CN103409100A - Epoxy-resin-modified water-based polyurethane adhesive and preparation method thereof - Google Patents
Epoxy-resin-modified water-based polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN103409100A CN103409100A CN2013103587592A CN201310358759A CN103409100A CN 103409100 A CN103409100 A CN 103409100A CN 2013103587592 A CN2013103587592 A CN 2013103587592A CN 201310358759 A CN201310358759 A CN 201310358759A CN 103409100 A CN103409100 A CN 103409100A
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Abstract
The invention provides an epoxy-resin-modified water-based polyurethane adhesive and a preparation method thereof, belonging to the field of environment-friendly water-based adhesives. The invention solves the problems of poor storage stability and poor binding property in the existing epoxy-resin-modified water-based polyurethane adhesive. The adhesive comprises 85-100 parts of epoxy-resin-modified water-based polyurethane, 0.15-0.3 part of water-based thickener, 0.10-0.35 part of water-based leveling agent, 8-15 parts of plasticizer, 0.03-0.08 part of antioxidant and 2.5-4.5 parts of water-based curing agent. The epoxy-resin-modified water-based polyurethane is prepared from a diamido-modified epoxy resin. The invention also provides a preparation method of the epoxy-resin-modified water-based polyurethane adhesive. After the epoxy-resin-modified water-based polyurethane adhesive is prepared into a sample, the sample does not stratify after being stored in a sealed condition at 23-25 DEG C for 24 months; and the peel force exceeds 65 N/cm.
Description
Technical field
The invention belongs to environment-friendly type aqueous adhesive area, be specifically related to water-based polyurethane adhesive of a kind of epoxy resin modification and preparation method thereof.
Technical background
Water-based polyurethane adhesive refers to urethane is water-soluble or be dispersed in water and the tackiness agent that forms, and such tackiness agent has following advantage: (1) be take water and is dispersion medium, does not nontoxicly fire, nuisanceless, without dangerous, smell is little, free from environmental pollution, save the energy; (2) viscosity is lower, can regulate with water-soluble thickener and water, easy to operate, and cull can the water cleaning.As the aqueous polyurethane of the adhesion component of such tackiness agent in process of production organic solvent can recycle by underpressure distillation, reduce using and volatilizing of organic solvent, construction safety, easy and simple to handle.Yet, with the solvent borne polyurethane tackiness agent, compare, the performance of water-based polyurethane adhesive still has a certain distance, existence due to the hydrophilic radical in aqueous polyurethane molecular backbone chain structure, caused water tolerance, tack and the solvent-resisting of water-based polyurethane adhesive poor, and the defect such as the solid content of water-based polyurethane adhesive is low, activation temperature is high.
In order to improve the over-all properties of aqueous polyurethane, usually the modification by aqueous polyurethane improves its performance, comprises epoxy resin modification, acrylic graft-modified etc., and wherein, epoxy resin modification is particularly important a kind of method of modifying.Traditional epoxy resin modification, normally utilize hydroxyl and di-isocyanate reaction in epoxy resin, epoxy resin is introduced on polyurethane backbone, can the forming section reticulated structure and make performance more excellent, in addition, utilize the high reactivity of epoxide group in epoxy resin, by introducing in other molecule open loop access aqueous polyurethanes, the water-base polyurethane material of functional ternary copolymerization system be can obtain, thereby mechanical property, temperature tolerance and water tolerance etc. that aqueous polyurethane drags improved.The people such as Deng Yanwen have reported study on the synthesis (the Chinese tackiness agent of epoxy resin modified aqueous polyurethane tackiness agent, 2006,15(5): 18), its core technology is to use epoxy resin E44 and the common cross-linking modified aqueous polyurethane of internal crosslinker TriMethylolPropane(TMP), the employing butyleneglycol is chainextender, hydrophilic chain extender is dimethylol propionic acid, obtains the aqueous polyurethane emulsion of epoxy resin modification.Traditional epoxy resin modified aqueous polyurethane is less by epoxy addition, but because the β of the epoxide group in epoxy resin-position carbon atom easily is subject to the attack of the nucleophilic reagents such as triethylamine, hydroxyl, water in the later stage, Sauerstoffatom is subjected to the electrophilic reagent attack generation ring-opening reactions such as proton and Lewis acid, and then, cause stability in storage and the cementability variation of emulsion.
Summary of the invention
The objective of the invention is water-based polyurethane adhesive stability in storage and the poor problem of cementability in order to solve existing epoxy resin modification, and water-based polyurethane adhesive of a kind of epoxy resin modification and preparation method thereof is provided.
At first the present invention provides a kind of water-based polyurethane adhesive of epoxy resin modification, comprises according to the parts by weight meter:
The aqueous polyurethane of described epoxy resin modification is to take the epoxy resin of diamino modification to prepare as raw material;
The structural formula of the epoxy resin of described diamino modification is suc as formula shown in I:
Formula I
Wherein, n=3～12, m=2～10.
Preferably, the preparation method of the aqueous polyurethane of described epoxy resin modification comprises:
Step 1: by polymer diatomic alcohol, TriMethylolPropane(TMP) and di-isocyanate reaction, obtain the first intermediate;
Step 2: the first intermediate that step 1 is obtained reacts with dimethylolpropionic acid, obtains the second intermediate;
Step 3: by the second intermediate reaction that the epoxy resin of glycol ether, dimethylethanolamine, diamino modification and step 2 obtain, obtain the aqueous polyurethane of epoxy resin modification.
Preferably, the molecular weight of described polymer diatomic alcohol is 2000-8000 dalton.
Preferably, described polymer diatomic alcohol is selected from a kind of in polybutylene glyool adipate, polycarbonate diol or polytetrahydrofuran diol.
Preferably, described vulcabond is selected from a kind of in hexamethylene diisocyanate, isophorone diisocyanate, Methylcyclohexyl diisocyanate, dicyclohexyl methane diisocyanate.
Preferably, described water-based thickener is selected from a kind of in ROHM AND HAAS RM-12W, RM-2020 or RM-8W.
Preferably, described water-based flow agent is acrylate type flow agent or organosilicon type flow agent.
Preferably, described softening agent is a kind of in dibutyl phthalate, dioctyl phthalate (DOP);
Preferably, described oxidation inhibitor is selected from a kind of in irgasfos 168 or antioxidant 1010.
The present invention also provides a kind of preparation method of water-based polyurethane adhesive of epoxy resin modification, comprising:
The aqueous polyurethane of epoxy resin modification, water-based thickener, water-based flow agent, softening agent and oxidation inhibitor are joined to stirrer for mixing, and then add waterborne curing agent to stir, namely obtain the water-based polyurethane adhesive of epoxy resin modification.
Beneficial effect of the present invention
At first the present invention provides a kind of water-based polyurethane adhesive of epoxy resin modification, the main component of this tackiness agent is the aqueous polyurethane of epoxy resin modification, and the aqueous polyurethane of described epoxy resin modification is to take the epoxy resin of diamino modification to prepare as raw material; Compared with prior art, the present invention utilizes epoxy resin and excessive aliphatie diamine reaction, the epoxy resin ring-opening to improve performance thing of manufacturing side amino, utilize amino and remaining isocyanate reaction, epoxy resin is received in the aqueous polyurethane molecular chain, the whole open loops of epoxide group, the all epoxide groups in the structure have been eliminated, thereby, the attack of having avoided epoxide group in the resin structure to be subject to the nucleophilic reagents such as triethylamine, hydroxyl, water causes the situation of the stability in storage variation of emulsion, has greatly improved the stability in storage of aqueous polyurethane; And, the primary amino of the end group in the epoxy resin structural of the diamino modification that the present invention uses and the secondary amino group in chain structure, can form the urea key with two isocyanide acid numbers, in water, in emulsification, carried out chain extension, due to the existence that a plurality of amino avtive spots are arranged, the aqueous polyurethane obtained has network-like crosslinking structure, the molecule quantitative change is large, thereby, greatly improved the cementability of water-based polyurethane adhesive.Experimental result shows: after the water-based polyurethane adhesive of epoxy resin modification of the present invention was made sample, under 23-25 ℃ of condition, sealing was placed 24 months, had no demixing phenomenon; Peeling force surpasses 65N/cm.
The present invention also provides a kind of preparation method of water-based polyurethane adhesive of epoxy resin modification, and this preparation method's technique is simple, with low cost, and the water-based polyurethane adhesive of the epoxy resin modification prepared has excellent cementability and stability in storage.
Embodiment
At first the present invention provides a kind of water-based polyurethane adhesive of epoxy resin modification, comprises according to the parts by weight meter:
85～100 parts of the aqueous polyurethanes of epoxy resin modification, 0.15～0.3 part of water-based thickener, 0.10～0.35 part of water-based flow agent, 8～15 parts, softening agent, 0.03～0.08 part, oxidation inhibitor, 2.5～4.5 parts of waterborne curing agents; The aqueous polyurethane of described epoxy resin modification is to take the epoxy resin of diamino modification to prepare as raw material;
The structural formula of the epoxy resin of described diamino modification is suc as formula shown in I:
Formula I
Wherein, n=3～12, m=2～10.
Preferably, the preparation method of the aqueous polyurethane of described epoxy resin modification comprises:
Step 1: by polymer diatomic alcohol, TriMethylolPropane(TMP) and di-isocyanate reaction, obtain the first intermediate;
Step 2: the first intermediate that step 1 is obtained reacts with dimethylolpropionic acid, obtains the second intermediate;
Step 3: by the second intermediate reaction that the epoxy resin of glycol ether, dimethylethanolamine, diamino modification and step 2 obtain, obtain the aqueous polyurethane of epoxy resin modification.
Step 1 of the present invention is described first to be put into polymer diatomic alcohol and TriMethylolPropane(TMP) in reaction vessel and to reduce pressure and dewater, preferably, in temperature, be under 100～120 ℃ of conditions, decompression 1～1.5h, then under nitrogen protection, by the reaction vessel greenhouse cooling, add solvent and drip vulcabond, after dropwising, react, obtain the first intermediate;
Described temperature of reaction is preferably 80～85 ℃, reaction times is preferably 2.5～4h, solvent is preferably butanone, the molecular weight of described polymer diatomic alcohol is preferably 2000～8000 dalton, more preferably, to be selected from molecular weight be a kind of in 2000～8000 daltonian polybutylene glyool adipates, polycarbonate diol or polytetrahydrofuran diol for described polymer diatomic alcohol; Described vulcabond is preferably selected from aliphatic diisocyanate, comprises a kind of in hexamethylene diisocyanate, isophorone diisocyanate, Methylcyclohexyl diisocyanate, dicyclohexyl methane diisocyanate.The mass ratio of described polymer diatomic alcohol, TriMethylolPropane(TMP) and vulcabond is: (2000～8000): (126～165): (810～1125).
After obtaining the first intermediate, in order to reduce reaction system viscosity, in reaction vessel, add the solvent butanone, then add catalyzer and dimethylolpropionic acid hydrophilic chain extender, in order to make to react completely, hydrophilic chain extender can divide and joins several times in reaction vessel, be preferably three times, after adding, react, obtain the second intermediate; Described temperature of reaction is preferably 70-75 ℃, and the reaction times is preferably 0.5-2h, and catalyzer is preferably selected from a kind of in dibutyl tin laurate or stannous octoate; The mass ratio of described polymer diatomic alcohol, catalyzer and dimethylolpropionic acid is: (2000～8000): (0.002～0.003): (115～148).
After obtaining the second intermediate, in reaction vessel, add solvent butanone and glycol ether, preferably under 85～90 ℃ of conditions, react 2～3h, then cooling, add dimethylethanolamine to stir, preferably churning time is 10～15min, continue to add deionized water and diamino modified epoxy, stirring reaction, after having reacted, the removal of solvent under reduced pressure butanone, namely obtain the aqueous polyurethane of epoxy resin modification.Described temperature of reaction is preferably 40～45 ℃, and the reaction times is preferably 0.5～2h.The mass ratio of the epoxy resin of described polymer diatomic alcohol, glycol ether, dimethylethanolamine, diamino modification is: (2000～8000): (208～276): (65～118): (168～685).
The preparation method of the epoxy resin of diamino modification of the present invention comprises as follows:
In reaction vessel, add epoxy resin and 1-Methoxy-2-propyl acetate, temperature is warmed up to 40～45 ℃, after stirring 20～30min, in reaction vessel, drip the 1-Methoxy-2-propyl acetate solution of aliphatie diamine, after dropwising, continue again reaction 20～30min, namely obtain the epoxy resin of diamino modification.
Epoxy resin of the present invention is preferably selected from the dihydroxyphenyl propane based epoxy resin, more preferably model is a kind of in E51, E44 or E12, the 1-Methoxy-2-propyl acetate solution of described aliphatie diamine obtains after aliphatie diamine is dissolved in to the solvent 1-Methoxy-2-propyl acetate, the present invention has used 1-Methoxy-2-propyl acetate, the use of this solvent has reduced the concentration of reactant, makes this reaction more stablize controlled.The concentration of aliphatie diamine in solution is preferably 20%, described aliphatie diamine preferably includes 1,3-propylene diamine, Putriscine, 1,5-pentamethylene diamine, 1,6-hexanediamine, 1,7-heptamethylene diamine, 1,8-octamethylenediamine, 1,9-nonamethylene diamine, 1,10-decamethylene diamine, 1, a kind of in 11-11 diamines or 1,12-amino dodecane.The mass ratio of the 1-Methoxy-2-propyl acetate solution of described epoxy resin and aliphatie diamine is: (196～835): (155～1595), the rate of addition of the 1-Methoxy-2-propyl acetate solution of aliphatie diamine is preferably 1～4ml/min.
Water-based thickener of the present invention is preferably the polyurethanes thickening material, more preferably a kind of in ROHM AND HAAS RM-12W, RM-2020 or RM-8W.
Water-based flow agent preferred acrylate type flow agent of the present invention or organosilicon type flow agent, the model of more preferably BYK company production is one or more in BYK-380N, BYK-381, BYK-307, BYK-341, BYK-345, BYK-346 or BYK-348.
Softening agent of the present invention is preferably a kind of in dibutyl phthalate, dioctyl phthalate (DOP);
Oxidation inhibitor of the present invention is preferably selected from a kind of in irgasfos 168 (three (2,4-di-tert-butyl-phenyl) phosphorous acid ester) or antioxidant 1010 (four ［ β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid ］ pentaerythritol ester).
It is a kind of in DesmodurD, BayhydurXP2655 or BayhydurXP2547 that waterborne curing agent of the present invention is preferably selected from model.
The present invention also provides a kind of preparation method of water-based polyurethane adhesive of epoxy resin modification, comprising:
The aqueous polyurethane of epoxy resin modification, water-based thickener, water-based flow agent, softening agent and oxidation inhibitor are joined in homogenizer and is uniformly mixed, described stirring velocity is preferably 1100～1800rpm, churning time is preferably 10～15min, and then add waterborne curing agent to stir, described stirring velocity is preferably 2000～2200rpm, churning time is preferably 2～5min, namely obtains the water-based polyurethane adhesive of epoxy resin modification.
For making those skilled in the art understand better the present invention, further illustrate content of the present invention below in conjunction with embodiment.In embodiment, mentioned chemical reagent all can obtain by being purchased method.
The preparation of embodiment 1 diamino modified epoxy
Under drying nitrogen, in there-necked flask, add 196g epoxy resin E51 and 120ml 1-Methoxy-2-propyl acetate, temperature is warmed up to 40 ℃, after stirring 20min, with the speed of 1ml/min by 155g 20% 1, the 1-Methoxy-2-propyl acetate solution of 3-propylene diamine is added drop-wise in there-necked flask, after dropwising, continues reaction 20min, stopped reaction, obtain the epoxy resin of diamino modification.
The preparation of embodiment 2 diamino modified epoxies
Under drying nitrogen, in there-necked flask, add 835g epoxy resin E12 and 230ml 1-Methoxy-2-propyl acetate, temperature is warmed up to 45 ℃, after stirring 30min, with the speed of 4ml/min by 1595g 20% 1, the 1-Methoxy-2-propyl acetate solution of 12-amino dodecane is added drop-wise in there-necked flask, after dropwising, continues reaction 30min, stopped reaction, obtain the diamino modified epoxy.
The preparation of embodiment 3 diamino modified epoxies
Under drying nitrogen, in there-necked flask, add 231g epoxy resin E44 and 210ml 1-Methoxy-2-propyl acetate, temperature is warmed up to 42 ℃, after stirring 25min, with the speed of 2ml/min 20% fat 1 by 856g, the 1-Methoxy-2-propyl acetate solution of 6-hexanediamine is added drop-wise in there-necked flask, after dropwising, continues reaction 25min, stopped reaction, obtain the diamino modified epoxy.
The preparation of the aqueous polyurethane of embodiment 4 epoxy resin modifications
In there-necked flask, add 2000g polybutylene glyool adipate (molecular weight 2000 dalton) and 126g TriMethylolPropane(TMP), be warmed up to 100 ℃, reduced pressure 1 hour, and under nitrogen protection, cooled to 80 ℃, the butanone that adds 180ml, drip the hexamethylene diisocyanate of 810g, after dropwising, reacted 2.5 hours, and obtained the first intermediate;
Toward the butanone that adds 120ml in the first intermediate, greenhouse cooling to 70 ℃, add the 0.002g dibutyl tin laurate, adds in three batches 115g dimethylolpropionic acid hydrophilic chain extender, after adding, reacted 0.5 hour, obtains the second intermediate;
Toward the butanone that adds 100ml in the second intermediate, add the 208g glycol ether, be warmed up to 85 ℃, reacted 3 hours, cool to 40 ℃, add the 65g dimethylethanolamine, stir 10min, the diamino modified epoxy that adds 1200ml deionized water and 168g embodiment 1 to obtain, stirred 0.5 hour, then, butanone is removed in decompression, obtains the aqueous polyurethane of epoxy resin modification.
The preparation of the aqueous polyurethane of embodiment 5 epoxy resin modifications
In there-necked flask, add 8000g polybutylene glyool adipate (molecular weight 8000 dalton) and 165g TriMethylolPropane(TMP), be warmed up to 120 ℃, reduced pressure 1.5 hours, under nitrogen protection, cool to 85 ℃, add the butanone of 260ml, drip the 1125g dicyclohexyl methane diisocyanate, after dropwising, reacted 4 hours, obtain the first intermediate;
Toward the butanone that adds 200ml in the first intermediate, greenhouse cooling to 75 ℃, add the 0.003g stannous octoate, adds in three batches 148g dimethylolpropionic acid hydrophilic chain extender, after adding, reacted 2 hours, obtains the second intermediate;
Toward the butanone that adds 270ml in the second intermediate, add the 276g glycol ether, be warmed up to 90 ℃, reacted 2 hours, cool to 45 ℃, add the 118g dimethylethanolamine, stir 15min, the diamino modified epoxy that adds 7890ml deionized water and 685g embodiment 2 to obtain, stirred 2 hours, then, butanone is removed in decompression, obtains the aqueous polyurethane of epoxy resin modification.
The preparation of the aqueous polyurethane of embodiment 6 epoxy resin modifications
In there-necked flask, add 3000g polycarbonate diol (molecular weight 3000 dalton) and 138g TriMethylolPropane(TMP), be warmed up to 110 ℃, reduced pressure 1 hour, under nitrogen protection, cool to 82 ℃, add the butanone of 200ml, drip the 920g isophorone diisocyanate, after dropwising, reacted 3 hours, obtain the first intermediate;
Toward the butanone that adds 180ml in the first intermediate, greenhouse cooling to 72 ℃, add the 0.0025g stannous octoate, adds in three batches 121g dimethylolpropionic acid hydrophilic chain extender, after adding, reacted 1 hour, obtains the second intermediate;
Toward the butanone that adds 200ml in the second intermediate, add the 216g glycol ether, be warmed up to 88 ℃, reacted 2.5 hours, cool to 42 ℃, add the 76g dimethylethanolamine, stir 12min, the diamino modified epoxy that adds 2350ml deionized water and 235g embodiment 3 to obtain, stirred 1.5 hours, then, butanone is removed in decompression, obtains the aqueous polyurethane of epoxy resin modification.
The preparation of the aqueous polyurethane of embodiment 7 epoxy resin modifications
In there-necked flask, add 4000g polytetrahydrofuran diol (molecular weight is 4000 dalton) and 145g TriMethylolPropane(TMP), be warmed up to 120 ℃, reduced pressure 1 hour, under nitrogen protection, cool to 80 ℃, add the butanone of 220ml, drip the 1058g Methylcyclohexyl diisocyanate, after dropwising, reacted 3.5 hours, obtain the first intermediate;
Toward the butanone that adds 150ml in the first intermediate, greenhouse cooling to 70 ℃, add the 0.002g dibutyl tin laurate, adds in three batches 126g dimethylolpropionic acid hydrophilic chain extender, after adding, reacted 1.5 hours, obtains the second intermediate;
Toward the butanone that adds 230ml in the second intermediate, add the 242g glycol ether, be warmed up to 90 ℃, reacted 2.5 hours, cool to 40 ℃, add the 95g dimethylethanolamine, stir 10min, the diamino modified epoxy that adds 4200ml deionized water and 356g embodiment 2 to obtain, stirred 1.5 hours, then, butanone is removed in decompression, obtains the aqueous polyurethane of epoxy resin modification.
The preparation of the aqueous polyurethane of embodiment 8 epoxy resin modifications
In there-necked flask, add 6000g polycarbonate diol (molecular weight 6000 dalton) and 152g TriMethylolPropane(TMP), be warmed up to 120 ℃, reduced pressure 1 hour, under nitrogen protection, cool to 85 ℃, add the butanone of 240ml, drip the 965g isophorone diisocyanate, after dropwising, reacted 3 hours, obtain the first intermediate;
Toward the butanone that adds 180ml in the first intermediate, greenhouse cooling to 70 ℃, add the 0.003g stannous octoate, adds in three batches 128g dimethylolpropionic acid hydrophilic chain extender, after adding, reacted 2 hours, obtains the second intermediate;
Toward the butanone that adds 245ml in the second intermediate, add the 237g glycol ether, be warmed up to 87 ℃, reacted 2.5 hours, cool to 43 ℃, add the 102g dimethylethanolamine, stir 13min, the diamino modified epoxy that adds 6200ml deionized water and 458g embodiment 3 to obtain, stirred 1 hour, then, butanone is removed in decompression, obtains the aqueous polyurethane of epoxy resin modification.
Embodiment 9
Aqueous polyurethane, 0.15g water-based thickener RM-12W, 0.1g water-based flow agent BYK-380N, 8g plasticizer phthalic acid dibutylester and the 0.03g irgasfos 168 of the epoxy resin modification that 85g embodiment 4 is obtained rotating speed with 1100rpm in high speed agitator stirs 15min, then add 2.5g waterborne curing agent DesmodurD to stir 5min with the rotating speed of 2000rpm, obtain the water-based polyurethane adhesive of epoxy resin modification.
Embodiment 10
Aqueous polyurethane, 0.3g water-based thickener RM-2020,0.35g water-based flow agent BYK-381,15g plasticizer phthalic acid dioctyl ester and the 0.08g antioxidant 1010 of the epoxy resin modification that 100g embodiment 5 is obtained rotating speed with 1800rpm in high speed agitator stirs 10min, then add 4.5g waterborne curing agent BayhydurXP2655 to stir 2min with the rotating speed of 2200rpm, obtain the water-based polyurethane adhesive of epoxy resin modification.
Embodiment 11
Aqueous polyurethane, 0.2g water-based thickener RM-8W, 0.2g water-based flow agent BYK-307,10g plasticizer phthalic acid dibutylester and the 0.05g antioxidant 1010 of the epoxy resin modification that 90g embodiment 6 is obtained rotating speed with 1500rpm in high speed agitator stirs 12min, then add 3g waterborne curing agent BayhydurXP2547 to stir 3min with the rotating speed of 2100rpm, obtain the water-based polyurethane adhesive of epoxy resin modification.
Embodiment 12
Aqueous polyurethane, 0.25g water-based thickener RM-2020,0.3g water-based flow agent BYK-381,9g plasticizer phthalic acid dioctyl ester and the 0.06g irgasfos 168 of the epoxy resin modification that 95g embodiment 7 is obtained rotating speed with 1700rpm in high speed agitator stirs 12min, then add 3.5g waterborne curing agent BayhydurXP2655 to stir 2min with the rotating speed of 2200rpm, obtain the water-based polyurethane adhesive of epoxy resin modification.
Embodiment 13
Aqueous polyurethane, 0.2g water-based thickener RM-12W, 0.25g water-based flow agent BYK-380N, 12g plasticizer phthalic acid dibutylester and the 0.07g antioxidant 1010 of the epoxy resin modification that 88g embodiment 8 is obtained rotating speed with 1700rpm in high speed agitator stirs 15min, then add 4g waterborne curing agent BayhydurXP2547 to stir 2min with the rotating speed of 2000rpm, obtain the water-based polyurethane adhesive of epoxy resin modification.
The water-based polyurethane adhesive of the epoxy resin modification that embodiment 9-13 is obtained carries out performance test, concrete grammar is: the water-based polyurethane adhesive of the epoxy resin modification that embodiment 9-13 is obtained is sprayed on respectively on exemplar, quantity for spray is 240g/m2,75 ℃ of activation 2min, then, treat that the sticky object room temperature carries out pressing 2min, tested in 48 hours.Test result is as shown in table 1.
Table 1
The explanation of above embodiment is just be used to helping to understand method of the present invention and core concept thereof.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, make professional and technical personnel in the field can realize or use the present invention.Multiple modification to these embodiment will be apparent for those skilled in the art, and General Principle as defined herein can be in the situation that do not break away from the spirit or scope of the present invention, realization in other embodiments.Therefore, the present invention will can not be restricted to these embodiment shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. the water-based polyurethane adhesive of epoxy resin modification, is characterized in that, comprises according to the parts by weight meter:
The aqueous polyurethane of described epoxy resin modification is to take the epoxy resin of diamino modification to prepare as raw material;
The structural formula of the epoxy resin of described diamino modification is suc as formula shown in I:
Formula I
Wherein, n=3～12, m=2～10.
2. the water-based polyurethane adhesive of epoxy resin modification according to claim 1, is characterized in that, the preparation method of the aqueous polyurethane of described epoxy resin modification comprises:
Step 1: by polymer diatomic alcohol, TriMethylolPropane(TMP) and di-isocyanate reaction, obtain the first intermediate;
Step 2: the first intermediate that step 1 is obtained reacts with dimethylolpropionic acid, obtains the second intermediate;
Step 3: by the second intermediate reaction that the epoxy resin of glycol ether, dimethylethanolamine, diamino modification and step 2 obtain, obtain the aqueous polyurethane of epoxy resin modification.
3. the water-based polyurethane adhesive of epoxy resin modification according to claim 2, is characterized in that, the molecular weight of described polymer diatomic alcohol is 2000-8000 dalton.
4. the water-based polyurethane adhesive of epoxy resin modification according to claim 3, is characterized in that, described polymer diatomic alcohol is selected from a kind of in polybutylene glyool adipate, polycarbonate diol or polytetrahydrofuran diol.
5. the water-based polyurethane adhesive of epoxy resin modification according to claim 2, it is characterized in that, described vulcabond is selected from a kind of in hexamethylene diisocyanate, isophorone diisocyanate, Methylcyclohexyl diisocyanate, dicyclohexyl methane diisocyanate.
6. the water-based polyurethane adhesive of epoxy resin modification according to claim 1, is characterized in that, described water-based thickener is selected from a kind of in ROHM AND HAAS RM-12W, RM-2020 or RM-8W.
7. the water-based polyurethane adhesive of epoxy resin modification according to claim 1, is characterized in that, described water-based flow agent is acrylate type flow agent or organosilicon type flow agent.
8. the water-based polyurethane adhesive of epoxy resin modification according to claim 1, is characterized in that, described softening agent is a kind of in dibutyl phthalate, dioctyl phthalate (DOP);
9. the water-based polyurethane adhesive of epoxy resin modification according to claim 1, is characterized in that, described oxidation inhibitor is selected from a kind of in irgasfos 168 or antioxidant 1010.
10. according to the preparation method of the water-based polyurethane adhesive of any one described epoxy resin modification of claim 1-9, it is characterized in that, comprising:
The aqueous polyurethane of epoxy resin modification, water-based thickener, water-based flow agent, softening agent and oxidation inhibitor are joined to stirrer for mixing, and then add waterborne curing agent to stir, namely obtain the water-based polyurethane adhesive of epoxy resin modification.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104032578A (en) * | 2014-06-26 | 2014-09-10 | 江苏宝泽高分子材料股份有限公司 | Waterborne oily leather treatment agent for synthetic leather and preparation method of leather treatment agent |
| CN104119499A (en) * | 2013-12-16 | 2014-10-29 | 安徽安大华泰新材料有限公司 | Method for preparing epoxy-modified aromatic polysulfideurethane |
| CN107602803A (en) * | 2017-09-22 | 2018-01-19 | 苏州博莱特新材料有限公司 | A kind of waterborne polyurethane resin and preparation method thereof |
| CN108034399A (en) * | 2017-12-26 | 2018-05-15 | 芜湖市长江起重设备制造有限公司 | A kind of preparation method of the cross-linking modified polycarbonate waterborne polyurethane adhesive of uvioresistant |
| CN109355055A (en) * | 2018-09-26 | 2019-02-19 | 上海维凯光电新材料有限公司 | Aqueous Polyurethane Adhesives emulsion compositions and preparation method thereof |
| CN109749690A (en) * | 2018-11-28 | 2019-05-14 | 耿佃勇 | Epoxy resin modified aqueous polyurethane adhesive for building and preparation method thereof |
| CN111234765A (en) * | 2020-03-12 | 2020-06-05 | 江西正博实业有限公司 | Glue for shoemaking and preparation method thereof |
| CN111378091A (en) * | 2018-12-28 | 2020-07-07 | 财团法人工业技术研究院 | Waterborne polyurethane and preparation method thereof |
| CN115466589A (en) * | 2022-09-20 | 2022-12-13 | 武汉纺织大学 | Modified epoxy resin encapsulating structural adhesive and preparation method thereof |
| CN116200112A (en) * | 2021-11-30 | 2023-06-02 | 浙江洛克新材料股份有限公司 | Protective coating for lithium battery and preparation process thereof |
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| CN104119499A (en) * | 2013-12-16 | 2014-10-29 | 安徽安大华泰新材料有限公司 | Method for preparing epoxy-modified aromatic polysulfideurethane |
| CN104119499B (en) * | 2013-12-16 | 2016-03-30 | 安徽安大华泰新材料有限公司 | A kind of preparation method of epoxide modified aromatic series polythiourethane |
| CN104032578A (en) * | 2014-06-26 | 2014-09-10 | 江苏宝泽高分子材料股份有限公司 | Waterborne oily leather treatment agent for synthetic leather and preparation method of leather treatment agent |
| CN107602803A (en) * | 2017-09-22 | 2018-01-19 | 苏州博莱特新材料有限公司 | A kind of waterborne polyurethane resin and preparation method thereof |
| CN107602803B (en) * | 2017-09-22 | 2020-07-14 | 苏州博莱特新材料有限公司 | Waterborne polyurethane resin and preparation method thereof |
| CN108034399A (en) * | 2017-12-26 | 2018-05-15 | 芜湖市长江起重设备制造有限公司 | A kind of preparation method of the cross-linking modified polycarbonate waterborne polyurethane adhesive of uvioresistant |
| CN109355055A (en) * | 2018-09-26 | 2019-02-19 | 上海维凯光电新材料有限公司 | Aqueous Polyurethane Adhesives emulsion compositions and preparation method thereof |
| CN109749690A (en) * | 2018-11-28 | 2019-05-14 | 耿佃勇 | Epoxy resin modified aqueous polyurethane adhesive for building and preparation method thereof |
| CN111378091A (en) * | 2018-12-28 | 2020-07-07 | 财团法人工业技术研究院 | Waterborne polyurethane and preparation method thereof |
| CN111234765A (en) * | 2020-03-12 | 2020-06-05 | 江西正博实业有限公司 | Glue for shoemaking and preparation method thereof |
| CN116200112A (en) * | 2021-11-30 | 2023-06-02 | 浙江洛克新材料股份有限公司 | Protective coating for lithium battery and preparation process thereof |
| CN115466589A (en) * | 2022-09-20 | 2022-12-13 | 武汉纺织大学 | Modified epoxy resin encapsulating structural adhesive and preparation method thereof |
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