司 | Crosslinking agent, the manufacturing method of crosslinking agent and solar cell backboard |
| CN112266457A (en) * | 2020-11-06 | 2021-01-26 | 广州市嵩达新材料科技有限公司 | Photocuring hydrophilic polyurea nano particle and preparation method and application thereof |
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