CN103409100B - 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
- Publication number
- CN103409100B CN103409100B CN201310358759.2A CN201310358759A CN103409100B CN 103409100 B CN103409100 B CN 103409100B CN 201310358759 A CN201310358759 A CN 201310358759A CN 103409100 B CN103409100 B CN 103409100B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- water
- polyurethane adhesive
- resin modification
- based polyurethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- MIYJLAGQVFNIJE-UHFFFAOYSA-N C=[IH+][F](C1CC1)#C Chemical compound C=[IH+][F](C1CC1)#C MIYJLAGQVFNIJE-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
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 tackiness agent that is urethane is water-soluble or that be dispersed in water and formed, and such tackiness agent has following advantage: (1) take water as 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, and easy to operate, cull can be cleared up with water.As the adhesion component of such tackiness agent aqueous polyurethane in process of production organic solvent can be recycled by underpressure distillation, reduce the using and volatilize, construction safety of organic solvent, easy and simple to handle.But, compared with solvent borne polyurethane tackiness agent, the performance of water-based polyurethane adhesive still has a certain distance, due to the existence of the hydrophilic radical in aqueous polyurethane molecular backbone chain structure, result in the water tolerance of water-based polyurethane adhesive, tack and solvent-resisting 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, the modification often through aqueous polyurethane improves its performance, and comprise epoxy resin modification, acrylic graft-modified etc., wherein, epoxy resin modification is particularly important a kind of method of modifying.Traditional epoxy resin modification, normally utilize the hydroxyl in epoxy resin and di-isocyanate reaction, epoxy resin is introduced in polyurethane backbone, can forming section reticulated structure and make performance more excellent, in addition, utilize the high reactivity that epoxy resin epoxy group is rolled into a ball, by introducing in other molecule open loops access aqueous polyurethane, the water-base polyurethane material of functional ternary copolymerization system can be obtained, thus mechanical property, temperature tolerance and water tolerance etc. that raising aqueous polyurethane drags.The people such as Deng Yanwen report study on the synthesis (the Chinese tackiness agent of epoxy resin modified aqueous polyurethane tackiness agent, 2006,15(5): 18), its core technology uses epoxy resin E44 and the common cross-linking modified aqueous polyurethane of internal crosslinker TriMethylolPropane(TMP), employing butyleneglycol is chainextender, hydrophilic chain extender is dimethylol propionic acid, obtains the aqueous polyurethane emulsion of epoxy resin modification.Less by epoxy addition of traditional epoxy resin modified aqueous polyurethane, but because the β-position carbon atom of the epoxide group in epoxy resin to be easily subject to the attack of the nucleophilic reagents such as triethylamine, hydroxyl, water in the later stage, Sauerstoffatom is by the electrophilic reagent such as proton and Lewis acid attack generation ring-opening reaction, and then, cause the stability in storage of emulsion and cementability to be deteriorated.
Summary of the invention
The object of the invention is the problem in order to the water-based polyurethane adhesive stability in storage and cementability difference solving existing epoxy resin modification, and water-based polyurethane adhesive of a kind of epoxy resin modification and preparation method thereof is provided.
First the present invention provides a kind of water-based polyurethane adhesive of epoxy resin modification, comprises according to weight parts:
The aqueous polyurethane of described epoxy resin modification is for raw material prepares with the epoxy resin of diamino modification;
The structural formula of the epoxy resin of described diamino modification is such 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, comprising:
Step one: by polymer diatomic alcohol, TriMethylolPropane(TMP) and di-isocyanate reaction, obtains the first intermediate;
Step 2: the first intermediate step one obtained and dimethylolpropionic acid react, and obtain the second intermediate;
Step 3: the second intermediate reaction epoxy resin of glycol ether, dimethylethanolamine, diamino modification and step 2 obtained, obtains 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 the one in polybutylene glyool adipate, polycarbonate diol or polytetrahydrofuran diol.
Preferably, described vulcabond is selected from the one in hexamethylene diisocyanate, isophorone diisocyanate, Methylcyclohexyl diisocyanate, dicyclohexyl methane diisocyanate.
Preferably, described water-based thickener is selected from the one in ROHM AND HAAS RM-12W, RM-2020 or RM-8W.
Preferably, described water-based flow agent is acrylate type flow agent or organic silicon type flow agent.
Preferably, described softening agent is the one in dibutyl phthalate, dioctyl phthalate (DOP);
Preferably, described oxidation inhibitor is selected from the one 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 stirrer for mixing, and then adds waterborne curing agent stirring, namely obtain the water-based polyurethane adhesive of epoxy resin modification.
Beneficial effect of the present invention
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 for raw material prepares with the epoxy resin of diamino modification; Compared with prior art, the present invention utilizes epoxy resin and the reaction of excessive aliphatie diamine, the epoxy resin ring-opening to improve performance thing of manufacturing side amino, utilize amino and remaining isocyanate reaction, epoxy resin is received in aqueous polyurethane molecular chain, the whole open loop of epoxide group, eliminate all epoxide groups in structure, thus, avoid the situation that attack that resin structure epoxy group group is subject to the nucleophilic reagents such as triethylamine, hydroxyl, water causes the stability in storage of emulsion to be deteriorated, substantially increase the stability in storage of aqueous polyurethane; And, the primary amino of end group in the epoxy resin structural of the diamino modification that the present invention uses and the secondary amino group in chain structure, urea key can be formed with two isocyanide acid numbers, in water while emulsification, carry out chain extension, owing to there being the existence of multiple amino avtive spot, the aqueous polyurethane obtained has network-like crosslinking structure, molecule quantitative change is large, thus, substantially increase the cementability of water-based polyurethane adhesive.Experimental result shows: after the water-based polyurethane adhesive of epoxy resin modification of the present invention makes sample, under 23-25 DEG C of condition, and sealing placement 24 months, has no demixing phenomenon; Peeling force is more than 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
First the present invention provides a kind of water-based polyurethane adhesive of epoxy resin modification, comprises according to weight parts:
The aqueous polyurethane of epoxy resin modification 85 ~ 100 parts, water-based thickener 0.15 ~ 0.3 part, water-based flow agent 0.10 ~ 0.35 part, 8 ~ 15 parts, softening agent, 0.03 ~ 0.08 part, oxidation inhibitor, waterborne curing agent 2.5 ~ 4.5 parts; The aqueous polyurethane of described epoxy resin modification is for raw material prepares with the epoxy resin of diamino modification;
The structural formula of the epoxy resin of described diamino modification is such 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, comprising:
Step one: by polymer diatomic alcohol, TriMethylolPropane(TMP) and di-isocyanate reaction, obtains the first intermediate;
Step 2: the first intermediate step one obtained and dimethylolpropionic acid react, and obtain the second intermediate;
Step 3: the second intermediate reaction epoxy resin of glycol ether, dimethylethanolamine, diamino modification and step 2 obtained, obtains the aqueous polyurethane of epoxy resin modification.
First polymer diatomic alcohol and TriMethylolPropane(TMP) being put in reaction vessel described in step one of the present invention is carried out decompression and is dewatered, preferably, under temperature is 100 ~ 120 DEG C of conditions, decompression 1 ~ 1.5h, then under nitrogen protection, by reaction vessel greenhouse cooling, add solvent and drip vulcabond, after dropwising, react, obtain the first intermediate;
Described temperature of reaction is preferably 80 ~ 85 DEG C, reaction times is preferably 2.5 ~ 4h, solvent is preferably butanone, the molecular weight of described polymer diatomic alcohol is preferably 2000 ~ 8000 dalton, it is further preferred that it is one in 2000 ~ 8000 daltonian polybutylene glyool adipates, polycarbonate diol or polytetrahydrofuran diol that described polymer diatomic alcohol is selected from molecular weight; Described vulcabond is preferably selected from aliphatic diisocyanate, comprises the one 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, solvent butanone is added in reaction vessel, 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 DEG C, and the reaction times is preferably 0.5-2h, and catalyzer is preferably selected from the one 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, solvent butanone and glycol ether is added in reaction vessel, preferably under 85 ~ 90 DEG C of conditions, react 2 ~ 3h, then lower the temperature, add dimethylethanolamine and stir, preferred churning time is 10 ~ 15min, continue to add deionized water and diamino modified epoxy, stirring reaction, after having reacted, removal of solvent under reduced pressure butanone, namely obtains the aqueous polyurethane of epoxy resin modification.Described temperature of reaction is preferably 40 ~ 45 DEG C, 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:
Epoxy resin and 1-Methoxy-2-propyl acetate is added in reaction vessel, temperature is to 40 ~ 45 DEG C, after stirring 20 ~ 30min, the 1-Methoxy-2-propyl acetate solution of aliphatie diamine is dripped in reaction vessel, after dropwising, continue reaction 20 ~ 30min again, namely obtain the epoxy resin of diamino modification.
Epoxy resin of the present invention is preferably selected from bisphenol A type epoxy resin, being more preferably model is one in E51, E44 or E12, obtain after aliphatie diamine is dissolved in solvent propylene glycol methyl ether acetate by the 1-Methoxy-2-propyl acetate solution of described aliphatie diamine, present invention uses 1-Methoxy-2-propyl acetate, the use of this solvent reduces the concentration of reactant, makes this reaction more stablize controlled.Aliphatie diamine concentration is in the solution 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, one in 10-decamethylene diamine, 1,11-ten one 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), and 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 polyurethanes thickening material, is more preferably the one 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 organic silicon type flow agent, being more preferably the model that BYK company produces 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 the one in dibutyl phthalate, dioctyl phthalate (DOP);
Oxidation inhibitor of the present invention is preferably selected from the one 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 one 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 stirring, 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 the present invention better, illustrate content of the present invention further below in conjunction with embodiment.In embodiment, mentioned chemical reagent all obtains 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, to 40 DEG C, stirs after 20min, with the speed of 1ml/min by 20% of 155g 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, obtains the epoxy resin of diamino modification.
The preparation of embodiment 2 diamino modified epoxy
Under drying nitrogen, in there-necked flask, add 835g epoxy resin E12 and 230ml 1-Methoxy-2-propyl acetate, temperature, to 45 DEG C, stirs after 30min, with the speed of 4ml/min by 20% of 1595g 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, obtains diamino modified epoxy.
The preparation of embodiment 3 diamino modified epoxy
Under drying nitrogen, in there-necked flask, add 231g epoxy resin E44 and 210ml 1-Methoxy-2-propyl acetate, temperature, to 42 DEG C, stirs after 25min, with the speed of 2ml/min by the fat 1 of 20% of 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, obtains diamino modified epoxy.
The preparation of the aqueous polyurethane of embodiment 4 epoxy resin modification
2000g polybutylene glyool adipate (molecular weight 2000 dalton) and 126g TriMethylolPropane(TMP) is added in there-necked flask, be warmed up to 100 DEG C, reduce pressure 1 hour, under nitrogen protection, cool to 80 DEG C, add the butanone of 180ml, drip the hexamethylene diisocyanate of 810g, after dropwising, react 2.5 hours, obtain the first intermediate;
In the first intermediate, add the butanone of 120ml, greenhouse cooling, to 70 DEG C, adds 0.002g dibutyl tin laurate, adds 115g dimethylolpropionic acid hydrophilic chain extender in three batches, after adding, reacts 0.5 hour, obtains the second intermediate;
The butanone of 100ml is added in the second intermediate, add 208g glycol ether, be warmed up to 85 DEG C, react 3 hours, cool to 40 DEG C, add 65g dimethylethanolamine, stir 10min, add the diamino modified epoxy that 1200ml deionized water and 168g embodiment 1 obtain, stir 0.5 hour, then, decompression removing butanone, obtains the aqueous polyurethane of epoxy resin modification.
The preparation of the aqueous polyurethane of embodiment 5 epoxy resin modification
8000g polybutylene glyool adipate (molecular weight 8000 dalton) and 165g TriMethylolPropane(TMP) is added in there-necked flask, be warmed up to 120 DEG C, reduce pressure 1.5 hours, under nitrogen protection, cool to 85 DEG C, add the butanone of 260ml, drip 1125g dicyclohexyl methane diisocyanate, after dropwising, react 4 hours, obtain the first intermediate;
In the first intermediate, add the butanone of 200ml, greenhouse cooling, to 75 DEG C, adds 0.003g stannous octoate, adds 148g dimethylolpropionic acid hydrophilic chain extender in three batches, after adding, reacts 2 hours, obtains the second intermediate;
The butanone of 270ml is added in the second intermediate, add 276g glycol ether, be warmed up to 90 DEG C, react 2 hours, cool to 45 DEG C, add 118g dimethylethanolamine, stir 15min, add the diamino modified epoxy that 7890ml deionized water and 685g embodiment 2 obtain, stir 2 hours, then, decompression removing butanone, obtains the aqueous polyurethane of epoxy resin modification.
The preparation of the aqueous polyurethane of embodiment 6 epoxy resin modification
3000g polycarbonate diol (molecular weight 3000 dalton) and 138g TriMethylolPropane(TMP) is added in there-necked flask, be warmed up to 110 DEG C, reduce pressure 1 hour, under nitrogen protection, cool to 82 DEG C, add the butanone of 200ml, drip 920g isophorone diisocyanate, after dropwising, react 3 hours, obtain the first intermediate;
In the first intermediate, add the butanone of 180ml, greenhouse cooling, to 72 DEG C, adds 0.0025g stannous octoate, adds 121g dimethylolpropionic acid hydrophilic chain extender in three batches, after adding, reacts 1 hour, obtains the second intermediate;
The butanone of 200ml is added in the second intermediate, add 216g glycol ether, be warmed up to 88 DEG C, react 2.5 hours, cool to 42 DEG C, add 76g dimethylethanolamine, stir 12min, add the diamino modified epoxy that 2350ml deionized water and 235g embodiment 3 obtain, stir 1.5 hours, then, decompression removing butanone, obtains the aqueous polyurethane of epoxy resin modification.
The preparation of the aqueous polyurethane of embodiment 7 epoxy resin modification
4000g polytetrahydrofuran diol (molecular weight is 4000 dalton) and 145g TriMethylolPropane(TMP) is added in there-necked flask, be warmed up to 120 DEG C, reduce pressure 1 hour, under nitrogen protection, cool to 80 DEG C, add the butanone of 220ml, drip 1058g Methylcyclohexyl diisocyanate, after dropwising, react 3.5 hours, obtain the first intermediate;
In the first intermediate, add the butanone of 150ml, greenhouse cooling, to 70 DEG C, adds 0.002g dibutyl tin laurate, adds 126g dimethylolpropionic acid hydrophilic chain extender in three batches, after adding, reacts 1.5 hours, obtains the second intermediate;
The butanone of 230ml is added in the second intermediate, add 242g glycol ether, be warmed up to 90 DEG C, react 2.5 hours, cool to 40 DEG C, add 95g dimethylethanolamine, stir 10min, add the diamino modified epoxy that 4200ml deionized water and 356g embodiment 2 obtain, stir 1.5 hours, then, decompression removing butanone, obtains the aqueous polyurethane of epoxy resin modification.
The preparation of the aqueous polyurethane of embodiment 8 epoxy resin modification
6000g polycarbonate diol (molecular weight 6000 dalton) and 152g TriMethylolPropane(TMP) is added in there-necked flask, be warmed up to 120 DEG C, reduce pressure 1 hour, under nitrogen protection, cool to 85 DEG C, add the butanone of 240ml, drip 965g isophorone diisocyanate, after dropwising, react 3 hours, obtain the first intermediate;
In the first intermediate, add the butanone of 180ml, greenhouse cooling, to 70 DEG C, adds 0.003g stannous octoate, adds 128g dimethylolpropionic acid hydrophilic chain extender in three batches, after adding, reacts 2 hours, obtains the second intermediate;
The butanone of 245ml is added in the second intermediate, add 237g glycol ether, be warmed up to 87 DEG C, react 2.5 hours, cool to 43 DEG C, add 102g dimethylethanolamine, stir 13min, add the diamino modified epoxy that 6200ml deionized water and 458g embodiment 3 obtain, stir 1 hour, then, decompression removing butanone, obtains the aqueous polyurethane of epoxy resin modification.
Embodiment 9
The aqueous polyurethane of epoxy resin modification 85g embodiment 4 obtained, 0.15g water-based thickener RM-12W, 0.1g water-based flow agent BYK-380N, 8g plasticizer phthalic acid dibutylester and 0.03g irgasfos 168 stir 15min with the rotating speed of 1100rpm in high speed agitator, then add 2.5g waterborne curing agent DesmodurD and stir 5min with the rotating speed of 2000rpm, obtain the water-based polyurethane adhesive of epoxy resin modification.
Embodiment 10
The aqueous polyurethane of epoxy resin modification 100g embodiment 5 obtained, 0.3g water-based thickener RM-2020,0.35g water-based flow agent BYK-381,15g plasticizer phthalic acid dioctyl ester and 0.08g antioxidant 1010 stir 10min with the rotating speed of 1800rpm in high speed agitator, then add 4.5g waterborne curing agent BayhydurXP2655 and stir 2min with the rotating speed of 2200rpm, obtain the water-based polyurethane adhesive of epoxy resin modification.
Embodiment 11
The aqueous polyurethane of epoxy resin modification 90g embodiment 6 obtained, 0.2g water-based thickener RM-8W, 0.2g water-based flow agent BYK-307,10g plasticizer phthalic acid dibutylester and 0.05g antioxidant 1010 stir 12min with the rotating speed of 1500rpm in high speed agitator, then add 3g waterborne curing agent BayhydurXP2547 and stir 3min with the rotating speed of 2100rpm, obtain the water-based polyurethane adhesive of epoxy resin modification.
Embodiment 12
The aqueous polyurethane of epoxy resin modification 95g embodiment 7 obtained, 0.25g water-based thickener RM-2020,0.3g water-based flow agent BYK-381,9g plasticizer phthalic acid dioctyl ester and 0.06g irgasfos 168 stir 12min with the rotating speed of 1700rpm in high speed agitator, then add 3.5g waterborne curing agent BayhydurXP2655 and stir 2min with the rotating speed of 2200rpm, obtain the water-based polyurethane adhesive of epoxy resin modification.
Embodiment 13
The aqueous polyurethane of epoxy resin modification 88g embodiment 8 obtained, 0.2g water-based thickener RM-12W, 0.25g water-based flow agent BYK-380N, 12g plasticizer phthalic acid dibutylester and 0.07g antioxidant 1010 stir 15min with the rotating speed of 1700rpm in high speed agitator, then add 4g waterborne curing agent BayhydurXP2547 and 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 obtained by embodiment 9-13 carries out performance test, concrete grammar is: the water-based polyurethane adhesive of the epoxy resin modification obtained by embodiment 9-13 is sprayed on exemplar respectively, quantity for spray is 240g/m2,75 DEG C of activation 2min, then, treat that sticky object room temperature carries out pressing 2min, within 48 hours, test.Test result is as shown in table 1.
Table 1
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.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 improve and modify and also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (8)
1. the water-based polyurethane adhesive of epoxy resin modification, is characterized in that, comprises according to weight parts:
The aqueous polyurethane of described epoxy resin modification is for raw material prepares with the epoxy resin of diamino modification;
The structural formula of the epoxy resin of described diamino modification is such as formula shown in I:
Wherein, n=3 ~ 12, m=2 ~ 10;
The preparation method of the aqueous polyurethane of described epoxy resin modification, comprising:
Step one: by polymer diatomic alcohol, TriMethylolPropane(TMP) and di-isocyanate reaction, obtains the first intermediate; Described polymer diatomic alcohol is selected from the one in polybutylene glyool adipate, polycarbonate diol or polytetrahydrofuran diol;
Step 2: the first intermediate step one obtained and dimethylolpropionic acid react, and obtain the second intermediate;
Step 3: the second intermediate reaction epoxy resin of glycol ether, dimethylethanolamine, diamino modification and step 2 obtained, obtains the aqueous polyurethane of epoxy resin modification.
2. the water-based polyurethane adhesive of epoxy resin modification according to claim 1, is characterized in that, the molecular weight of described polymer diatomic alcohol is 2000-8000 dalton.
3. the water-based polyurethane adhesive of epoxy resin modification according to claim 1, it is characterized in that, described vulcabond is selected from the one in hexamethylene diisocyanate, isophorone diisocyanate, Methylcyclohexyl diisocyanate, dicyclohexyl methane diisocyanate.
4. the water-based polyurethane adhesive of epoxy resin modification according to claim 1, is characterized in that, described water-based thickener is selected from the one in ROHM AND HAAS RM-12W, RM-2020 or RM-8W.
5. 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 organic silicon type flow agent.
6. the water-based polyurethane adhesive of epoxy resin modification according to claim 1, is characterized in that, described softening agent is the one in dibutyl phthalate, dioctyl phthalate (DOP);
7. the water-based polyurethane adhesive of epoxy resin modification according to claim 1, is characterized in that, described oxidation inhibitor is selected from the one in irgasfos 168 or antioxidant 1010.
8., according to the preparation method of the water-based polyurethane adhesive of the epoxy resin modification of claim 1-7 described in any one, 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 stirrer for mixing, and then adds waterborne curing agent stirring, namely obtain the water-based polyurethane adhesive of epoxy resin modification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310358759.2A CN103409100B (en) | 2013-08-16 | 2013-08-16 | Epoxy-resin-modified water-based polyurethane adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310358759.2A CN103409100B (en) | 2013-08-16 | 2013-08-16 | Epoxy-resin-modified water-based polyurethane adhesive and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103409100A CN103409100A (en) | 2013-11-27 |
| CN103409100B true CN103409100B (en) | 2015-04-22 |
Family
ID=49602144
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310358759.2A Active CN103409100B (en) | 2013-08-16 | 2013-08-16 | Epoxy-resin-modified water-based polyurethane adhesive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103409100B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN109355055B (en) * | 2018-09-26 | 2021-02-19 | 上海维凯光电新材料有限公司 | Aqueous polyurethane adhesive emulsion composition 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09235352A (en) * | 1995-12-27 | 1997-09-09 | Mitsui Toatsu Chem Inc | Curing agent for resin |
| CN103045150B (en) * | 2013-01-15 | 2014-04-09 | 中国科学院长春应用化学研究所 | Waterborne polyurethane adhesive and preparation method thereof |
-
2013
- 2013-08-16 CN CN201310358759.2A patent/CN103409100B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103409100A (en) | 2013-11-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103409100B (en) | Epoxy-resin-modified water-based polyurethane adhesive and preparation method thereof | |
| CN101270221B (en) | Method for preparing composite emulsion of epoxy resin-polyurethane | |
| CN103483539B (en) | Poly-(carbonic ether-ether) type aqueous polyurethane, water-based polyurethane adhesive and preparation method thereof | |
| CN103450792B (en) | Hyperbranched water-based polyurethane coating and preparation method thereof | |
| CN102391458B (en) | Methods for preparing aqueous polyurethane, auxiliary agent slurry and aqueous polyurethane finishing agent | |
| CN101629050B (en) | Urethane acrylate waterborne UV coating and preparation method thereof | |
| CN105131239A (en) | Water resistance solvent-free polyurethane emulsion and preparation method thereof | |
| CN103467693B (en) | A kind of preparation method of the aqueous polyurethane with good freeze/thaw stability | |
| CN102703015B (en) | Preparation method of low monomer-residual acrylic ester modified aqueous polyurethane pressure-sensitive adhesive | |
| CN106589281B (en) | Carbon dioxide-based waterborne polyurethane-polyurea, preparation method and coating/adhesive | |
| CN102702471A (en) | Method for preparing solvent-free aqueous polyurethane dispersion | |
| CN103881049A (en) | Preparation method of eleostearic acid monoglyceride modified waterborne polyurethane emulsion | |
| CN105368291A (en) | Water-borne woodware coating containing modified polyurethane emulsion and preparation method thereof | |
| CN103554430B (en) | A kind of preparation method of blocked polyisocyanate linking agent water miscible liquid | |
| CN103408715A (en) | Internal crosslinking polypropylene carbonate waterborne polyurethane emulsion and preparation method and application thereof | |
| CN101838383A (en) | Aqueous fluoro modified urethane resin and preparation of aqueous fluoro modified urethane resin paint | |
| CN105462536A (en) | Waterborne silane modified polyurethane bonding agent and preparation method thereof | |
| CN104031233A (en) | Acrylic polyurethane emulsion as well as preparation method and application thereof | |
| CN102070759A (en) | Method for preparing water-based polyurethane leather retanning agent | |
| CN103409101A (en) | Polybutadiene rubber modified waterborne polyurethane adhesive and preparation method thereof | |
| CN104693994A (en) | Ultraviolet photocuring coating containing inorganic pigment and filler and preparation method thereof | |
| CN108164678A (en) | A kind of soybean oil base water polyurethane of UV curable and preparation method thereof | |
| CN109293846A (en) | The preparation method of fluorinated silicone modified multi-arm type polyurethane-hydroxy acrylate lotion | |
| CN107151520B (en) | A kind of tung oil base water polyurethane coating and preparation method thereof | |
| CN105462479B (en) | A kind of weather-proof self demixing single-component waterproof coating material of environment-friendly type and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |