CN104087235A - Water-based polyurethane adhesive and preparation method thereof - Google Patents
Water-based polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN104087235A CN104087235A CN201410324567.4A CN201410324567A CN104087235A CN 104087235 A CN104087235 A CN 104087235A CN 201410324567 A CN201410324567 A CN 201410324567A CN 104087235 A CN104087235 A CN 104087235A
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- polyurethane adhesives
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Abstract
The invention provides a water-based polyurethane adhesive and a preparation method thereof. The water-based polyurethane adhesive comprises a prepolymer and water, wherein the prepolymer is dispersed into the water to form a solution, solid content of the solution is 50%, the prepolymer is prepared from the following raw materials: polyethylene glycol, polyester dihydric alcohol, carboxylic acid type hydrophilic chain extender, diisocyanate and a micromolecule chain extender, the mole ratio of polyethylene glycol to polyester dihydric alcohol to carboxylic acid type hydrophilic chain extender to diisocyanate to a micromolecule chain extender is (25-40):X:(10-X):(7.5-15):(7.5-15), and X is any numerical value from 0 to 10. The invention also provides a preparation method of the water-based polyurethane adhesive. The prepared water-based polyurethane adhesive has high solid content and good dispersion stability, maintains some good performances of the traditional solvent type polyurethane adhesive and also has the advantages of safety, difficulty in combustion, no pollution to the environment and high peeling strength.
Description
Technical field
The present invention relates to a kind of Aqueous Polyurethane Adhesives and preparation method thereof, belong to sizing agent technical field.
Background technology
In prior art, most of adhesive for polyurethane that domestic research and development are produced are all solvent type, use Zhe Dui China environment of this solvent type sizing agent has caused very large pressure, in order to respond the requirement of environmental protection, increasing people, at the Aqueous Polyurethane Adhesives of research and development excellent performance, replaces solvent type sizing agent with this both at home and abroad now.But the stripping strength of existing Aqueous Polyurethane Adhesives is generally very low, do not reach the stripping strength of solvent-based adhesive far away, can not meet service requirements.
In China, owing to being subject to the impact of the aspects such as price, raw material, the polyvalent alcohol that Aqueous Polyurethane Adhesives is used is mainly the alcohol that uses polyether-type, and conventional is main raw material mainly with polyoxytrimethylene ether glycol, and the glued membrane of this emulsion has some defects aspect intensity; And external polyvalent alcohol is mainly used polyester type, conventional have a poly adipate succinic acid ester (PBA), and because of the strong polarity ester group containing in its structure, so good with the bonding force of polar substrates, resistance to thermooxidation is also good than polyether-type.Polycaprolactone polyol and the comparison of conventional polyester polyol phase, the urethane of preparation is even better aspect wear-resisting, resistance to oxidation, resistant to chemical media and anti tear, but the domestic product of preparing with polycaprolactone dibasic alcohol is less, in patent CN102827570A, adopt polyester polyol to prepare the adhesives for shoes that solid content is 50%, but the initial bonding strength of the sizing agent obtaining is on the low side, to be improved.
Summary of the invention
Defect in view of above-mentioned prior art exists, the object of the invention is a kind of Aqueous Polyurethane Adhesives and preparation method thereof, and the adhesive for polyurethane solid content that can solve aqueous, environmental protective is low, the problem that stripping strength is low.
Object of the present invention is achieved by the following technical programs:
An Aqueous Polyurethane Adhesives, comprises prepolymer and water, after described prepolymer is distributed in water, forms solution, and the solid content of solution is 50% (can for more than 50%); Wherein, described prepolymer comprises that following raw material forms:
Polyoxyethylene glycol (PEG), polyester diol, carboxylic acid type wetting ability chainextender, vulcabond and small molecule chain extender; With molar ratio computing, Er Yi Qing Suan Zhi ︰ Ju Yi bis-Chun ︰ polyester Er Yuan Chun ︰ carboxylic acid type wetting ability Kuo Lian Ji ︰ small molecule chain extender=(25-40): X: (10-X): (7.5-15): (7.5-15), wherein, between X value 0 to 10, comprise 0 and 10 any number.
In above-mentioned Aqueous Polyurethane Adhesives, polyoxyethylene glycol, polyester diol are respectively the polyvalent alcohol of polyether-type and polyester type, both mix and use according to different ratios, and the Performance Ratio of the sizing agent obtaining is used separately polyether-type or uses separately polyester type all will exceed a lot; Preferably, described polyoxyethylene glycol is PEG2k, and described polyester diol is the polyester diol of molecular weight 2000, but is not limited to this.
According to specific embodiments, in above-mentioned Aqueous Polyurethane Adhesives, during solid content 50% actually operating, refer to that the part by weight of prepolymer and water equals 1:1.
In above-mentioned Aqueous Polyurethane Adhesives, preferred, the raw material of described prepolymer also comprises catalyzer, and its consumption is the 0.01wt%-0.1wt% of prepolymer gross weight; Preferred, described catalyzer comprises stannous octoate and/or dibutyl tin laurate, but is not limited to this.
In above-mentioned Aqueous Polyurethane Adhesives, preferred, the raw material of described prepolymer also comprises neutralizing agent, with molar ratio computing, and carboxylic acid type wetting ability Kuo Lian Ji ︰ neutralizing agent=1: 1; Preferred, described neutralizing agent is triethylamine (TEA), but is not limited to this.
Above-mentioned triethylamine is neutralizing agent, neutralizing agent can in and carboxylic acid type wetting ability chainextender in-COOH.
In above-mentioned Aqueous Polyurethane Adhesives, preferably, described polyester diol comprises poly-hexanodioic acid-BDO ester, poly-hexanodioic acid-1, the combination of one or more in 6-butanediol ester, poly-epsilon-caprolactone, PCDL, PTMG etc.
In above-mentioned Aqueous Polyurethane Adhesives, preferred, described vulcabond comprises one or more the combination in aliphatic vulcabond, alicyclic vulcabond, aromatic vulcabond etc.; Described aliphatic vulcabond comprises ONC-(CH
2)
4-NCO, ONC-(CH
2)
6-NCO, ONC-(CH
2)
8-NCO, ONC-(CH
2)
12-NCO, 1, the combination of one or more in 5-bis-isocyanic acids-2-methylpentane etc.; Described alicyclic vulcabond comprises
deng in one or more combination; Described aromatic vulcabond comprises
deng in one or more combination.
In above-mentioned Aqueous Polyurethane Adhesives, preferred, described carboxylic acid type wetting ability chainextender comprises one or more the combination in dimethylolpropionic acid (DMBA), dimethylol propionic acid (DMPA), diaminobenzoic acid, dihydroxyl half ester etc.
In above-mentioned Aqueous Polyurethane Adhesives, described small molecule chain extender is the combination of monomer or monomer; Preferably, described small molecule chain extender comprises Isosorbide-5-Nitrae butyleneglycol, HO-(CH
2)
2-OH, H
2n-(CH
2)
2-NH
2, H
2n-(CH
2)
6-NH
2, H
2n-(CH
2)
8-NH
2, H
2n-(CH
2)
10-NH
2,
deng in one or more combination.
The present invention also provides the preparation method of above-mentioned Aqueous Polyurethane Adhesives, comprises the steps:
Polyoxyethylene glycol (PEG), polyester diol, carboxylic acid type wetting ability chainextender are dissolved in organic solvent, then add vulcabond and catalyzer, at 70 ℃-80 ℃, stirring reaction 3h-4h, obtains just poly-liquid;
In just poly-liquid, add small molecule chain extender, at 50 ℃-70 ℃, stirring reaction 1h-2h, obtains mixed with polymers liquid;
In mixed with polymers liquid, add neutralizing agent triethylamine (TEA), completely in and carboxylic acid type wetting ability chainextender, in temperature, be 40 ℃-50 ℃, stir 0.5h, obtain prepolymer;
In prepolymer, slowly drip water, stirring and emulsifying is disperseed, and then organic solvent is sloughed in underpressure distillation, obtains Aqueous Polyurethane Adhesives.
In above-mentioned preparation method, organic solvent is conventional solvent, preferably acetone; Its consumption is excessive, can dissolve all raw materials of prepolymer completely.
The Aqueous Polyurethane Adhesives of gained of the present invention, initial and final stripping strength can reach the highest 48Ncm respectively
-1and 55Ncm
-1.
Gained Aqueous Polyurethane Adhesives of the present invention preferably can be used as adhesives for shoes.
Outstanding effect of the present invention is:
1. the Aqueous Polyurethane Adhesives solid content that prepared by the present invention is high, and up to 50%, viscosity is little, and good fluidity is easy to use; And there is good dispersion stabilization, and make it not only retain some premium propertiess of conventional solvent type polyurethane sizing agent, have more the advantage safe, nonflammable, free from environmental pollution, stripping strength is high.
2. preparation technology is simple, and raw material is easy to get, and can realize industrial production, and preparation process is pollution-free, and solvent is recyclable, to human body without injury, can meet the requirement of environmental protection;
3. polyester type and polyether polyol mix and use according to different ratios, and the Performance Ratio of the sizing agent obtaining is used separately polyether-type or uses separately polyester type all will get well;
4. adopt just polymers of single stage method preparation, the better performances of the sizing agent obtaining, stripping strength is high.
Accompanying drawing explanation
Fig. 1 is the preparation flow figure of the Aqueous Polyurethane Adhesives of embodiment 1-8;
Fig. 2 is the Aqueous Polyurethane Adhesives WPUD of embodiment 1-8 and the infrared spectrum of feed composition thereof;
Fig. 3 a is the initial stripping strength figure of the synthetic adhesive for polyurethane of the polyester of different ratios of embodiment 1-8;
Fig. 3 b is the final stripping strength figure of the synthetic adhesive for polyurethane of the polyester of different ratios of embodiment 1-8;
Fig. 3 c is the water contact angle trend map of the synthetic adhesive for polyurethane glued membrane of the polyester of different ratios of embodiment 1-8;
Fig. 3 d is the water contact angle schematic diagram of the synthetic adhesive for polyurethane glued membrane of the polyester of different ratios of embodiment 1-8;
Fig. 3 e is the viscosity profile figure of the synthetic adhesive for polyurethane of the polyester of different ratios of embodiment 1-8;
Embodiment
Below by specific embodiment, method of the present invention is described, so that technical solution of the present invention is easier to understand, grasp, but the present invention is not limited thereto.Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
Explanation of nouns:
PEG refers to: polyoxyethylene glycol;
TEA refers to: triethylamine;
PBA refers to: poly-hexanodioic acid BDO ester;
IPDI refers to: isophorone diisocyanate, chemical name 3-isocyanic ester methylene-3,5,5-3-methyl cyclohexanol based isocyanate;
HDI refers to hexamethylene diisocyanate;
MDI refers to 4,4-diphenylmethanediisocyanate;
DMPA refers to 2,2-dimethylol propionic acid;
DMBA refers to: 2,2-dimethylolpropionic acid;
NCO refers to: isocyanate group in chemical material, and its value refers to the quality of the contained isocyanic ester of 100g sample (NCO) group;
BDO refers to: BDO;
EDA refers to quadrol.
Embodiment 1
The present embodiment provides a kind of Aqueous Polyurethane Adhesives, comprises prepolymer and water, and described prepolymer comprises that following raw material forms:
Polyester diol PBA2k, carboxylic acid type wetting ability chainextender DMBA, vulcabond IPDI, small molecule chain extender BDO and TEA, with molar ratio computing, IPDI: PBA: DMBA: BDO: TEA=35: 10: 7.5: 7.5: 7.5.
The Aqueous Polyurethane Adhesives of the present embodiment prepares by following method, as shown in Figure 1:
40gPBA2k is warming up to 120 ℃, dehydration 30min, pour in the 250ml there-necked flask that thermometer, reflux condensing tube and agitator are housed, 50 ℃ of insulations, then add wherein the acetone soln of 15.5gIPDI and 2.25gDMBA (in molar weight DMBA: acetone=1:1), be warmed up to 75 ℃, at the uniform velocity stirring reaction 3h, obtains just poly-liquid;
In just poly-liquid, add 1.35gBDO chain extension, 70 ℃ of reaction 1h, obtain mixed with polymers liquid, for guaranteeing that sufficient reacting carries out, observe viscosity in reaction process, find when viscosity is excessive to add acetone to be reduced;
Reaction system is down to 20 ℃, adds acetone solvent regulation system viscosity, with dropping funnel, slowly drip 1.5g triethylamine and neutralize, and strong stirring half an hour, prepolymer obtained;
In to the water that slowly drips massfraction 50% in prepolymer to system, stirring and emulsifying is disperseed, and then lower boiling acetone is sloughed in underpressure distillation, obtains Aqueous Polyurethane Adhesives.
Embodiment 2
The present embodiment provides a kind of Aqueous Polyurethane Adhesives, comprises prepolymer and water, and described prepolymer comprises that following raw material forms:
Polyester diol PBA2k, PEG2k, carboxylic acid type wetting ability chainextender DMBA, vulcabond IPDI, small molecule chain extender BDO and TEA, with molar ratio computing, IPDI: PEG: PBA: DMBA: BDO: TEA=35: 0.5: 9.5: 7.5: 7.5: 7.5.
The Aqueous Polyurethane Adhesives of the present embodiment prepares by following method, as shown in Figure 1:
38gPBA2k and 2gPEG2k are warming up to 120 ℃, dehydration 30min, pour in the 250ml there-necked flask that thermometer, reflux condensing tube and agitator are housed, 50 ℃ of insulations, then add wherein the acetone soln of 15.5gIPDI and 2.25gDMBA (in molar weight DMBA: acetone=1:1), be warmed up to 75 ℃, at the uniform velocity stirring reaction 3h, obtains just poly-liquid;
In just poly-liquid, add 1.35gBDO chain extension, 70 ℃ of reaction 1h, obtain mixed with polymers liquid, for guaranteeing that sufficient reacting carries out, observe viscosity in reaction process, find when viscosity is excessive to add acetone to be reduced;
Reaction system is down to 20 ℃, adds acetone solvent regulation system viscosity, with dropping funnel, slowly drip 1.5g triethylamine and neutralize, and strong stirring half an hour, prepolymer obtained;
In to the water that slowly drips massfraction 50% in prepolymer to system, stirring and emulsifying is disperseed, and then lower boiling acetone is sloughed in underpressure distillation, obtains Aqueous Polyurethane Adhesives.
Embodiment 3
The present embodiment provides a kind of Aqueous Polyurethane Adhesives, comprises prepolymer and water, and described prepolymer comprises that following raw material forms:
Polyester diol PBA2k, PEG, carboxylic acid type wetting ability chainextender DMBA, vulcabond IPDI, small molecule chain extender BDO and TEA, with molar ratio computing, IPDI: PEG: PBA: DMBA: BDO: TEA=35: 1: 9: 7.5: 7.5: 7.5.
The Aqueous Polyurethane Adhesives of the present embodiment prepares by following method, as shown in Figure 1:
36gPBA2k and 4gPEG2k are warming up to 120 ℃, dehydration 30min, pour in the 250ml there-necked flask that thermometer, reflux condensing tube and agitator are housed, 50 ℃ of insulations, then add wherein the acetone soln of 15.5gIPDI and 2.25gDMBA (in molar weight DMBA: acetone=1:1), be warmed up to 75 ℃, at the uniform velocity stirring reaction 3h, obtains just poly-liquid;
In just poly-liquid, add 1.35gBDO chain extension, 70 ℃ of reaction 1h, obtain mixed with polymers liquid, for guaranteeing that sufficient reacting carries out, observe viscosity in reaction process, find when viscosity is excessive to add acetone to be reduced;
Reaction system is down to 20 ℃, adds acetone solvent regulation system viscosity, with dropping funnel, slowly drip 1.5g triethylamine and neutralize, and strong stirring half an hour, prepolymer obtained;
In to the water that slowly drips massfraction 50% in prepolymer to system, stirring and emulsifying is disperseed, and then lower boiling acetone is sloughed in underpressure distillation, obtains Aqueous Polyurethane Adhesives.
Embodiment 4
The present embodiment provides a kind of Aqueous Polyurethane Adhesives, comprises prepolymer and water, and described prepolymer comprises that following raw material forms:
Polyester diol PBA2k, PEG, carboxylic acid type wetting ability chainextender DMBA, vulcabond IPDI, small molecule chain extender BDO and TEA, with molar ratio computing, IPDI: PEG: PBA: DMBA: BDO: TEA=35: 2: 8: 7.5: 7.5: 7.5.
The Aqueous Polyurethane Adhesives of the present embodiment prepares by following method, as shown in Figure 1:
32gPBA2k and 8gPEG2k are warming up to 120 ℃, dehydration 30min, pour in the 250ml there-necked flask that thermometer, reflux condensing tube and agitator are housed, 50 ℃ of insulations, then add wherein the acetone soln of 15.5gIPDI and 2.25gDMBA (in molar weight DMBA: acetone=1:1), be warmed up to 75 ℃, at the uniform velocity stirring reaction 3h, obtains just poly-liquid;
In just poly-liquid, add 1.35gBDO chain extension, 70 ℃ of reaction 1h, obtain mixed with polymers liquid, for guaranteeing that sufficient reacting carries out, observe viscosity in reaction process, find when viscosity is excessive to add acetone to be reduced;
Reaction system is down to 20 ℃, adds acetone solvent regulation system viscosity, with dropping funnel, slowly drip 1.5g triethylamine and neutralize, and strong stirring half an hour, prepolymer obtained;
In to the water that slowly drips massfraction 50% in prepolymer to system, stirring and emulsifying is disperseed, and then lower boiling acetone is sloughed in underpressure distillation, obtains Aqueous Polyurethane Adhesives.
Embodiment 5
The present embodiment provides a kind of Aqueous Polyurethane Adhesives, comprises prepolymer and water, and described prepolymer comprises that following raw material forms:
Polyester diol PBA2k, PEG, carboxylic acid type wetting ability chainextender DMBA, vulcabond IPDI, small molecule chain extender BDO and TEA, with molar ratio computing, IPDI: PEG: PBA: DMBA: BDO: TEA=35: 3: 7: 7.5: 7.5: 7.5.
The Aqueous Polyurethane Adhesives of the present embodiment prepares by following method, as shown in Figure 1:
28gPBA2k and 12gPEG2k are warming up to 120 ℃, dehydration 30min, pour in the 250ml there-necked flask that thermometer, reflux condensing tube and agitator are housed, 50 ℃ of insulations, then add wherein the acetone soln of 15.5gIPDI and 2.25gDMBA (in molar weight DMBA: acetone=1:1), be warmed up to 75 ℃, at the uniform velocity stirring reaction 3h, obtains just poly-liquid;
In just poly-liquid, add 1.35gBDO chain extension, 70 ℃ of reaction 1h, obtain mixed with polymers liquid, for guaranteeing that sufficient reacting carries out, observe viscosity in reaction process, find when viscosity is excessive to add acetone to be reduced;
Reaction system is down to 20 ℃, adds acetone solvent regulation system viscosity, with dropping funnel, slowly drip 1.5g triethylamine and neutralize, and strong stirring half an hour, prepolymer obtained;
In to the water that slowly drips massfraction 50% in prepolymer to system, stirring and emulsifying is disperseed, and then lower boiling acetone is sloughed in underpressure distillation, obtains Aqueous Polyurethane Adhesives.
Embodiment 6
The present embodiment provides a kind of Aqueous Polyurethane Adhesives, comprises prepolymer and water, and described prepolymer comprises that following raw material forms:
Polyester diol PBA2k, PEG, carboxylic acid type wetting ability chainextender DMBA, vulcabond IPDI, small molecule chain extender BDO and TEA, with molar ratio computing, IPDI: PEG: PBA: DMBA: BDO: TEA=35: 4: 6: 7.5: 7.5: 7.5.
The Aqueous Polyurethane Adhesives of the present embodiment prepares by following method, as shown in Figure 1:
24gPBA2k and 16gPEG2k are warming up to 120 ℃, dehydration 30min, pour in the 250ml there-necked flask that thermometer, reflux condensing tube and agitator are housed, 50 ℃ of insulations, then add wherein the acetone soln of 15.5gIPDI and 2.25gDMBA (in molar weight DMBA: acetone=1:1), be warmed up to 75 ℃, at the uniform velocity stirring reaction 3h, obtains just poly-liquid;
In just poly-liquid, add 1.35gBDO chain extension, 70 ℃ of reaction 1h, obtain mixed with polymers liquid, for guaranteeing that sufficient reacting carries out, observe viscosity in reaction process, find when viscosity is excessive to add acetone to be reduced;
Reaction system is down to 20 ℃, adds acetone solvent regulation system viscosity, with dropping funnel, slowly drip 1.5g triethylamine and neutralize, and strong stirring half an hour, prepolymer obtained;
In to the water that slowly drips massfraction 50% in prepolymer to system, stirring and emulsifying is disperseed, and then lower boiling acetone is sloughed in underpressure distillation, obtains Aqueous Polyurethane Adhesives.
Embodiment 7
The present embodiment provides a kind of Aqueous Polyurethane Adhesives, comprises prepolymer and water, and described prepolymer comprises that following raw material forms:
Polyester diol PBA2k, PEG, carboxylic acid type wetting ability chainextender DMBA, vulcabond IPDI, small molecule chain extender BDO and TEA, with molar ratio computing, IPDI: PEG: PBA: DMBA: BDO: TEA=35: 5: 5: 7.5: 7.5: 7.5.
The Aqueous Polyurethane Adhesives of the present embodiment prepares by following method, as shown in Figure 1:
20gPBA2k and 20gPEG2k are warming up to 120 ℃, dehydration 30min, pour in the 250ml there-necked flask that thermometer, reflux condensing tube and agitator are housed, 50 ℃ of insulations, then add wherein the acetone soln of 15.5gIPDI and 2.25gDMBA (in molar weight DMBA: acetone=1:1), be warmed up to 75 ℃, at the uniform velocity stirring reaction 3h, obtains just poly-liquid;
In just poly-liquid, add 1.35gBDO chain extension, 70 ℃ of reaction 1h, obtain mixed with polymers liquid, for guaranteeing that sufficient reacting carries out, observe viscosity in reaction process, find when viscosity is excessive to add acetone to be reduced;
Reaction system is down to 20 ℃, adds acetone solvent regulation system viscosity, with dropping funnel, slowly drip 1.5g triethylamine and neutralize, and strong stirring half an hour, prepolymer obtained;
In to the water that slowly drips massfraction 50% in prepolymer to system, stirring and emulsifying is disperseed, and then lower boiling acetone is sloughed in underpressure distillation, obtains Aqueous Polyurethane Adhesives.
Embodiment 8
The present embodiment provides a kind of Aqueous Polyurethane Adhesives, comprises prepolymer and water, and described prepolymer comprises that following raw material forms:
PEG2k, carboxylic acid type wetting ability chainextender DMBA, vulcabond IPDI, small molecule chain extender BDO and TEA, with molar ratio computing, IPDI: PEG: DMBA: BDO: TEA=35: 10: 7.5: 7.5: 7.5.
The Aqueous Polyurethane Adhesives of the present embodiment prepares by following method, as shown in Figure 1:
40gPEG2k is warming up to 120 ℃, dehydration 30min, pour in the 250ml there-necked flask that thermometer, reflux condensing tube and agitator are housed, 50 ℃ of insulations, then add wherein the acetone soln of 15.5gIPDI and 2.25gDMBA (in molar weight DMBA: acetone=1:1), be warmed up to 75 ℃, at the uniform velocity stirring reaction 3h, obtains just poly-liquid;
In just poly-liquid, add 1.35gBDO chain extension, 70 ℃ of reaction 1h, obtain mixed with polymers liquid, for guaranteeing that sufficient reacting carries out, observe viscosity in reaction process, find when viscosity is excessive to add acetone to be reduced;
Reaction system is down to 20 ℃, adds acetone solvent regulation system viscosity, with dropping funnel, slowly drip 1.5g triethylamine and neutralize, and strong stirring half an hour, prepolymer obtained;
In to the water that slowly drips massfraction 50% in prepolymer to system, stirring and emulsifying is disperseed, and then lower boiling acetone is sloughed in underpressure distillation, obtains Aqueous Polyurethane Adhesives.
Embodiment 9
The present embodiment provides a kind of Aqueous Polyurethane Adhesives, comprises prepolymer and water, and described prepolymer comprises that following raw material forms:
Polyester diol PBA, carboxylic acid type wetting ability chainextender DMPA, vulcabond MDI, small molecule chain extender EDA and TEA, with molar ratio computing, MDI: PBA: DMPA: EDA: TEA=30: 10: 7.5: 7.5: 7.5.
The Aqueous Polyurethane Adhesives of the present embodiment prepares by following method, as shown in Figure 1:
PBA is warming up to 120 ℃, dehydration 30min, pour in the there-necked flask that thermometer, reflux condensing tube and agitator are housed, 50 ℃ of insulations, then add wherein the acetone soln of MDI and DMPA (in molar weight DMPA: acetone=1:1), be warmed up to 75 ℃, at the uniform velocity stirring reaction 3h, obtains just poly-liquid;
In just poly-liquid, add EDA chain extension, 70 ℃ of reaction 1h, obtain mixed with polymers liquid, for guaranteeing that sufficient reacting carries out, observe viscosity in reaction process, find when viscosity is excessive to add acetone to be reduced;
Reaction system is down to room temperature, adds acetone solvent regulation system viscosity, with dropping funnel, slowly drip triethylamine and neutralize, and strong stirring half an hour, prepolymer obtained;
In to the water that slowly drips massfraction 50% in prepolymer to system, stirring and emulsifying is disperseed, and then lower boiling acetone is sloughed in underpressure distillation, obtains Aqueous Polyurethane Adhesives.
The present embodiment adopts single stage method first to use excessive aromatic diisocyanate, polyester diol and carboxylic acid type wetting ability chainextender carry out the first aggressiveness of synthesis of polyurethane, then just aggressiveness again with the further chain extension of amine small molecules, generate urea chain prepolymer, last prepolymer and water carry out stirring and emulsifying and disperse to have obtained aqueous polyurethaneurea sizing agent.
Embodiment 10
The present embodiment provides a kind of Aqueous Polyurethane Adhesives, comprises prepolymer and water, and described prepolymer comprises that following raw material forms:
Polyester diol PBA, carboxylic acid type wetting ability chainextender DMPA, vulcabond MDI, small molecule chain extender EDA and TEA, with molar ratio computing, MDI: PBA: DMPA: EDA: TEA=30: 10: 7.5: 7.5: 7.5.
The Aqueous Polyurethane Adhesives of the present embodiment prepares by following method, as shown in Figure 1:
PBA is warming up to 120 ℃, and dehydration 30min, pours in the there-necked flask that thermometer, reflux condensing tube and agitator are housed, and 50 ℃ of insulations, then add MDI wherein, are warmed up to 75 ℃, and at the uniform velocity stirring reaction 2h, obtains just poly-liquid;
To adding in first poly-liquid the acetone soln of DMPA (in molar weight DMPA: acetone=1:1), stirring reaction 1h at the uniform velocity, add again EDA chain extension, 70 ℃ of reaction 1h, obtain mixed with polymers liquid, for guaranteeing that sufficient reacting carries out, in reaction process, observe viscosity, find when viscosity is excessive to add acetone to be reduced;
Reaction system is down to room temperature, adds acetone solvent regulation system viscosity, with dropping funnel, slowly drip triethylamine and neutralize, and strong stirring half an hour, prepolymer obtained;
In to the water that slowly drips massfraction 50% in prepolymer to system, stirring and emulsifying is disperseed, and then lower boiling acetone is sloughed in underpressure distillation, obtains Aqueous Polyurethane Adhesives.
The present embodiment is to adopt two-step approach, first with excessive vulcabond and polyester diol reaction, react again the first aggressiveness of synthesis of polyurethane with carboxylic acid type wetting ability chainextender, and then with the further chain extension of small molecule chain extender, finally form prepolymer and water and carry out stirring and emulsifying and disperse to obtain aqueous polyurethaneurea sizing agent.
Aqueous Polyurethane Adhesives to embodiment 1-8 gained is tested, result is as shown in table 1 (polyester of different ratios mixes the experimental result of soft section of synthetic adhesive for polyurethane) and Fig. 2, Fig. 3 (a-e), embodiment 1-8 adopts acetone method, take PEG and PBA as mixing soft section, and the ratio adding is as follows respectively: m (PEG/PBA)=0/10; 0.5/9.5; 1/9; 2/8; 3/7; 4/6; 5/5; 10/0, the Performance Ratio of the sizing agent obtaining is used separately polyether-type or uses separately polyester type all will exceed a lot.
Table 1
As seen from Figure 2, in figure, demonstrated the infrared spectrum of Aqueous Polyurethane Adhesives (WPUD).In figure, also show other raw-material infrared spectrum.2275-2250cm as seen from the figure
-1the NCO base peak at place disappears substantially, illustrates that NCO group has participated in reaction substantially completely; And 3419cm
-1and 1653cm
-1there is the charateristic avsorption band of N-H in place, shows that NCO group has generated carbamate groups, urea groups etc. with hydroxyl and amino reaction;
By Fig. 3 a, can be found out, initial stripping strength, along with the increase of PEG/PBA ratio, first increases afterwards and declines, and when PEG/PBA=3/7, initial stripping strength reaches maximum value.
By Fig. 3 b, can be found out, final stripping strength, along with the increase of PEG/PBA ratio, first increases afterwards and declines, and when PEG/PBA=3/7, final stripping strength reaches maximum value.
By Fig. 3 c, can be found out, along with the increase of PEG/PBA ratio, water contact angle declines gradually.
By Fig. 3 d, can be found out, the water contact angle 0<90 ° of aqueous polyurethane film, illustrate that it is lyophily, it is the wettable polyurethane film of water, this is due to self-emulsification aqueous polyaminoester emulsion, in building-up process, need in polyurethane molecular chain, introduce hydrophilic radical, contain-COO in the polyurethane latex film finally forming
-and H
+polarity ionic group, so the wettable polyurethane film of water.
By Fig. 3 e, can be found out, along with the increase of PEG/PBA ratio, PEG content improves gradually, and viscosity reduces gradually, and when m (PEG/PBA)=1/9, reducing sharply appears in viscosity.
Embodiment 9 and 10 two kind of method are compared, and result is as shown in table 2 (experimental result of the single stage method that embodiment 9 and 10 provides and the adhesive for polyurethane of two step synthesis):
Table 2
| ? | Initial stripping strength (Ncm -1) | Final stripping strength (Ncm -1) | Viscosity (mpas) |
| Single stage method | 23 | 28.3 | 1800 |
| Two-step approach | 7.5 | 20 | 360 |
As can be seen from Table 2, the initial and final stripping strength of the adhesive for polyurethane that single stage method obtains all exceeds much than two-step approach, but the viscosity ratio single stage method of the sizing agent that two-step approach obtains is little a lot.Because during with single stage method synthesis of polyurethane, DMPA preferentially reacts with IPDI, has formed long hard section and than the hydrophilic radical sequence of comparatively dense; Be distributed in molecular chain, so its hard segment length is narrow the polyalcohols molecule interval that two-step approach is grown due to hydrophilic ionic group.Therefore the urethane that single stage method polymerization obtains divides and gives interchain and strengthen containing electrostatic forcing and hydrogen bond action between hard section of hydrophilic radical, hard section easily self is assembled, from soft section, dissociate, form certain hard segment microcell, impel soft or hard section to be separated more complete.
Claims (8)
1. an Aqueous Polyurethane Adhesives, comprises prepolymer and water, after described prepolymer is distributed in water, forms solution, and the solid content of solution is 50%; Wherein, described prepolymer comprises that following raw material forms:
Polyoxyethylene glycol, polyester diol, carboxylic acid type wetting ability chainextender, vulcabond and small molecule chain extender; With molar ratio computing, Er Yi Qing Suan Zhi ︰ Ju Yi bis-Chun ︰ polyester Er Yuan Chun ︰ carboxylic acid type wetting ability Kuo Lian Ji ︰ small molecule chain extender=(25-40): X: (10-X): (7.5-15): (7.5-15), wherein, between X value 0 to 10, comprise 0 and 10 any number.
2. Aqueous Polyurethane Adhesives according to claim 1, is characterized in that: the raw material of described prepolymer also comprises catalyzer, and its consumption is the 0.01wt%-0.1wt% of prepolymer gross weight; Preferably, described catalyzer comprises stannous octoate and/or dibutyl tin laurate.
3. Aqueous Polyurethane Adhesives according to claim 1, is characterized in that: the raw material of described prepolymer also comprises neutralizing agent, with molar ratio computing, and carboxylic acid type wetting ability Kuo Lian Ji ︰ neutralizing agent=1: 1; Preferably, described neutralizing agent is triethylamine.
4. Aqueous Polyurethane Adhesives according to claim 1, it is characterized in that: described polyester diol comprises poly-hexanodioic acid-1,4-butanediol ester, poly-hexanodioic acid-1, the combination of one or more in 6-butanediol ester, poly-epsilon-caprolactone, PCDL, PTMG.
5. Aqueous Polyurethane Adhesives according to claim 1, is characterized in that: described vulcabond comprises one or more the combination in aliphatic vulcabond, alicyclic vulcabond, aromatic vulcabond; Described aliphatic vulcabond comprises ONC-(CH
2)
4-NCO, ONC-(CH
2)
6-NCO, ONC-(CH
2)
8-NCO, ONC-(CH
2)
12-NCO, 1, the combination of one or more in 5-bis-isocyanic acids-2-methylpentane; Described alicyclic vulcabond comprises
in one or more combination; Described aromatic vulcabond comprises
in one or more combination.
6. Aqueous Polyurethane Adhesives according to claim 1, is characterized in that: described carboxylic acid type wetting ability chainextender comprises one or more the combination in dimethylolpropionic acid, dimethylol propionic acid, diaminobenzoic acid, dihydroxyl half ester.
7. Aqueous Polyurethane Adhesives according to claim 1, is characterized in that: described small molecule chain extender comprises BDO, HO-(CH
2)
2-OH, H
2n-(CH
2)
2-NH
2, H
2n-(CH
2)
6-NH
2, H
2n-(CH
2)
8-NH
2, H
2n-(CH
2)
10-NH
2,
in one or more combination.
8. the preparation method of the Aqueous Polyurethane Adhesives described in claim 1-7 any one, comprises the steps:
Polyoxyethylene glycol, polyester diol, carboxylic acid type wetting ability chainextender are dissolved in organic solvent, then add vulcabond and catalyzer, at 70 ℃-80 ℃, stirring reaction 3h-4h, obtains just poly-liquid;
In just poly-liquid, add small molecule chain extender, at 50 ℃-70 ℃, stirring reaction 1h-2h, obtains mixed with polymers liquid;
In mixed with polymers liquid, add neutralizing agent triethylamine, completely in and carboxylic acid type wetting ability chainextender, in temperature, be 40 ℃-50 ℃, stir 0.5h, obtain prepolymer;
In prepolymer, slowly drip water, stirring and emulsifying is disperseed, and then organic solvent is sloughed in underpressure distillation, obtains Aqueous Polyurethane Adhesives.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108373900A (en) * | 2018-03-09 | 2018-08-07 | 广东泰强化工实业有限公司 | A kind of Aqueous Polyurethane Adhesives and preparation method thereof |
| CN108752552A (en) * | 2018-06-06 | 2018-11-06 | 上海华谊精细化工有限公司 | A kind of preparation method of branching type water-based polyurethane nano composite material |
| CN110181806A (en) * | 2019-06-03 | 2019-08-30 | 北京科技大学 | The low temperature 3D printing method of degradable aqueous polyurethane with biocompatible |
| CN113831583A (en) * | 2021-10-29 | 2021-12-24 | 盐城工学院 | Preparation method and application of OPUSA composite aerogel |
| CN115124968A (en) * | 2022-07-28 | 2022-09-30 | 扬州市伟业消防器材有限公司 | Preparation method of adhesive for fire hose |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649039A (en) * | 2008-08-15 | 2010-02-17 | 段友芦 | Aqueous polyurethane dispersion with high solid content and low activation temperature, preparation method and application thereof |
| WO2010118949A2 (en) * | 2009-04-14 | 2010-10-21 | Basf Se | Use of polyurethane adhesive made of polyester diols, polyether diols and silane compounds for producing film-coated furniture |
-
2014
- 2014-07-08 CN CN201410324567.4A patent/CN104087235B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101649039A (en) * | 2008-08-15 | 2010-02-17 | 段友芦 | Aqueous polyurethane dispersion with high solid content and low activation temperature, preparation method and application thereof |
| WO2010118949A2 (en) * | 2009-04-14 | 2010-10-21 | Basf Se | Use of polyurethane adhesive made of polyester diols, polyether diols and silane compounds for producing film-coated furniture |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108373900A (en) * | 2018-03-09 | 2018-08-07 | 广东泰强化工实业有限公司 | A kind of Aqueous Polyurethane Adhesives and preparation method thereof |
| CN108752552A (en) * | 2018-06-06 | 2018-11-06 | 上海华谊精细化工有限公司 | A kind of preparation method of branching type water-based polyurethane nano composite material |
| CN110181806A (en) * | 2019-06-03 | 2019-08-30 | 北京科技大学 | The low temperature 3D printing method of degradable aqueous polyurethane with biocompatible |
| CN110181806B (en) * | 2019-06-03 | 2021-05-04 | 北京科技大学 | Low-temperature 3D printing method of biodegradable waterborne polyurethane with biocompatibility |
| CN113831583A (en) * | 2021-10-29 | 2021-12-24 | 盐城工学院 | Preparation method and application of OPUSA composite aerogel |
| CN115124968A (en) * | 2022-07-28 | 2022-09-30 | 扬州市伟业消防器材有限公司 | Preparation method of adhesive for fire hose |
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