CN104087235B - A kind of Aqueous Polyurethane Adhesives and preparation method thereof - Google Patents
A kind of Aqueous Polyurethane Adhesives and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of Aqueous Polyurethane Adhesives and preparation method thereof.This Aqueous Polyurethane Adhesives includes prepolymer and water, and described prepolymer forms solution after being distributed in water, and the solid content of solution is 50%；Wherein, described prepolymer includes that following raw material forms: Polyethylene Glycol, polyester diol, carboxylic acid type hydrophilic chain extender, diisocyanate and small molecule chain extender；With molar ratio computing, diisocyanate polyethylene glycol polyester diol carboxylic acids's type hydrophilic chain extender small molecule chain extender=(25 40): X: (10 X): (7.5 15): (7.5 15), wherein, between X value 0 to 10 any number of 0 and 10, is included.The present invention also provides for the preparation method of above-mentioned Aqueous Polyurethane Adhesives.Aqueous Polyurethane Adhesives solid content prepared by the present invention is high, and dispersion stabilization is good, makes it not only remain some premium properties of traditional solvent-borne adhesive for polyurethane, has more advantage safe, nonflammable, free from environmental pollution, that peel strength is high.
Description
Technical field
The present invention relates to a kind of Aqueous Polyurethane Adhesives and preparation method thereof, belong to adhesive technical field.
Background technology
In prior art, most of adhesive for polyurethane of domestic development & production are all solvent type, this solvent type
Adhesive use this that China's environment is caused the biggest pressure, in response to the requirement of environmental protection, the most increasingly
Many people at the Aqueous Polyurethane Adhesives of research and development excellent performance, replace solvent type adhesive with this.But existing water
Property adhesive for polyurethane peel strength generally the lowest, do not reach far away the peel strength of solvent type adhesive, can not meet and make
With requiring.
In China, owing to being affected by the aspect such as price, raw material, the polyhydric alcohol master that Aqueous Polyurethane Adhesives is used
If using the alcohol of polyether-type, conventional is many with polypropylene oxide ether glycol as primary raw material, and the glued membrane of this emulsion is in intensity
Aspect has some defects；And abroad polyhydric alcohol mainly uses polyester-type, conventional has poly adipate succinic acid ester (PBA), because of
The highly polar ester group contained in its structure, so good with the bonding force of polar substrates, resistance to thermooxidation is also good than polyether-type.Poly-own
Lactone polyols is compared with conventional polyester polyhydric alcohol, and the polyurethane of preparation is in wear-resisting, resistance to oxidation, resistant to chemical media and anti tear
Aspect is even better, but the domestic product prepared with polycaprolactone diols is less, uses polyester in patent CN102827570A
Polyhydric alcohol is prepared for the adhesives for shoes that solid content is 50%, but the initial bonding strength of the adhesive obtained is on the low side, to be improved.
Summary of the invention
The defect existed in view of above-mentioned prior art, it is an object of the invention to a kind of Aqueous Polyurethane Adhesives and preparation thereof
Method, it is possible to the adhesive for polyurethane solid content solving aqueous, environmental protective is low, the problem that peel strength is low.
The purpose of the present invention is achieved by the following technical programs:
A kind of Aqueous Polyurethane Adhesives, including prepolymer and water, described prepolymer forms solution after being distributed in water, molten
The solid content of liquid is 50% (can be more than 50%)；Wherein, described prepolymer includes that following raw material forms:
Polyethylene Glycol (PEG), polyester diol, carboxylic acid type hydrophilic chain extender, diisocyanate and small molecule chain extender；
With molar ratio computing, diisocyanate polyethylene glycol polyester diol carboxylic acids's type hydrophilic chain extender small molecule chain extender=
(25-40) any number of 0 and 10: X: (10-X): (7.5-15): (7.5-15), wherein, between X value 0 to 10, is included.
In above-mentioned Aqueous Polyurethane Adhesives, Polyethylene Glycol, polyester diol are respectively polyether-type and polyester-type is many
Unit's alcohol, both are used in mixed way according to different proportion, and the performance ratio of the adhesive obtained is used alone polyether-type or is used alone poly-
Ester type will exceed a lot；Preferably, described Polyethylene Glycol is PEG2k, and described polyester diol is the polyester of molecular weight 2000
Dihydroxylic alcohols, but it is not limited to this.
According to specific embodiments, in above-mentioned Aqueous Polyurethane Adhesives, refer to pre-during solid content 50% practical operation
The part by weight of polymers and water is equal to 1:1.
In above-mentioned Aqueous Polyurethane Adhesives, it is preferred that the raw material of described prepolymer also includes catalyst, its consumption is
The 0.01wt%-0.1wt% of prepolymer gross weight；It is furthermore preferred that described catalyst includes stannous octoate and/or tin dilaurate two
Butyl tin, but it is not limited to this.
In above-mentioned Aqueous Polyurethane Adhesives, it is preferred that the raw material of described prepolymer also includes nertralizer, with mol ratio
Meter, carboxylic acid type hydrophilic chain extender nertralizer=1: 1；It is furthermore preferred that described nertralizer is triethylamine (TEA), but it is not limited to
This.
Above-mentioned triethylamine is nertralizer, and nertralizer can neutralize-the COOH in carboxylic acid type hydrophilic chain extender.
In above-mentioned Aqueous Polyurethane Adhesives, it is preferred that described polyester diol includes polyadipate-BDO
One or several in ester, polyadipate-1,6-butanediol ester, poly-epsilon-caprolactone, PCDL, PTMG etc.
The combination planted.
In above-mentioned Aqueous Polyurethane Adhesives, it is preferred that described diisocyanate includes aliphatic diisocyanate, fat
The combination of one or more in the diisocyanate of ring race, aromatic diisocyanate etc.；Described aliphatic diisocyanate includes
ONC-(CH2)4-NCO、ONC-(CH2)6-NCO、ONC-(CH2)8-NCO、ONC-(CH2)12In-NCO, 1,5-bis-Carbimide .-2-methylpentane etc. one
Kind or several combinations；Described alicyclic diisocyanate includes The combination of one or more in Deng；Described aromatic diisocyanate includes The combination of one or more in Deng.
In above-mentioned Aqueous Polyurethane Adhesives, it is preferred that described carboxylic acid type hydrophilic chain extender includes dihydroxymethyl fourth
The combination of one or more in acid (DMBA), dihydromethyl propionic acid (DMPA), diaminobenzoic acid, dihydroxy half ester etc..
In above-mentioned Aqueous Polyurethane Adhesives, described small molecule chain extender is the combination of monomer or monomer；Preferably, institute
State small molecule chain extender and include 1,4 butanediols, HO-(CH2)2-OH、H2N-(CH2)2-NH2、H2N-(CH2)6-NH2、H2N-
(CH2)8-NH2、H2N-(CH2)10-NH2、 One in Deng
Or several combinations.
The present invention also provides for the preparation method of above-mentioned Aqueous Polyurethane Adhesives, comprises the steps:
Polyethylene Glycol (PEG), polyester diol, carboxylic acid type hydrophilic chain extender are dissolved in organic solvent, add
Diisocyanate and catalyst, at 70 DEG C-80 DEG C, stirring reaction 3h-4h, obtain just poly-liquid；
Small molecule chain extender is added in first poly-liquid, at 50 DEG C-70 DEG C, stirring reaction 1h-2h, obtain polymer mixed
Liquid；
In polymer mixed liquid, add nertralizer triethylamine (TEA), neutralize carboxylic acid type hydrophilic chain extender completely, in temperature
Degree is 40 DEG C-50 DEG C, stirs 0.5h, obtains prepolymer；
Being slowly added dropwise water in prepolymer, stirring and emulsifying is disperseed, and then organic solvent is sloughed in decompression distillation, i.e. obtains aqueous
Adhesive for polyurethane.
In above-mentioned preparation method, organic solvent is Conventional solvents, preferably acetone；Its consumption is excess, it is possible to the most molten
Solve all raw materials of prepolymer.
The Aqueous Polyurethane Adhesives of gained of the present invention, initially and finally peel strength respectively reaches the highest 48N
cm-1With 55N cm-1。
Gained Aqueous Polyurethane Adhesives of the present invention preferably can serve as adhesives for shoes.
The prominent 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, good fluidity, uses
Convenient；And there is preferable dispersion stabilization, make it not only remain some of traditional solvent-borne adhesive for polyurethane excellent
Performance, has more advantage safe, nonflammable, free from environmental pollution, that peel strength is high.
2. preparation technology is simple, and raw material is easy to get, and can realize commercial production, and preparation process is pollution-free, and solvent is recyclable, to people
Body fanout free region, can reach environmental requirement；
3. polyester-type and polyether polyol are used in mixed way according to different proportion, and the performance ratio of the adhesive obtained individually makes
With polyether-type or be used alone polyester-type and will get well；
4. using one-step method preparation just polymers, the better performances of the adhesive obtained, peel 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 Aqueous Polyurethane Adhesives WPUD and the infrared spectrum of raw material components thereof of embodiment 1-8；
Fig. 3 a is the initial peel strength figure of the adhesive for polyurethane of the polyester synthesis of the different proportion of embodiment 1-8；
Fig. 3 b is the final peel strength figure of the adhesive for polyurethane of the polyester synthesis of the different proportion of embodiment 1-8；
Fig. 3 c is the water contact angle trend of the adhesive for polyurethane glued membrane of the polyester synthesis of the different proportion of embodiment 1-8
Figure；
Fig. 3 d is the water contact angle signal of the adhesive for polyurethane glued membrane of the polyester synthesis of the different proportion of embodiment 1-8
Figure；
Fig. 3 e is the viscosity profile figure of the adhesive for polyurethane of the polyester synthesis of the different proportion of embodiment 1-8；
Detailed description of the invention
Below by specific embodiment, the method for the present invention is illustrated, so that technical solution of the present invention is easier to reason
Solve, grasp, but the invention is not limited in this.Experimental technique described in following embodiment, if no special instructions, is routine side
Method；Described reagent and material, if no special instructions, the most commercially obtain.
Explanation of nouns:
PEG refers to: Polyethylene Glycol；
TEA refers to: triethylamine；
PBA refers to: polyadipate BDO ester；
IPDI refers to: isophorone diisocyanate, chemical name 3-isocyanates methylene-3,5,5-3-methyl cyclohexanols
Based isocyanate；
HDI refers to hexamethylene diisocyanate；
MDI refers to 4,4-methyl diphenylene diisocyanate；
DMPA refers to 2,2-dihydromethyl propionic acid；
DMBA refers to: 2,2-dimethylolpropionic acid；
NCO refers to: NCO in chemical material, and its value refers to the isocyanates (-NCO) group contained by 100g sample
Quality；
BDO refers to: 1,4-butanediol；
EDA refers to ethylenediamine.
Embodiment 1
The present embodiment provides a kind of Aqueous Polyurethane Adhesives, and including prepolymer and water, described prepolymer includes the most former
Material composition:
Polyester diol PBA2k, carboxylic acid type hydrophilic chain extender DMBA, diisocyanate 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 is prepared by following method, as shown in Figure 1:
40gPBA2k is warming up to 120 DEG C, is dehydrated 30min, pours into equipped with thermometer, reflux condensing tube and agitator
In 250ml there-necked flask, 50 DEG C of insulations, be then added thereto to 15.5gIPDI and 2.25gDMBA acetone soln (with mole
, it is warmed up to 75 DEG C, at the uniform velocity stirring reaction 3h, obtains just poly-liquid gauge DMBA: acetone=1:1)；
In first poly-liquid, add 1.35gBDO chain extension, 70 DEG C of reaction 1h, obtain polymer mixed liquid, for ensureing that reaction is fully
Carry out, course of reaction is observed viscosity, find that adding acetone when viscosity is excessive is reduced；
Reaction system is down to 20 DEG C, adds acetone solvent regulation system viscosity, be slowly added dropwise 1.5g tri-second with Dropping funnel
Amine is neutralized, and strong stirring half an hour, obtains prepolymer；
The water being slowly added dropwise mass fraction 50% in prepolymer disperses to stirring and emulsifying in system, and then decompression distillation is de-
Remove lower boiling acetone, i.e. obtain Aqueous Polyurethane Adhesives.
Embodiment 2
The present embodiment provides a kind of Aqueous Polyurethane Adhesives, and including prepolymer and water, described prepolymer includes the most former
Material composition:
Polyester diol PBA2k, PEG2k, carboxylic acid type hydrophilic chain extender DMBA, diisocyanate IPDI, little molecule expand
Chain agent 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 is prepared by following method, as shown in Figure 1:
38gPBA2k and 2gPEG2k is warming up to 120 DEG C, be dehydrated 30min, pour into equipped with thermometer, reflux condensing tube and
In the 250ml there-necked flask of agitator, 50 DEG C of insulations, then it is added thereto to the acetone soln of 15.5gIPDI and 2.25gDMBA
(with molar amount DMBA: acetone=1:1), is warmed up to 75 DEG C, at the uniform velocity stirring reaction 3h, obtains just poly-liquid；
In first poly-liquid, add 1.35gBDO chain extension, 70 DEG C of reaction 1h, obtain polymer mixed liquid, for ensureing that reaction is fully
Carry out, course of reaction is observed viscosity, find that adding acetone when viscosity is excessive is reduced；
Reaction system is down to 20 DEG C, adds acetone solvent regulation system viscosity, be slowly added dropwise 1.5g tri-second with Dropping funnel
Amine is neutralized, and strong stirring half an hour, obtains prepolymer；
The water being slowly added dropwise mass fraction 50% in prepolymer disperses to stirring and emulsifying in system, and then decompression distillation is de-
Remove lower boiling acetone, i.e. obtain Aqueous Polyurethane Adhesives.
Embodiment 3
The present embodiment provides a kind of Aqueous Polyurethane Adhesives, and including prepolymer and water, described prepolymer includes the most former
Material composition:
Polyester diol PBA2k, PEG, carboxylic acid type hydrophilic chain extender DMBA, diisocyanate IPDI, little molecule chain extension
Agent 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 is prepared by following method, as shown in Figure 1:
36gPBA2k and 4gPEG2k is warming up to 120 DEG C, be dehydrated 30min, pour into equipped with thermometer, reflux condensing tube and
In the 250ml there-necked flask of agitator, 50 DEG C of insulations, then it is added thereto to the acetone soln of 15.5gIPDI and 2.25gDMBA
(with molar amount DMBA: acetone=1:1), is warmed up to 75 DEG C, at the uniform velocity stirring reaction 3h, obtains just poly-liquid；
In first poly-liquid, add 1.35gBDO chain extension, 70 DEG C of reaction 1h, obtain polymer mixed liquid, for ensureing that reaction is fully
Carry out, course of reaction is observed viscosity, find that adding acetone when viscosity is excessive is reduced；
Reaction system is down to 20 DEG C, adds acetone solvent regulation system viscosity, be slowly added dropwise 1.5g tri-second with Dropping funnel
Amine is neutralized, and strong stirring half an hour, obtains prepolymer；
The water being slowly added dropwise mass fraction 50% in prepolymer disperses to stirring and emulsifying in system, and then decompression distillation is de-
Remove lower boiling acetone, i.e. obtain Aqueous Polyurethane Adhesives.
Embodiment 4
The present embodiment provides a kind of Aqueous Polyurethane Adhesives, and including prepolymer and water, described prepolymer includes the most former
Material composition:
Polyester diol PBA2k, PEG, carboxylic acid type hydrophilic chain extender DMBA, diisocyanate IPDI, little molecule chain extension
Agent 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 is prepared by following method, as shown in Figure 1:
32gPBA2k and 8gPEG2k is warming up to 120 DEG C, be dehydrated 30min, pour into equipped with thermometer, reflux condensing tube and
In the 250ml there-necked flask of agitator, 50 DEG C of insulations, add the acetone soln of 15.5gIPDI and 2.25gDMBA the most wherein
(with molar amount DMBA: acetone=1:1), is warmed up to 75 DEG C, at the uniform velocity stirring reaction 3h, obtains just poly-liquid；
In first poly-liquid, add 1.35gBDO chain extension, 70 DEG C of reaction 1h, obtain polymer mixed liquid, for ensureing that reaction is fully
Carry out, course of reaction is observed viscosity, find that adding acetone when viscosity is excessive is reduced；
Reaction system is down to 20 DEG C, adds acetone solvent regulation system viscosity, be slowly added dropwise 1.5g tri-second with Dropping funnel
Amine is neutralized, and strong stirring half an hour, obtains prepolymer；
The water being slowly added dropwise mass fraction 50% in prepolymer disperses to stirring and emulsifying in system, and then decompression distillation is de-
Remove lower boiling acetone, i.e. obtain Aqueous Polyurethane Adhesives.
Embodiment 5
The present embodiment provides a kind of Aqueous Polyurethane Adhesives, and including prepolymer and water, described prepolymer includes the most former
Material composition:
Polyester diol PBA2k, PEG, carboxylic acid type hydrophilic chain extender DMBA, diisocyanate IPDI, little molecule chain extension
Agent 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 is prepared by following method, as shown in Figure 1:
28gPBA2k and 12gPEG2k is warming up to 120 DEG C, be dehydrated 30min, pour into equipped with thermometer, reflux condensing tube and
In the 250ml there-necked flask of agitator, 50 DEG C of insulations, then it is added thereto to the acetone soln of 15.5gIPDI and 2.25gDMBA
(with molar amount DMBA: acetone=1:1), is warmed up to 75 DEG C, at the uniform velocity stirring reaction 3h, obtains just poly-liquid；
In first poly-liquid, add 1.35gBDO chain extension, 70 DEG C of reaction 1h, obtain polymer mixed liquid, for ensureing that reaction is fully
Carry out, course of reaction is observed viscosity, find that adding acetone when viscosity is excessive is reduced；
Reaction system is down to 20 DEG C, adds acetone solvent regulation system viscosity, be slowly added dropwise 1.5g tri-second with Dropping funnel
Amine is neutralized, and strong stirring half an hour, obtains prepolymer；
The water being slowly added dropwise mass fraction 50% in prepolymer disperses to stirring and emulsifying in system, and then decompression distillation is de-
Remove lower boiling acetone, i.e. obtain Aqueous Polyurethane Adhesives.
Embodiment 6
The present embodiment provides a kind of Aqueous Polyurethane Adhesives, and including prepolymer and water, described prepolymer includes the most former
Material composition:
Polyester diol PBA2k, PEG, carboxylic acid type hydrophilic chain extender DMBA, diisocyanate IPDI, little molecule chain extension
Agent 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 is prepared by following method, as shown in Figure 1:
24gPBA2k and 16gPEG2k is warming up to 120 DEG C, be dehydrated 30min, pour into equipped with thermometer, reflux condensing tube and
In the 250ml there-necked flask of agitator, 50 DEG C of insulations, then it is added thereto to the acetone soln of 15.5gIPDI and 2.25gDMBA
(with molar amount DMBA: acetone=1:1), is warmed up to 75 DEG C, at the uniform velocity stirring reaction 3h, obtains just poly-liquid；
In first poly-liquid, add 1.35gBDO chain extension, 70 DEG C of reaction 1h, obtain polymer mixed liquid, for ensureing that reaction is fully
Carry out, course of reaction is observed viscosity, find that adding acetone when viscosity is excessive is reduced；
Reaction system is down to 20 DEG C, adds acetone solvent regulation system viscosity, be slowly added dropwise 1.5g tri-second with Dropping funnel
Amine is neutralized, and strong stirring half an hour, obtains prepolymer；
The water being slowly added dropwise mass fraction 50% in prepolymer disperses to stirring and emulsifying in system, and then decompression distillation is de-
Remove lower boiling acetone, i.e. obtain Aqueous Polyurethane Adhesives.
Embodiment 7
The present embodiment provides a kind of Aqueous Polyurethane Adhesives, and including prepolymer and water, described prepolymer includes the most former
Material composition:
Polyester diol PBA2k, PEG, carboxylic acid type hydrophilic chain extender DMBA, diisocyanate IPDI, little molecule chain extension
Agent 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 is prepared by following method, as shown in Figure 1:
20gPBA2k and 20gPEG2k is warming up to 120 DEG C, be dehydrated 30min, pour into equipped with thermometer, reflux condensing tube and
In the 250ml there-necked flask of agitator, 50 DEG C of insulations, then it is added thereto to the acetone soln of 15.5gIPDI and 2.25gDMBA
(with molar amount DMBA: acetone=1:1), is warmed up to 75 DEG C, at the uniform velocity stirring reaction 3h, obtains just poly-liquid；
In first poly-liquid, add 1.35gBDO chain extension, 70 DEG C of reaction 1h, obtain polymer mixed liquid, for ensureing that reaction is fully
Carry out, course of reaction is observed viscosity, find that adding acetone when viscosity is excessive is reduced；
Reaction system is down to 20 DEG C, adds acetone solvent regulation system viscosity, be slowly added dropwise 1.5g tri-second with Dropping funnel
Amine is neutralized, and strong stirring half an hour, obtains prepolymer；
The water being slowly added dropwise mass fraction 50% in prepolymer disperses to stirring and emulsifying in system, and then decompression distillation is de-
Remove lower boiling acetone, i.e. obtain Aqueous Polyurethane Adhesives.
Embodiment 8
The present embodiment provides a kind of Aqueous Polyurethane Adhesives, and including prepolymer and water, described prepolymer includes the most former
Material composition:
PEG2k, carboxylic acid type hydrophilic chain extender DMBA, diisocyanate IPDI, small molecule chain extender BDO and TEA, to rub
You count by ratio, and IPDI: PEG: DMBA: BDO: TEA=35: 10: 7.5: 7.5: 7.5.
The Aqueous Polyurethane Adhesives of the present embodiment is prepared by following method, as shown in Figure 1:
40gPEG2k is warming up to 120 DEG C, is dehydrated 30min, pours into equipped with thermometer, reflux condensing tube and agitator
In 250ml there-necked flask, 50 DEG C of insulations, be then added thereto to 15.5gIPDI and 2.25gDMBA acetone soln (with mole
, it is warmed up to 75 DEG C, at the uniform velocity stirring reaction 3h, obtains just poly-liquid gauge DMBA: acetone=1:1)；
In first poly-liquid, add 1.35gBDO chain extension, 70 DEG C of reaction 1h, obtain polymer mixed liquid, for ensureing that reaction is fully
Carry out, course of reaction is observed viscosity, find that adding acetone when viscosity is excessive is reduced；
Reaction system is down to 20 DEG C, adds acetone solvent regulation system viscosity, be slowly added dropwise 1.5g tri-second with Dropping funnel
Amine is neutralized, and strong stirring half an hour, obtains prepolymer；
The water being slowly added dropwise mass fraction 50% in prepolymer disperses to stirring and emulsifying in system, and then decompression distillation is de-
Remove lower boiling acetone, i.e. obtain Aqueous Polyurethane Adhesives.
Embodiment 9
The present embodiment provides a kind of Aqueous Polyurethane Adhesives, and including prepolymer and water, described prepolymer includes the most former
Material composition:
Polyester diol PBA, carboxylic acid type hydrophilic chain extender DMPA, diisocyanate 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 is prepared by following method, as shown in Figure 1:
PBA is warming up to 120 DEG C, is dehydrated 30min, pours three mouthfuls of burnings equipped with thermometer, reflux condensing tube and agitator into
In Ping, 50 DEG C of insulations, then it is added thereto to the acetone soln (with molar amount DMPA: acetone=1:1) of MDI and DMPA, rises
Temperature is to 75 DEG C, and 3h is reacted at the uniform velocity stirring, obtains just poly-liquid；
In first poly-liquid, add EDA chain extension, 70 DEG C of reaction 1h, obtain polymer mixed liquid, for ensureing that reaction is fully carried out,
Course of reaction is observed viscosity, finds that adding acetone when viscosity is excessive is reduced；
Reaction system is down to room temperature, adds acetone solvent regulation system viscosity, be slowly added dropwise triethylamine with Dropping funnel and enter
Row neutralizes, and strong stirring half an hour, obtains prepolymer；
The water being slowly added dropwise mass fraction 50% in prepolymer disperses to stirring and emulsifying in system, and then decompression distillation is de-
Remove lower boiling acetone, i.e. obtain Aqueous Polyurethane Adhesives.
The present embodiment uses one-step method first with the aromatic diisocyanate of excess, polyester diol and carboxylic acid type hydrophilic
Chain extender carrys out the first aggressiveness of synthesis of polyurethane, and then first aggressiveness chain extension further with amine micromolecular again, generates urea chain prepolymer,
Last prepolymer is stirred emulsion dispersion with water and has obtained aqueous polyurethaneurea adhesive.
Embodiment 10
The present embodiment provides a kind of Aqueous Polyurethane Adhesives, and including prepolymer and water, described prepolymer includes the most former
Material composition:
Polyester diol PBA, carboxylic acid type hydrophilic chain extender DMPA, diisocyanate 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 is prepared by following method, as shown in Figure 1:
PBA is warming up to 120 DEG C, is dehydrated 30min, pours three mouthfuls of burnings equipped with thermometer, reflux condensing tube and agitator into
In Ping, 50 DEG C of insulations, then it is added thereto to MDI, is warmed up to 75 DEG C, at the uniform velocity stirring reaction 2h, obtain just poly-liquid；
In first poly-liquid, add the acetone soln (with molar amount DMPA: acetone=1:1) of DMPA, at the uniform velocity stir reaction
1h, adds EDA chain extension, 70 DEG C of reaction 1h, obtains polymer mixed liquid, for ensureing that reaction is fully carried out, see in course of reaction
Examine viscosity, find that adding acetone when viscosity is excessive is reduced；
Reaction system is down to room temperature, adds acetone solvent regulation system viscosity, be slowly added dropwise triethylamine with Dropping funnel and enter
Row neutralizes, and strong stirring half an hour, obtains prepolymer；
The water being slowly added dropwise mass fraction 50% in prepolymer disperses to stirring and emulsifying in system, and then decompression distillation is de-
Remove lower boiling acetone, i.e. obtain Aqueous Polyurethane Adhesives.
The present embodiment is to use two-step method, first with diisocyanate and the polyester diol reaction of excess, then and carboxylic acid type
Hydrophilic chain extender reaction carrys out the first aggressiveness of synthesis of polyurethane, and chain extension further with small molecule chain extender, eventually forms the most again
Prepolymer and water are stirred emulsion dispersion and obtain aqueous polyurethaneurea adhesive.
Testing the Aqueous Polyurethane Adhesives of embodiment 1-8 gained, (polyester of different proportion mixes result such as table 1
Close the experimental result of adhesive for polyurethane of soft section of synthesis) and Fig. 2, Fig. 3 (a-e) shown in, embodiment 1-8 employing acetone method, with
PEG and PBA is soft section of mixing, and the ratio of addition is as follows: 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 adhesive obtained is used alone polyether-type or is used alone polyester-type and will exceed a lot.
Table 1
As seen from Figure 2, figure shows the infrared spectrum of Aqueous Polyurethane Adhesives (WPUD).Figure also shows
There is other raw-material infrared spectrum.2275-2250cm as seen from the figure-1The NCO base peak at place substantially disappears, and NCO base is described
Group substantially completely take part in reaction；And 3419cm-1And 1653cm-1There is the characteristic absorption peak of N-H in place, show NCO group with
Hydroxyl and amino reaction generate carbamate groups, urea groups etc.；
By Fig. 3 a it can be seen that initially peel strength is along with the increase of PEG/PBA ratio, first increase and decline afterwards, work as PEG/
During PBA=3/7, initial peel strength reaches maximum.
By Fig. 3 b it can be seen that final peel strength is along with the increase of PEG/PBA ratio, first increase and decline afterwards, work as PEG/
During PBA=3/7, final peel strength reaches maximum.
By Fig. 3 c it can be seen that along with the increase of PEG/PBA ratio, water contact angle is gradually reduced.
By Fig. 3 d it can be seen that the water contact angle of aqueous polyurethane film 0 < 90 °, illustrate that it is lyophily, i.e. water is wettable
Polyurethane film, this is due to self-emulsification aqueous polyaminoester emulsion, and in building-up process, needs introduce hydrophilic in polyurethane molecular chain
Property group, containing-COO in the polyurethane latex film eventually formed-And H+Polar ionic groups, the therefore wettable polyurethane film of water.
By Fig. 3 e it can be seen that along with the increase of PEG/PBA ratio, i.e. PEG content gradually step up, viscosity gradually decreases,
As m (PEG/PBA)=1/9, reducing sharply occurs in viscosity.
Embodiment 9 and 10 two kind of method are compared, result such as table 2 (one-step method of embodiment 9 and 10 offer and two steps
The experimental result of the adhesive for polyurethane of method synthesis) shown in:
Table 2
| Initially peel strength (N cm-1) | Final peel strength (N cm-1) | Viscosity (mpa s) | |
| One-step method | 23 | 28.3 | 1800 |
| Two-step method | 7.5 | 20 | 360 |
As can be seen from Table 2, the initially and finally peel strength of the adhesive for polyurethane that one-step method obtains is all than two-step method
Exceed a lot, but the ratio of viscosities one-step method of adhesive that two-step method obtains is much smaller.Because during with one-step synthesis method polyurethane,
DMPA preferentially reacts with IPDI, defines longer hard section and the hydrophilic group sequence than comparatively dense；Two-step method is then due to parent
It is distributed in strand, so its hard section length is narrow the polyalcohols molecule interval that the ionic group of aqueous is grown.Therefore one
The polyurethane that footwork polymerization obtains divides the electrostatic force given between the interchain hard section containing hydrophilic group and hydrogen bond action to strengthen,
The easy self assemble of hard section, separates out from soft section of middle reaches, constitutes certain hard segment microcell, promotes soft or hard section to be separated and more adds
Entirely.
Claims (9)
1. an Aqueous Polyurethane Adhesives, including prepolymer and water, described prepolymer forms solution, solution after being distributed in water
Solid content be 50%；Wherein, described prepolymer includes that following raw material forms:
Polyethylene Glycol, polyester diol, carboxylic acid type hydrophilic chain extender, diisocyanate and small molecule chain extender；With mol ratio
Meter, diisocyanate polyethylene glycol polyester diol carboxylic acids's type hydrophilic chain extender small molecule chain extender=(25-40): X:
(10-X) any number of 0.5 and 5: (7.5-15): (7.5-15), wherein, between X value 0.5 to 5, is included.
Aqueous Polyurethane Adhesives the most according to claim 1, it is characterised in that: the raw material of described prepolymer also includes urging
Agent, described catalyst includes stannous octoate and/or dibutyl tin laurate, and its consumption is prepolymer gross weight
0.01wt%-0.1wt%.
Aqueous Polyurethane Adhesives the most according to claim 1, it is characterised in that: during the raw material of described prepolymer also includes
Mediating recipe, with molar ratio computing, carboxylic acid type hydrophilic chain extender nertralizer=1: 1.
Aqueous Polyurethane Adhesives the most according to claim 3, it is characterised in that: described nertralizer is triethylamine.
Aqueous Polyurethane Adhesives the most according to claim 1, it is characterised in that: described polyester diol include poly-oneself two
The combination of one or more in acid-1,4-butanediol ester, poly-epsilon-caprolactone, PCDL.
Aqueous Polyurethane Adhesives the most according to claim 1, it is characterised in that: described diisocyanate includes aliphatic
Diisocyanate, alicyclic diisocyanate, the combination of one or more in aromatic diisocyanate；Described fat
The diisocyanate of fat race includes OCN-(CH2)4-NCO、OCN(CH2)6-NCO、OCN-(CH2)8-NCO、OCN-(CH2)12-NCO、
The combination of one or more in 1,5-bis-Carbimide .-2-methylpentane；Described alicyclic diisocyanate includes
In the combination of one or more；Described aromatic diisocyanate includes
In the combination of one or more.
Aqueous Polyurethane Adhesives the most according to claim 1, it is characterised in that: described carboxylic acid type hydrophilic chain extender bag
Include the combination of one or more in dimethylolpropionic acid, dihydromethyl propionic acid, diaminobenzoic acid, dihydroxy half ester.
Aqueous Polyurethane Adhesives the most according to claim 1, it is characterised in that: described small molecule chain extender include Isosorbide-5-Nitrae-
Butanediol, HO-(CH2)2-OH、H2N-(CH2)2-NH2、H2N-(CH2)6-NH2、H2N-(CH2)8-NH2、H2N-(CH2)10-NH2、In the combination of one or more.
9. the preparation method of the Aqueous Polyurethane Adhesives described in any one of claim 1-8, comprises the steps:
Polyethylene Glycol, polyester diol, carboxylic acid type hydrophilic chain extender are dissolved in organic solvent, add diisocyanate
And catalyst, at 70 DEG C-80 DEG C, stirring reaction 3h-4h, obtain just poly-liquid；
Small molecule chain extender is added in first poly-liquid, at 50 DEG C-70 DEG C, stirring reaction 1h-2h, obtain polymer mixed liquid；
In polymer mixed liquid, add nertralizer triethylamine, neutralize carboxylic acid type hydrophilic chain extender completely, temperature be 40 DEG C-
50 DEG C, stir 0.5h, obtain prepolymer；
Being slowly added dropwise water in prepolymer, stirring and emulsifying is disperseed, and then organic solvent is sloughed in decompression distillation, i.e. obtains the poly-ammonia of aqueous
Ester adhesive.
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| CN108752552B (en) * | 2018-06-06 | 2020-12-01 | 上海华谊精细化工有限公司 | Preparation method of branched waterborne polyurethane nanocomposite |
| 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 |
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| 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 |
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| 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 |
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