CN103030775B - For aqueous polyurethane emulsion making water-proof strip and preparation method thereof - Google Patents
For aqueous polyurethane emulsion making water-proof strip and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of aqueous polyurethane emulsion for making water-proof strip, its raw material consists of the aqueous polyurethane and water that mass ratio is 0.5-0.9:1; Described aqueous polyurethane raw material composition and weight percentage as follows: the vulcabond of (a) 8-50wt%; The polyvalent alcohol of (b) 25-80wt%; The non-hydrophilic chainextender of (c) 0-10wt%; The hydrophilic chain extender of (d) 0.5-15wt%; The chainextender containing active hydrogen of (e) 0-8wt%; The summation of above-mentioned raw materials is 100%; In the raw material of above-mentioned aqueous polyurethane, the mol ratio of isocyanate group NCO and hydroxyl OH is 2-5:1.The present invention does not contain for the preparation of the aqueous polyurethane emulsion of water-proof strip or only contains the volatile organic solvent of minute quantity, solid content 25-50%, viscosity is less, obtained high performance water-proof strip after realizing high speed curing of coating, it is large that this water-proof strip has bonding intensity, intensity is high, and bonding part is soft, the features such as waterproofing and moisture-penetration performances is good.
Description
Technical field
The invention belongs to hot melt adhesive technical field, particularly relate to a kind of for aqueous polyurethane emulsion making water-proof strip and preparation method thereof.
Background technology
Water-proof strip is to coordinate the waterproof idea of the products such as clothes, shoes and outdoor goods to give birth to, and this series products is mainly used in the waterproof, windproof process etc. of pin sealing of the waterproof of PU, PVC coating fabric, warm wear and goods thereof.This series products mainly uses oiliness polyurethane standby at present, in preparation process, a large amount of consumption arene organic solvent, environmental pollution is large, generally all need to prepare polyurethane elastomer in advance, then casting film-forming, complex process under this kind of mode, needs to reclaim organic solvent, easily causes environmental pollution, consumes a large amount of energy; At present, also have and obtain polyurethane aqueous dispersion body by letex polymerization, through breakdown of emulsion, the dry technique then preparing water-proof strip, but this technical sophistication, and its product performance and oiliness polyurethane products have larger gap.And aqueous polyurethane bonding intensity prepared by general traditional method is low, seldom there is commercial aqueous polyurethane water-proof strip.
Aqueous polyurethane (WPU) adopts water as the polyaminoester emulsion of dispersion medium, except the excellent properties with solvent borne polyurethane, also there is the advantages such as construction process is nonflammable, explosive, nontoxic, non-environmental-pollution, along with the continuous enhancing of people's environmental consciousness, the intersection that the technology of preparing of urethane extremely goods also experienced by from traditional solvent-borne type to water-based changes.At present, aqueous product has been successfully applied to the industries such as light textile, leather, wood working, building, papermaking.
Therefore, develop for the preparation of water-proof strip, both had environmental protection and energy saving feature, the aqueous polyurethane emulsion again with good water proof wind proof effect is current extremely important research topic.
At present, considerable research work is done to aqueous polyurethane product both at home and abroad, but for the rare patent of aqueous polyurethane product of water-proof strip and bibliographical information.
Summary of the invention
Based on this, the object of this invention is to provide a kind of aqueous polyurethane emulsion for making water-proof strip.
For making an aqueous polyurethane emulsion for water-proof strip, its raw material consists of the aqueous polyurethane and water that mass ratio is 0.5-0.9:1;
Described aqueous polyurethane raw material composition and weight percentage as follows:
The vulcabond of (a) 8-50wt%;
The polyvalent alcohol of (b) 25-80wt%;
The non-hydrophilic chainextender of (c) 0-10wt%;
The hydrophilic chain extender of (d) 0.5-15wt%;
The chainextender containing active hydrogen of (e) 0-8wt%; The summation of above-mentioned raw materials is 100%;
In the raw material of above-mentioned aqueous polyurethane, the mol ratio of isocyanate group and polyol hydroxyls is 2-5:1.
Wherein in some embodiments, the raw material of described aqueous polyurethane composition and weight percentage as follows:
The vulcabond of (a) 19-42wt%;
The polyvalent alcohol of (b) 45-80wt%;
The non-hydrophilic chainextender of (c) 1.5-7wt%;
The hydrophilic chain extender of (d) 0.5-5.5wt%;
The chainextender containing active hydrogen of (e) 0-1.5wt%; The summation of above-mentioned raw materials is 100%.
Wherein in some embodiments, described vulcabond is tolylene diisocyanate, ditan-4, one or more in 4 '-vulcabond, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, tetramethylxylylene diisocyanate, Methylcyclohexyl diisocyanate, isophorone diisocyanate.
Wherein in some embodiments, described polyvalent alcohol is polyoxypropyleneglycol, polyoxytrimethylene triol, polyoxytrimethylene-castor oil polyhydric alcohol, polytetrahydrofuran diol, Polyoxyethylene glycol, polycaprolactone diols, PCDL, polyethylene glycol adipate glycol, poly-adipate glycol-propylene glycol ester glycol, poly-hexanodioic acid glycol ether esterdiol, poly-adipate glycol-glycol ether esterdiol, poly-hexanodioic acid-1, 4-butanediol ester glycol, poly-adipate glycol-1, 4-butanediol ester glycol, poly-hexanodioic acid neopentyl glycol-1, 6-hexylene glycol esterdiol, poly-hexanodioic acid Viscotrol C esterdiol, poly-carbonic acid 1, 6-adipate diol, polyhutadiene dibasic alcohol, Polybutadiene-acrylonitrile copolymer glycols, Viscotrol C, modified soybean oil, one or more in epoxy resin.
Wherein in some embodiments, the number-average molecular weight scope of described polyvalent alcohol is between 400-6000.
Wherein in some embodiments, described non-hydrophilic chainextender is ethylene glycol, neopentyl glycol, BDO, 1,6-hexylene glycol, 2,3-butanediol, glycol ether, glycerine, TriMethylolPropane(TMP) or sorbyl alcohol.
Wherein in some embodiments, described hydrophilic chain extender is dimethylol propionic acid or dimethylolpropionic acid.
Wherein in some embodiments, the described chainextender containing active hydrogen is quadrol, butanediamine, hexanediamine, Diethylenetriaminee (DETA), triethylenetetramine, tetraethylenepentamine or N-(2-amino-ethyl)-aminoethane sulphonic acid sodium.
The present invention also provides the preparation method of the above-mentioned aqueous polyurethane emulsion for making water-proof strip.
Concrete technical scheme is as follows:
The preparation method of the above-mentioned aqueous polyurethane emulsion for making water-proof strip, comprises the steps:
Polyvalent alcohol is added reactor, under 100-120 ° of C, vacuum hydro-extraction 2h, then 70 ° of C are cooled the temperature to, add vulcabond, hydrophilic chain extender, non-hydrophilic chainextender and catalyzer, 2-4h is reacted under 80-95 ° of C, after NCO content reaches theoretical value, temperature of reaction is down to 30-40 ° of C, add neutralizing agent and carry out neutralization reaction, after sustained reaction 0.5-1h, add deionized water emulsion dispersion, finally add the chainextender containing active hydrogen, stirring reaction 0.5-1h, obtains described for making the aqueous polyurethane emulsion of water-proof strip.
Wherein in some embodiments, described catalyzer is organic tin catalyzer, and add-on is the 0-0.1% of aqueous polyurethane amount; Described neutralizing agent is triethylamine, and add-on is the 2.5-7% of aqueous polyurethane amount.
Beneficial effect of the present invention:
The invention provides and a kind ofly can be used in aqueous polyurethane emulsion preparing water-proof strip and preparation method thereof, the water-proof strip using this aqueous polyurethane emulsion to prepare has comparatively high-peeling strength, water proof wind proof effect is good, moisture transmission is high, this aqueous polyurethane emulsion synthetic method is simple, and easy handling, uses this aqueous polyurethane to prepare water-proof strip technique simple, energy consumption is low, non-environmental-pollution.
The invention provides the preparation method of the aqueous polyurethane emulsion that may be used for preparing water-proof strip.This aqueous polyurethane emulsion does not contain or only contains the volatile organic solvent of minute quantity, solid content 25-50%, and viscosity is less, obtained high performance water-proof strip after realizing high speed curing of coating, it is large that this water-proof strip has bonding intensity, and intensity is high, bonding part is soft, the features such as waterproofing and moisture-penetration performances is good.
Embodiment
A kind of aqueous polyurethane emulsion for making water-proof strip of the embodiment of the present invention, its raw material consists of the aqueous polyurethane and water that mass ratio is 0.5-0.9:1;
Described aqueous polyurethane raw material composition and weight percentage as follows:
The vulcabond of (a) 8-50wt%;
The polyvalent alcohol of (b) 25-80wt%;
The non-hydrophilic chainextender of (c) 0-10wt%;
The hydrophilic chain extender of (d) 0.5-15%;
The chainextender containing active hydrogen of (e) 0-8%; The summation of above-mentioned raw materials is 100%;
In the raw material of above-mentioned aqueous polyurethane, the mol ratio of isocyanate group and polyol hydroxyls is 2-5:1.
The preparation method of the above-mentioned aqueous polyurethane emulsion for making water-proof strip, comprises the steps:
Polyvalent alcohol is added reactor, under 100-120 ° of C, vacuum hydro-extraction 2h, then 70 ° of C are cooled the temperature to, add vulcabond, hydrophilic chain extender, non-hydrophilic chainextender and catalyzer, 2-4h is reacted under 80-95 ° of C, after NCO content reaches theoretical value, temperature of reaction is down to 30-40 ° of C, add neutralizing agent and carry out neutralization reaction, after sustained reaction 0.5-1h, count deionized water emulsion dispersion, finally add the chainextender containing active hydrogen, stirring reaction 0.5-1h, obtains described for making the aqueous polyurethane emulsion of water-proof strip.
Described catalyzer is organic tin catalyzer, and add-on is the 0-0.1% of aqueous polyurethane amount; Described neutralizing agent is triethylamine, and add-on is the 2.5-7% of aqueous polyurethane amount.
By the following examples the present invention is further elaborated.
Embodiment 1
A kind of aqueous polyurethane emulsion for making water-proof strip described in the present embodiment, its raw material consists of the aqueous polyurethane and water that mass ratio is 0.76:1;
Described aqueous polyurethane raw material composition and weight percentage as follows:
The vulcabond (tolylene diisocyanate and hexamethylene diisocyanate) of (a) 24.1wt%;
The polyvalent alcohol (poly-adipate glycol-glycol ether esterdiol and polytetrahydrofuran diol) of (b) 68.7wt%;
The non-hydrophilic chainextender (ethylene glycol) of (c) 3.1wt%;
The hydrophilic chain extender (dimethylol propionic acid) of (d) 4.1wt%;
The chainextender containing active hydrogen of (e) 0%; The summation of above-mentioned raw materials is 100%;
In above-mentioned raw materials, the mol ratio of isocyanate group and hydroxyl is 1.2.
The preparation method of the above-mentioned aqueous polyurethane emulsion for making water-proof strip, comprises the steps:
Add 150g in a kettle. and gather adipate glycol-glycol ether esterdiol (number-average molecular weight 2000), 50g polytetrahydrofuran diol (number-average molecular weight 2000) is under 100-120 ° of C, vaccum dewatering 2 hours, temperature is reduced to 60 ° of C subsequently, add 40g tolylene diisocyanate, 30g 1, hexamethylene-diisocyanate, 12g dimethylol propionic acid, 9g ethylene glycol, react 4 hours under 70 ° of C, in reaction process, add proper amount of acetone reduce viscosity, after NCO content reaches theoretical value, reduce temperature of reaction to 40 ° of about C, add 12g triethylamine and carry out neutralization reaction 1 hour, add 380g deionized water emulsion dispersion and remove acetone under reduced pressure in 1 hour, namely the aqueous polyurethane emulsion of the present embodiment for the preparation of water-proof strip is obtained, solid content: 37%.
The water-proof strip performance using this aqueous polyurethane emulsion to prepare is as follows: stripping strength (6N/cm), resistance to hydrostatic pressure (>20kPa).
Embodiment 2
A kind of aqueous polyurethane emulsion for making water-proof strip described in the present embodiment, its raw material consists of the aqueous polyurethane and water that mass ratio is 0.51:1;
Described aqueous polyurethane raw material composition and weight percentage as follows:
The vulcabond (isophorone diisocyanate) of (a) 22.5wt%;
The polyvalent alcohol (polybutylene glyool adipate and Polyoxyethylene glycol) of (b) 70.2wt%;
The non-hydrophilic chainextender (BDO) of (c) 2.0wt%;
The hydrophilic chain extender (dimethylol propionic acid) of (d) 3.9wt%;
The chainextender (quadrol) containing active hydrogen of (e) 1.4%; The summation of above-mentioned raw materials is 100%;
In above-mentioned raw materials, the mol ratio of isocyanate group and hydroxyl is 1.0.
The preparation method of the above-mentioned aqueous polyurethane emulsion for making water-proof strip, comprises the steps:
Add 200g polybutylene glyool adipate (number-average molecular weight 3000) in a kettle., 50g Polyoxyethylene glycol (number-average molecular weight 2000) is under 100-120 ° of C, vaccum dewatering 2 hours, temperature is reduced to 70 ° of C subsequently, add 80g isophorone diisocyanate, 14g dimethylol propionic acid and 7g 1, 4-butyleneglycol, add proper catalyst, described catalyzer is organic tin catalyzer (dibutyl tin laurate), add-on is 0.1% of aqueous polyurethane amount, react 4 hours under 80-95 ° of C, in reaction process, add proper amount of acetone reduce viscosity, after NCO content reaches theoretical value, reduce temperature of reaction to 40 ° of about C, add the neutralization of 9.5g triethylamine, continue reaction 1 hour, add 500g deionized water emulsion dispersion, add 5g quadrol, continue stirring 1 hour, remove acetone under reduced pressure, namely the aqueous polyurethane emulsion of the present embodiment for the preparation of water-proof strip is obtained, solid content: 42%.
The water-proof strip performance using this aqueous polyurethane emulsion to prepare is as follows: stripping strength (5N/cm), resistance to hydrostatic pressure (>20kPa).
Embodiment 3
A kind of aqueous polyurethane emulsion for making water-proof strip described in the present embodiment, its raw material consists of the aqueous polyurethane and water that mass ratio is 0.56:1;
Described aqueous polyurethane raw material composition and weight percentage as follows:
The vulcabond (tolylene diisocyanate and hexamethylene diisocyanate) of (a) 21.3wt%;
The polyvalent alcohol (polycaprolactone diols and PTMG dibasic alcohol) of (b) 71.1wt%;
The non-hydrophilic chainextender (BDO) of (c) 4.6wt%;
The hydrophilic chain extender (dimethylol propionic acid) of (d) 3.0wt%;
The chainextender containing active hydrogen of (e) 0%; The summation of above-mentioned raw materials is 100%;
In above-mentioned raw materials, the mol ratio of isocyanate group and hydroxyl is 1.1.
The preparation method of the above-mentioned aqueous polyurethane emulsion for making water-proof strip, comprises the steps:
Add 160g polycaprolactone diols (number-average molecular weight 2000) in a kettle., 40g PTMG dibasic alcohol (number average molecular weight 2000) is under 100-120 ° of C, vaccum dewatering 2 hours, temperature is reduced to 70 ° of C subsequently, add 40g tolylene diisocyanate, 20g 1, hexamethylene-diisocyanate, 8.4g dimethylol propionic acid and 13g 1, 4-butyleneglycol, add catalyzer, described catalyzer is organic tin catalyzer (dibutyl tin laurate), add-on is 0.1% of aqueous polyurethane amount, react 4 hours under 80-95 ° of C, in reaction process, add proper amount of acetone reduce viscosity, after NCO content reaches theoretical value, reduce temperature of reaction to 40 ° of about C, add the neutralization of 5.9g triethylamine, continue reaction 1 hour, add 500g deionized water emulsion dispersion 1 hour, remove acetone under reduced pressure, namely the aqueous polyurethane emulsion for the preparation of water-proof strip is obtained, solid content: 38%.
The water-proof strip performance using this aqueous polyurethane emulsion to prepare is as follows: stripping strength (4.5N/cm), resistance to hydrostatic pressure (>20kPa).
Embodiment 4
A kind of aqueous polyurethane emulsion for making water-proof strip described in the present embodiment, its raw material consists of the aqueous polyurethane and water that mass ratio is 0.58:1;
Described aqueous polyurethane raw material composition and weight percentage as follows:
The vulcabond (isophorone diisocyanate) of (a) 21.2wt%;
The polyvalent alcohol (poly-hexanodioic acid hexylene glycol ester dibasic alcohol, polyneopentyl glycol adipate dibasic alcohol and Polyoxyethylene glycol) of (b) 76.9wt%;
The non-hydrophilic chainextender (ethylene glycol) of (c) 1.9wt%;
The hydrophilic chain extender of (d) 0wt%;
The chainextender containing active hydrogen of (e) 0%; The summation of above-mentioned raw materials is 100%;
In above-mentioned raw materials, the mol ratio of isocyanate group and hydroxyl is 1.4.
The preparation method of the above-mentioned aqueous polyurethane emulsion for making water-proof strip, comprises the steps:
Add 80g in a kettle. and gather hexanodioic acid hexylene glycol ester dibasic alcohol (number-average molecular weight 2000), 80g polyneopentyl glycol adipate dibasic alcohol (number-average molecular weight 2000), 40g Polyoxyethylene glycol (number-average molecular weight 1000) is under 100-120 ° of C, vaccum dewatering 2 hours, temperature is reduced to 70 ° of C subsequently, add 55g isophorone diisocyanate, with 5g ethylene glycol, add catalyzer, described catalyzer is organic tin catalyzer (dibutyl tin laurate), add-on is 0.1% of aqueous polyurethane amount, react 4 hours under 80-95 ° of C, in reaction process, add proper amount of acetone reduce viscosity, after NCO content reaches theoretical value, reduce temperature of reaction to 40 ° of about C, add 450g deionized water emulsion dispersion 1 hour, remove acetone under reduced pressure, namely the aqueous polyurethane emulsion of the present embodiment for the preparation of water-proof strip is obtained, solid content: 37%.
The water-proof strip performance using this aqueous polyurethane emulsion to prepare is as follows: stripping strength (5.5N/cm), resistance to hydrostatic pressure (>20kPa).
Embodiment 5
A kind of aqueous polyurethane emulsion for making water-proof strip described in the present embodiment, its raw material consists of the aqueous polyurethane and water that mass ratio is 0.54:1;
Described aqueous polyurethane raw material composition and weight percentage as follows:
The vulcabond (ditan-4,4 '-vulcabond) of (a) 41.5wt%;
The polyvalent alcohol (poly-hexanodioic acid hexylene glycol ester dibasic alcohol, poly adipate succinic acid ester dibasic alcohol and polyoxypropyleneglycol) of (b) 46.1wt%;
The non-hydrophilic chainextender (BDO) of (c) 6.9wt%;
The hydrophilic chain extender (dimethylol propionic acid) of (d) 5.5wt%;
The chainextender containing active hydrogen of (e) 0%; The summation of above-mentioned raw materials is 100%;
In above-mentioned raw materials, the mol ratio of isocyanate group and hydroxyl is 1.1.
The preparation method of the above-mentioned aqueous polyurethane emulsion for making water-proof strip, comprises the steps:
Add 80g in a kettle. and gather hexanodioic acid hexylene glycol ester dibasic alcohol (number-average molecular weight 2000), 80g poly adipate succinic acid ester dibasic alcohol (number-average molecular weight 2000), 40g polyoxypropyleneglycol (number-average molecular weight 2000) is under 100-120 ° of C, vaccum dewatering 2 hours, temperature is reduced to 60 ° of C subsequently, add 180g ditan-4, 4 '-vulcabond, 24g dimethylol propionic acid, 30g 1, 4-butyleneglycol, react 4 hours under 60 ° of C, in reaction process, add proper amount of acetone reduce viscosity, after NCO content reaches theoretical value, reduce temperature of reaction to 40 ° of about C, add 18g triethylamine and carry out neutralization reaction 1 hour, add 800g deionized water emulsion dispersion 1 hour, remove acetone under reduced pressure, namely the aqueous polyurethane emulsion of the present embodiment for the preparation of water-proof strip is obtained, solid content: 35%.
The water-proof strip performance using this aqueous polyurethane emulsion to prepare is as follows: stripping strength (7N/cm), resistance to hydrostatic pressure (>20kPa).
Embodiment 6
A kind of aqueous polyurethane emulsion for making water-proof strip described in the present embodiment, its raw material consists of the aqueous polyurethane and water that mass ratio is 0.66:1;
Described aqueous polyurethane raw material composition and weight percentage as follows:
The vulcabond (isophorone diisocyanate) of (a) 19.0wt%;
The polyvalent alcohol (polybutylene glyool adipate) of (b) 76.1wt%;
The non-hydrophilic chainextender (BDO) of (c) 1.5wt%;
The hydrophilic chain extender (dimethylol propionic acid) of (d) 3.0wt%;
The chainextender (quadrol) containing active hydrogen of (e) 0.4%; The summation of above-mentioned raw materials is 100%;
In institute's above-mentioned raw materials, the mol ratio of isocyanate group and hydroxyl is 1.0.
The preparation method of the above-mentioned aqueous polyurethane emulsion for making water-proof strip, comprises the steps:
Add 200g polybutylene glyool adipate (number-average molecular weight 2000) in a kettle., under 100-120 ° of C, vaccum dewatering 2 hours, temperature is reduced to 70 ° of C subsequently, add 50g isophorone diisocyanate, 7.8g dimethylol propionic acid and 4g 1, 4-butyleneglycol, add catalyzer, described catalyzer is organic tin catalyzer (dibutyl tin laurate), add-on is 0.1% of aqueous polyurethane amount, react 4 hours under 80-95 ° of C, in reaction process, add proper amount of acetone reduce viscosity, after NCO content reaches theoretical value, reduce temperature of reaction to 40 ° of about C, add the neutralization of 5.9g triethylamine, continue reaction 1 hour, add 400g deionized water emulsion dispersion, add 1g quadrol, continue stirring 1 hour, remove acetone under reduced pressure, namely the aqueous polyurethane emulsion of the present embodiment for the preparation of water-proof strip is obtained, solid content: 40%.
The water-proof strip performance using this aqueous polyurethane emulsion to prepare is as follows: stripping strength (6N/cm), resistance to hydrostatic pressure (>20kPa).
Embodiment 7
A kind of aqueous polyurethane emulsion for making water-proof strip described in the present embodiment, its raw material consists of the aqueous polyurethane and water that mass ratio is 0.70:1;
Described aqueous polyurethane raw material composition and weight percentage as follows:
The vulcabond (dicyclohexyl methane diisocyanate and hexamethylene diisocyanate) of (a) 29.9wt%;
The polyvalent alcohol (poly-hexanodioic acid neopentyl glycol-1,6-hexylene glycol esterdiol and polytetrahydrofuran diol) of (b) 59.9wt%;
The non-hydrophilic chainextender (1,6-hexylene glycol) of (c) 5.4wt%;
The hydrophilic chain extender (dimethylol propionic acid) of (d) 4.8wt%;
The chainextender containing active hydrogen of (e) 0%; The summation of above-mentioned raw materials is 100%;
In above-mentioned raw materials, the mol ratio of isocyanate group and hydroxyl is 1.3.
The preparation method of the above-mentioned aqueous polyurethane emulsion for making water-proof strip, comprises the steps:
Add 180g in a kettle. and gather hexanodioic acid neopentyl glycol-1, 6-hexylene glycol esterdiol (number-average molecular weight 2000), 20g polytetrahydrofuran diol (number-average molecular weight 1000) is under 100-120 ° of C, vaccum dewatering 2 hours, temperature is reduced to 60 ° of C subsequently, add 60g dicyclohexyl methane diisocyanate, 40g 1, hexamethylene-diisocyanate, 16g dimethylol propionic acid, 18g 1, 6-hexylene glycol, react 4 hours under 80 ° of C, in reaction process, add proper amount of acetone reduce viscosity, after NCO content reaches theoretical value, reduce temperature of reaction to 40 ° of about C, add 12g triethylamine and carry out neutralization reaction 1 hour, add 450g deionized water emulsion dispersion and remove acetone under reduced pressure in 1 hour, namely the aqueous polyurethane emulsion of the present embodiment for the preparation of water-proof strip is obtained, solid content: 43%.
The water-proof strip performance using this aqueous polyurethane emulsion to prepare is as follows: stripping strength (6.8N/cm), resistance to hydrostatic pressure (>20kPa).
Embodiment 8
A kind of aqueous polyurethane emulsion for making water-proof strip described in the present embodiment, its raw material consists of the aqueous polyurethane and water that mass ratio is 0.73:1;
Described aqueous polyurethane raw material composition and weight percentage as follows:
The vulcabond (tolylene diisocyanate) of (a) 24.1wt%;
The polyvalent alcohol (polycaprolactone glycol and poly-adipate glycol-glycol ether esterdiol) of (b) 68.7wt%;
The non-hydrophilic chainextender (ethylene glycol) of (c) 3.1wt%;
The hydrophilic chain extender (dimethylol propionic acid) of (d) 4.1wt%;
The chainextender containing active hydrogen of (e) 0%; The summation of above-mentioned raw materials is 100%;
In above-mentioned raw materials, the mol ratio of isocyanate group and hydroxyl is 1.2.
The preparation method of the above-mentioned aqueous polyurethane emulsion for making water-proof strip, comprises the steps:
Add 110g polycaprolactone glycol (number-average molecular weight 2000) in a kettle., 90g gathers adipate glycol-glycol ether esterdiol (number-average molecular weight 2000) under 100-120 ° of C, vaccum dewatering 2 hours, temperature is reduced to 60 ° of C subsequently, add 70g tolylene diisocyanate, 12g dimethylol propionic acid, 9g ethylene glycol, react 4 hours under 70 ° of C, in reaction process, add proper amount of acetone reduce viscosity, after NCO content reaches theoretical value, reduce temperature of reaction to 40 ° of about C, add 12g triethylamine and carry out neutralization reaction 1 hour, add 400g deionized water emulsion dispersion and remove acetone under reduced pressure in 1 hour, namely the aqueous polyurethane emulsion for the preparation of water-proof strip is obtained, solid content: 36%.
The water-proof strip performance using this aqueous polyurethane emulsion to prepare is as follows: stripping strength (5.7N/cm), resistance to hydrostatic pressure (>20kPa).
Embodiment 9
A kind of aqueous polyurethane emulsion for making water-proof strip described in the present embodiment, its raw material consists of the aqueous polyurethane and water that mass ratio is 0.90:1;
Described aqueous polyurethane raw material composition and weight percentage as follows:
The vulcabond (dicyclohexyl methane diisocyanate) of (a) 36.5wt%;
The polyvalent alcohol (poly-hexanodioic acid hexylene glycol ester dibasic alcohol and polyoxypropyleneglycol) of (b) 55.8wt%;
The non-hydrophilic chainextender (BDO) of (c) 3.3wt%;
The hydrophilic chain extender (dimethylol propionic acid) of (d) 3.9wt%;
Chainextender (N-(2-the amino-ethyl)-aminoethane sulphonic acid sodium containing active hydrogen of (e) 0.4%); The summation of above-mentioned raw materials is 100%;
The mass ratio of described vulcabond and polyvalent alcohol is 1.5.
The preparation method of the above-mentioned aqueous polyurethane emulsion for making water-proof strip, comprises the steps:
Add 100g in a kettle. and gather hexanodioic acid hexylene glycol ester dibasic alcohol (number-average molecular weight 2000), 100g polyoxypropyleneglycol (number-average molecular weight 2000), under 100-120 ° of C, vaccum dewatering 2 hours, temperature is reduced to 60 ° of C subsequently, add 131g dicyclohexyl methane diisocyanate, 14g dimethylol propionic acid, 12g 1, 4-butyleneglycol, react 4 hours under 80 ° of C, in reaction process, add proper amount of acetone reduce viscosity, after NCO content reaches theoretical value, reduce temperature of reaction to 40 ° of about C, add 10.5g triethylamine and carry out neutralization reaction 1 hour, add 400g deionized water, 1.6g N-(2-amino-ethyl)-aminoethane sulphonic acid sodium, emulsion dispersion removes acetone under reduced pressure in 1 hour, namely the aqueous polyurethane emulsion for the preparation of water-proof strip is obtained, solid content: 48%.The water-proof strip performance using this aqueous polyurethane emulsion to prepare is as follows: stripping strength (6.6N/cm), resistance to hydrostatic pressure (>20kPa).
Peel strength test is with reference to GA350-2001
Resistance to hydrostatic pressure test is with reference to GB/T 4744-1997
Water-proof strip prepared by the aqueous polyurethane that table 1 embodiment of the present invention 1-9 prepares and water-proof strip Performance comparision prepared by commercial solvents type polyurethane
As shown in Table 1.The performance of Waterproof bar of the present invention has met or exceeded the performance of solvent-borne type water-proof strip, in view of Waterproof bar of the present invention does not use volatile solvent in process of production, environmentally friendly, is significant.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (9)
1. for making an aqueous polyurethane emulsion for water-proof strip, it is characterized in that, its raw material consists of the aqueous polyurethane and water that mass ratio is 0.5-0.9:1;
Described aqueous polyurethane raw material composition and weight percentage as follows:
The vulcabond of (a) 8-50wt%;
The polyvalent alcohol of (b) 25-80wt%;
The non-hydrophilic chainextender of (c) 0.5-10wt%;
The hydrophilic chain extender of (d) 0.5-15wt%;
The chainextender containing active hydrogen of (e) 0-8wt%; The summation of above-mentioned raw materials is 100%;
In the raw material of above-mentioned aqueous polyurethane, the mol ratio of isocyanate group NCO and hydroxyl OH is 2-5:1, wherein, the described chainextender containing active hydrogen is hexanediamine, Diethylenetriaminee (DETA), triethylenetetramine, tetraethylenepentamine or N-(2-amino-ethyl)-aminoethane sulphonic acid sodium, the preparation method of described aqueous polyurethane emulsion, comprises the steps:
Polyvalent alcohol is added reactor, at 100-120 DEG C, vacuum hydro-extraction 2h, then 70 DEG C are cooled the temperature to, add vulcabond, hydrophilic chain extender, non-hydrophilic chainextender and catalyzer, 2-4h is reacted at 60-95 DEG C, after NCO content reaches theoretical value, temperature of reaction is down to 30-40 DEG C, add neutralizing agent and carry out neutralization reaction, after sustained reaction 0.5-1h, add deionized water emulsion dispersion, finally add the chainextender containing active hydrogen, stirring reaction 0.5-1h, obtains described for making the aqueous polyurethane emulsion of water-proof strip.
2. the aqueous polyurethane emulsion for making water-proof strip according to claim 1, is characterized in that, the raw material of described aqueous polyurethane composition and weight percentage as follows:
The vulcabond of (a) 19-42wt%;
The polyvalent alcohol of (b) 45-80wt%;
The non-hydrophilic chainextender of (c) 1.5-7wt%;
The hydrophilic chain extender of (d) 0.5-5.5wt%;
The chainextender containing active hydrogen of (e) 0-1.5wt%; The summation of above-mentioned raw materials is 100%.
3. the aqueous polyurethane emulsion for making water-proof strip according to claim 1 and 2, it is characterized in that, described vulcabond is tolylene diisocyanate, ditan-4, one or more in 4 '-vulcabond, hexamethylene diisocyanate, dicyclohexyl methane diisocyanate, tetramethylxylylene diisocyanate, Methylcyclohexyl diisocyanate, isophorone diisocyanate.
4. the aqueous polyurethane emulsion for making water-proof strip according to claim 1 and 2, it is characterized in that, described polyvalent alcohol is polyoxypropyleneglycol, polyoxytrimethylene triol, polyoxytrimethylene-castor oil polyhydric alcohol, polytetrahydrofuran diol, Polyoxyethylene glycol, polycaprolactone diols, PCDL, polyethylene glycol adipate glycol, poly-adipate glycol-propylene glycol ester glycol, poly-hexanodioic acid glycol ether esterdiol, poly-adipate glycol-glycol ether esterdiol, poly-hexanodioic acid-1, 4-butanediol ester glycol, poly-adipate glycol-1, 4-butanediol ester glycol, poly-hexanodioic acid neopentyl glycol-1, 6-hexylene glycol esterdiol, poly-hexanodioic acid Viscotrol C esterdiol, poly-carbonic acid 1, 6-adipate diol, polyhutadiene dibasic alcohol, Polybutadiene-acrylonitrile copolymer glycols, Viscotrol C, modified soybean oil, one or more in epoxy resin.
5. the aqueous polyurethane emulsion for making water-proof strip according to claim 4, is characterized in that, the number-average molecular weight scope of described polyvalent alcohol is between 400-6000.
6. the aqueous polyurethane emulsion for making water-proof strip according to claim 1 and 2, it is characterized in that, described non-hydrophilic chainextender is ethylene glycol, neopentyl glycol, BDO, 1,6-hexylene glycol, 2,3-butanediol, glycol ether, glycerine or TriMethylolPropane(TMP) or sorbyl alcohol.
7. the aqueous polyurethane emulsion for making water-proof strip according to claim 1 and 2, is characterized in that, described hydrophilic chain extender is dimethylol propionic acid or dimethylolpropionic acid.
8. the preparation method of the aqueous polyurethane emulsion for making water-proof strip described in any one of claim 1-7, is characterized in that, comprise the steps:
Polyvalent alcohol is added reactor, at 100-120 DEG C, vacuum hydro-extraction 2h, then 70 DEG C are cooled the temperature to, add vulcabond, hydrophilic chain extender, non-hydrophilic chainextender and catalyzer, 2-4h is reacted at 60-95 DEG C, after NCO content reaches theoretical value, temperature of reaction is down to 30-40 DEG C, add neutralizing agent and carry out neutralization reaction, after sustained reaction 0.5-1h, add deionized water emulsion dispersion, finally add the chainextender containing active hydrogen, stirring reaction 0.5-1h, obtains described for making the aqueous polyurethane emulsion of water-proof strip.
9. the preparation method of the aqueous polyurethane emulsion for making water-proof strip according to claim 8, is characterized in that, described catalyzer is organic tin catalyzer, and add-on is the 0-0.1% of aqueous polyurethane amount; Described neutralizing agent is triethylamine, and add-on is the 2.5-7% of aqueous polyurethane amount.
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| CN104311781A (en) * | 2014-10-29 | 2015-01-28 | 东南大学 | High-moisture-permeability aqueous polyurethane material and preparation method thereof |
| JP6285046B2 (en) * | 2014-11-04 | 2018-02-28 | 第一工業製薬株式会社 | Water-based polyurethane resin composition |
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| CN105801810B (en) * | 2016-05-18 | 2018-08-31 | 长春工业大学 | A kind of preparation method of bloom high water-permeability polyurethane resin |
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| WO2021084953A1 (en) * | 2019-10-28 | 2021-05-06 | Dic株式会社 | Foam sheet and synthetic leather |
| CN110818873B (en) * | 2019-11-20 | 2022-07-12 | 万华化学集团股份有限公司 | Waterborne polyurethane resin and preparation method and application thereof |
| CN111793352B (en) * | 2020-07-07 | 2022-10-04 | 惠州大亚湾达志精细化工有限公司 | Waterborne polyurethane powder adhesive, elastic material and preparation method thereof |
| CN114075322A (en) * | 2020-08-18 | 2022-02-22 | 上海名邦橡胶制品有限公司 | Waterborne polyurethane resin emulsion and preparation method thereof |
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