CN103012726B - 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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- CN103012726B CN103012726B CN201110289860.8A CN201110289860A CN103012726B CN 103012726 B CN103012726 B CN 103012726B CN 201110289860 A CN201110289860 A CN 201110289860A CN 103012726 B CN103012726 B CN 103012726B
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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 micro-cross-linking modified acrylic ester elastic emulsion of a kind of polyurethane-urea, this emulsion can be for exterior wall elastic emulsion paint in preparation high-decoration
Background technology
After acrylate copolymer emulsion film forming, there is high-decoration and film-forming properties, and urethane, polyureas and polyurethane-urea have snappiness, sticking power and water tolerance, by 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 to carry 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 micro-crosslinked acrylic ester elastic emulsion of a kind of polyurethane-urea, 2011, 41 (4): 31-34), to be 2000 with molecular weight Amino Terminated polyether(ATPE) and tolylene diisocyanate (TDI) pre-polymerization synthesize the polyurethane prepolymer of two ends with isocyanate group, by preparing after macromolecules cross-linking agent with Hydroxyethyl acrylate end-blocking, obtain the micro-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, in a macromole, only contain two ammonia ester bonds and two urea keys, in the time setting it as micro-linking agent participation copolymerization, the massfraction of the macromolecules cross-linking agent adding is in 2% left and right, otherwise easily breakdown of emulsion is cross-linked or generation gelation reaction, and make letex polymerization failed, and, now, the molar fraction of linking agent only has 0.08% left and right, like this, ammonia ester bond in introducing multipolymer and urea key are just few, the effect of modification is also not obvious.
Summary of the invention
The present invention overcomes the deficiency of the micro-cross linked acrylic elastic emulsion of existing polyurethane-urea technology of preparing, a kind of method of the macromolecules cross-linking agent that contains more ammonia ester bond and urea key is provided, and has synthesized the micro-cross linked acrylic elastic emulsion of the obvious polyurethane-urea of modified effect taking it as linking agent by emulsion copolymerization.
The preparation method of the linking agent that contains ammonia ester bond and urea key is:
1, polyurethane-urea prepolymer is synthetic
After small molecules dibasic alcohol and diamine is fully dry respectively, mix with vulcabond and carry out prepolymerization reaction 2-3 hour at 60-80 DEG C by a certain percentage, by controlling the mol ratio of vulcabond and dibasic alcohol and diamine, make vulcabond excessive, preparation has the ending isocyanate prepolymer of following structure, in this structural formula-O (CN)-refer to is likely Sauerstoffatom, be in structural formula for ammonia ester bond, be likely also hydrogen bound to nitrogen, in structural formula, be urea key.In the time that the total mole number of hydroxyl and amido in dibasic alcohol and diamine and the mol ratio of vulcabond are 2: 3, n=1; In the time that the mol ratio of the two is 3: 4, n=2 by that analogy, can introduce multiple ammonia ester bonds and urea key like this in prepolymer, controls n in the present invention between 1-4
2, the preparation of the crosslinked large monomer of polyurethane-urea
To in the prepolymer obtaining above, add and the equimolar propenoic acid beta-hydroxy base of isocyanate group ethyl ester, carry out end capping 3-4 hour according to following reaction formula in 70-80 DEG C, just obtained the polyurethane-urea linking agent that two keys are contained at two ends.
The preparation method of the micro-cross-linking modified acrylic ester elastic emulsion of polyurethane-urea:
Deionized water is placed in to reaction flask, add the anion surfactant of total monomer weight 0.5%-2% and the nonionogenic tenside of 1%-4% as compound emulsifying agent, the water-soluble persulfate initiator of total monomer weight 0.2-1%, stirring is warming up to 60-90 DEG C, 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 reaction flask, insulation reaction 2-3 hour again, has 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, decanediol are dibasic alcohol that hydroxyl is contained at two ends.Diamine is quadrol, 1, one or several in 6-hexanediamine and 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 comprises 2,4 toluene diisocyanate (2,4-TDI), 2,4 toluene diisocyanate/2,6-tolylene diisocyanate mixture, mainly comprise two kinds, one is commodity TDI (80/20), and one 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 is mainly 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, polyurethane-urea linking agent prepare example
Embodiment 1
By 18g (0.2mol) 1,4-butyleneglycol, 6g quadrol (0.1mol) are mixed in reaction flask with 69.6g (0.4mol) commodity TDI (80/20), be warming up to 60-80 DEG C 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 making (isocyanate terminated base content 0.2mol) is mixed in reaction flask with 21.2g propenoic acid beta-hydroxy base ethyl ester, under stirring, be warming up to 70-80 DEG C and carry out end capping 3-4 hour, just obtained the polyurethane-urea linking agent PUC-1 that two 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
By 13.5g (0.15mol) 1,4-butyleneglycol, 17.4g 1,6-hexanediamine (0.15mol) is mixed in reaction flask with 69.6g (0.4mol) commodity TDI (80/20), be warming up to 60-80 DEG C 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 making (isocyanate terminated base content 0.04mol) is mixed in reaction flask with 4.24g propenoic acid beta-hydroxy base ethyl ester, under stirring, be warming up to 70-80 DEG C and carry out end capping 3-4 hour, just obtained the polyurethane-urea linking agent PUC-2 that two 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
By 10.6g (0.1mol) glycol ether, 11.6g 1,6-hexanediamine (0.1mol) is mixed in reaction flask with 50.4g (0.3mol) HDI, be warming up to 60-80 DEG C 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 making (isocyanate terminated base content 0.2mol) is mixed in reaction flask with 21.2g propenoic acid beta-hydroxy base ethyl ester, under stirring, be warming up to 70-80 DEG C and carry out end capping 3-4 hour, just obtained the polyurethane-urea linking agent PUC-3 that two 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
By 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 reaction flask, be warming up to 40 DEG C of reactions 1 hour, after be warming up to 80 DEG C 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 making (isocyanate terminated base content 0.1mol) is mixed in reaction flask with 10.6g propenoic acid beta-hydroxy base ethyl ester, under stirring, be warming up to 70-80 DEG C and carry out end capping 3-4 hour, just obtained the polyurethane-urea linking agent PUC-1 that two 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
By 18.6g (0.3mol) ethylene glycol, 37.4g 1,10-decamethylene diamine (0.2mol) is mixed in reaction flask with 133.2g (0.6mol) IPDI, be warming up to 60-80 DEG C 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 making (isocyanate terminated base content 0.1mol) is mixed in reaction flask with 10.6g propenoic acid beta-hydroxy base ethyl ester, under stirring, be warming up to 80 DEG C and carry out end capping 3-4 hour, just obtained the polyurethane cross-linking agent PUC-5 that two 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
By 9g (0.1mol) 1,4-butyleneglycol, 11.6g 1,6-hexanediamine (0.1mol) is mixed in reaction flask with 50.4g (0.3mol) HDI, be warming up to 40 DEG C of reactions 1 hour, after be warming up to 80 DEG C 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 making (isocyanate terminated base content 0.2mol) is mixed in reaction flask with 21.2g propenoic acid beta-hydroxy base ethyl ester, under stirring, be warming up to 80 DEG C and carry out end capping 3-4 hour, just obtained the polyurethane-urea linking agent PUC-6 that two 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
In there-necked flask, add 45ml deionized water, add 0.5g sodium lauryl sulphate and 1g OP-10 as compound emulsifying agent, 0.4g ammonium persulfate initiator, stirs and is warming up to 60-90 DEG C.30g butyl acrylate, 20g methyl methacrylate are mixed with 1g vinylformic acid, aforementioned PUC-1 polyurethane-urea linking agent 1.28g is fully dissolved in above mix monomer, in 2-3 hour, be added drop-wise in reaction flask, insulation reaction 2-3 hour again, has just obtained the acrylic ester elastic emulsion PUA-1 of polyurethane-urea modification.
Embodiment 8
In there-necked flask, add 45ml deionized water, add 0.4g Sodium dodecylbenzene sulfonate and 0.8g OP-10 as compound emulsifying agent, 0.5g ammonium persulfate initiator, stirs and is warming up to 60-90 DEG C.32g butyl acrylate, 16g methyl methacrylate are mixed with 1g vinylformic acid, aforementioned PUC-1 polyurethane-urea linking agent 1.5g is fully dissolved in above mix monomer, in 2-3 hour, be added drop-wise in reaction flask, insulation reaction 2-3 hour again, has just obtained the acrylic ester elastic emulsion PUA-2 of polyurethane-urea modification.
Embodiment 9
In there-necked flask, add 45ml deionized water, add 0.45g sodium lauryl sulphate and 0.9g OP-10 as compound emulsifying agent, 0.45g ammonium persulfate initiator, stirs and is warming up to 60-90 DEG C.32g butyl acrylate, 16g methyl methacrylate are mixed with 1.3g vinylformic acid, aforementioned PUC-2 polyurethane-urea linking agent 1.7g is fully dissolved in above mix monomer, in 2-3 hour, be added drop-wise in reaction flask, insulation reaction 2-3 hour again, has just obtained the acrylic ester elastic emulsion PUA-3 of polyurethane-urea modification.
Embodiment 10
In there-necked flask, add 46ml deionized water, add 0.3g sodium lauryl sulphate and 0.6g OP-10 as compound emulsifying agent, 0.35g ammonium persulfate initiator, stirs and is warming up to 60-90 DEG C.30g butyl acrylate, 20g methyl methacrylate are mixed with 1.5g vinylformic acid, aforementioned PUC-2 polyurethane-urea linking agent 2g is fully dissolved in above mix monomer, in 2-3 hour, be added drop-wise in reaction flask, insulation reaction 2-3 hour again, has just obtained the acrylic ester elastic emulsion PUA-4 of polyurethane-urea modification.
Embodiment 11
In there-necked flask, add 48ml deionized water, add 0.45g Sodium dodecylbenzene sulfonate and 0.9g OP-10 as compound emulsifying agent, 0.41g ammonium persulfate initiator, stirs and is warming up to 60-90 DEG C.31g butyl acrylate, 17g methyl methacrylate are mixed with 1.8g vinylformic acid, aforementioned PUC-3 polyurethane-urea linking agent 1g is fully dissolved in above mix monomer, in 2-3 hour, be added drop-wise in reaction flask, insulation reaction 2-3 hour again, has just obtained the acrylic ester elastic emulsion PUA-5 of polyurethane-urea modification.
Embodiment 12
In there-necked flask, add 45ml deionized water, add 0.4g sodium lauryl sulphate and 0.8g OP-10 as compound emulsifying agent, 0.4g ammonium persulfate initiator, stirs and is warming up to 60-90 DEG C.29g butyl acrylate, 20g methyl methacrylate are mixed with 1.1g vinylformic acid, aforementioned PUC-4 polyurethane-urea linking agent 0.8g is fully dissolved in above mix monomer, in 2-3 hour, be added drop-wise in reaction flask, insulation reaction 2-3 hour again, has just obtained the acrylic ester elastic emulsion PUA-6 of polyurethane-urea modification.
Embodiment 13
In there-necked flask, add 46ml deionized water, add 0.43g sodium lauryl sulphate and 0.86g OP-10 as compound emulsifying agent, 0.365g ammonium persulfate initiator, stirs and is warming up to 60-90 DEG C.28g butyl acrylate, 22g methyl methacrylate are mixed with 1.3g vinylformic acid, aforementioned PUC-5 polyurethane-urea linking agent 2g is fully dissolved in above mix monomer, in 2-3 hour, be added drop-wise in reaction flask, insulation reaction 2-3 hour again, has just obtained the acrylic ester elastic emulsion PUA-7 of polyurethane-urea modification.
Embodiment 14
In there-necked flask, add 45ml deionized water, add 0.45g sodium lauryl sulphate and 0.9g OP-10 as compound emulsifying agent, 0.35g ammonium persulfate initiator, stirs and is warming up to 60-90 DEG C.28g butyl acrylate, 22g methyl methacrylate are mixed with 1.5g vinylformic acid, aforementioned PUC-6 polyurethane-urea linking agent 2g is fully dissolved in above mix monomer, in 2-3 hour, be added drop-wise in reaction flask, insulation reaction 2-3 hour again, has 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:
By table in data can find out the intensity of this polyurethane-modified elastic emulsion and elasticity all fine, also portion is higher than the related data (coatings industry of the micro-crosslinked acrylic ester elastic emulsion of urethane of the reports such as Yang Ning, 2011,41 (4): 31-34).
Claims (8)
1. a preparation method for polyurethane-urea linking agent, comprises the following steps:
1) small molecules dibasic alcohol, diamine are mixed after fully dry, carry out prepolymerization reaction 2-3 hour with excessive vulcabond at 60-80 DEG C, preparation has the ending isocyanate prepolymer of following structure;
2) will in the polyurethane-urea prepolymer preparing, add and the equimolar propenoic acid beta-hydroxy base of isocyanate group ethyl ester, carry out end capping 3-4 hour in 70-80 DEG C, just obtained the polyurethane-urea linking agent that two keys are contained at two ends;
Its polymerization degree n is between 1-4;
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, decanediol;
Described small molecules diamine is to be selected from quadrol, 1, one or several in 6-hexanediamine, 1，10-diaminodecane.
2. according to the preparation method of polyurethane-urea linking agent claimed in claim 1, it is characterized in that, described small molecules dibasic alcohol and the mol ratio of diamine are between 1: 2 to 2: 1.
3. according to the preparation method of 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).
4. an acrylic ester elastic emulsion for polyurethane-urea modification, is characterized in that: the formula of this emulsion comprises:
Connection agent
Anion surfactant 0.25-1
Nonionogenic tenside 0.5-2
Initiator 0.1-0.5
Deionized water surplus
Described acrylic monomer is selected from methyl acrylate, ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer.
5. according to the acrylic ester elastic emulsion of polyurethane-urea modification claimed in claim 4, its preparation method comprises the following steps:
Deionized water is placed in to reaction flask, add the anion surfactant of formula ratio and nonionogenic tenside as compound emulsifying agent, water-soluble persulfate initiator, stirring is warming up to 60-90 DEG C, to be dissolved according to polyurethane-urea linking agent synthetic described in claim 1 in acrylic monomer and methyl methacrylate and vinylformic acid mix monomer, in 2-3 hour, be added drop-wise in reaction flask, then insulation reaction 2-3 hour, just obtained the acrylic ester elastic emulsion of polyurethane-urea modification.
6. according to the acrylic ester elastic emulsion of the polyurethane-urea modification described in claim 4 and 5 any one, it is characterized in that, anion surfactant is sodium lauryl sulphate or Sodium dodecylbenzene sulfonate.
7. according to the acrylic ester elastic emulsion of the polyurethane-urea modification described in claim 4 and 5 any one, it is characterized in that, nonionogenic tenside is selected from alkylphenol polyoxyethylene.
8. according to the acrylic ester elastic emulsion of the polyurethane-urea modification described in claim 4 and 5 any one, it is characterized in that, initiator is selected from Potassium Persulphate, ammonium persulphate.
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| CN104311724B (en) * | 2014-10-11 | 2017-04-26 | 湖南中汉高分子材料科技有限公司 | Preparation method of volatile polyacrylate elastic resin |
| US20210301147A1 (en) * | 2016-07-15 | 2021-09-30 | Basf Coatings Gmbh | Aqueous basecoat and production of multi-coat paint systems using the basecoat |
| 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 |
| CN112266457B (en) * | 2020-11-06 | 2022-04-05 | 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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| CN102093516A (en) * | 2010-12-28 | 2011-06-15 | 东莞市英科水墨有限公司 | Waterborne polyurethane-acrylate emulsion prepared by seed emulsion polymerization method |
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