CN109456459A - A method of raising aqueous polyurethane is water-fast or solvent resistance - Google Patents

A method of raising aqueous polyurethane is water-fast or solvent resistance Download PDF

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CN109456459A
CN109456459A CN201811160030.3A CN201811160030A CN109456459A CN 109456459 A CN109456459 A CN 109456459A CN 201811160030 A CN201811160030 A CN 201811160030A CN 109456459 A CN109456459 A CN 109456459A
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water
aqueous polyurethane
fast
solvent resistance
reaction
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CN109456459B (en
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王军威
李晓云
亢茂青
赵雨花
冯月兰
李其峰
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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Abstract

A kind of water-fast or solvent resistance aqueous polyurethane preparation method is that cyclic carbonate ester and aminated compounds are carried out aminolysis alcoholamine chain extender；1,4-butanediol and solvent being added after polymer polyatomic alcohol, isocyanate compound, the hydrophilic agent prepolymerization reaction containing carboxyl, the reaction was continued, and salt forming agent is added into above-mentioned reaction product after reaction and reacts to obtain performed polymer；Chain extension after the chain extender that preparation is added after performed polymer plus water emulsification is carried out, obtains water-fast or solvent resistant aqueous polyurethane emulsion, pours into air drying in mold, aqueous polyurethane is made in evaporation solvent.The present invention has easy to operate, at low cost, water resistance and the good advantage of solvent resistance.

Description

A method of raising aqueous polyurethane is water-fast or solvent resistance
Technical field
The present invention relates to a kind of raising, aqueous polyurethane is water-fast or the method for solvent resistance, and in particular to arrives a kind of titanium dioxide Carbon sets out, and aqueous polyurethane is water-fast or the method for solvent resistance to improve for the aqueous polyurethane chain extender of preparation.
Technical background
Polyurethane has the characteristics that intensity is high, elasticity is good, high abrasion resistance as a kind of common high molecular material, Various fields have relatively broad application, but the polyurethane of currently used better performances is mostly solvent borne polyurethane, A large amount of solvent is not only consumed in process of production, can also be caused damages to environment and personal safety.As people's environmental protection is anticipated The use of the enhancing of knowledge, solvent borne polyurethane is increasingly restricted；Corresponding aqueous polyurethane product in the synthesis process with Water reduces solvent volatilization pollution environment as solvent, has the advantages that environment friendly and pollution-free, therefore its R and D at home and abroad Further extensively.
However aqueous polyurethane is using water as decentralized medium, and contains a large amount of hydrophilic radical in structure, it is dry after shape At polyurethane coating film meet water and be easy swelling, therefore the water resistance of aqueous polyurethane glue film can be made to decline, to limit Water-base polyurethane material applications in various fields.
CN107141438A discloses a kind of preparation method of the aqueous polyurethane emulsion of enhanced water resistance, with polymerized thylene carbonate third Ester polyol, aromatic diisocyanate, antioxidant and the chain extender containing carboxyl are reacted in a solvent for raw material, and And the silane coupling agent containing epoxy group, the water made is added in the stage that the reaction product and salt forming agent carry out neutralization reaction Property polyaminoester emulsion have good water resistance.CN102838724A discloses a kind of preparation side of strong water resistance aqueous polyurethane Method carries out the modification of enhancing water resistance using acrylate to aqueous polyurethane emulsion.First with TDI, PEG3000, BDO, DMPA is Material synthesis performed polymer, and HEA is then added and blocks to the end-NCO of performed polymer, is then added in triethylamine progress Salt is generated with reaction, TPGDA is eventually adding and water is emulsified.Made by the way that suitable initiator azodiisobutyronitrile is added TPGDA polymerize to obtain the lotion of acrylate Yu aqueous polyurethane modification by copolymerization with the double bond of HEA opening.CN105237727A is public A kind of enhanced water resistance water soluble polyurethane resin and preparation method thereof is opened, by the way that terephthalic anhydride polyester binary is pure and mild poly- Adipic acid -1,4-CHDM esterdiol heating melting, heat preservation, then vacuum dehydration obtains material a；Then by tetramethyl Benzene dimethylene diisocyanate is added in material a, heats up, and 1,5-PD, melamine-formaldehyde is added in heat preservation after cooling Resin and N-Methyl pyrrolidone add cobalt octoate, and heating, heat preservation obtains material b；After then material b is cooled down, then it is added dropwise The mixed solution of the diethanol amine of propyl containing N- and bis- (2- ethoxy) aniline, heating, heat preservation obtain material c；It is added dropwise into material c Vacuum distillation obtains enhanced water resistance water soluble polyurethane resin after propionic acid is neutralized.Invention additionally discloses a kind of enhanced water resistance water Soluble polyurethane resin.The present invention has excellent water resistance and hardness, and method is stablized, easily controllable.
Zhu Wanzhang improves the water resistance of aqueous polyurethane by the degree of cross linking before raising emulsification and when forming a film, with three hydroxyls Methylpropane (TMP) makees precondensation stage cross-linking monomer, is by by Diacetone Acrylamide in the crosslinking in final emulsion stage (DAAM) be introduced into the macromolecular that vinyl monomer aggregates into, film forming when with moisture release further with two acyl of adipic acid Hydrazine (ADH) occurs chemical reaction and is crosslinked, and prepares multiple cross-linked PUA aqueous dispersion, solid content 33%, water logging is not Whiting, storage stability was at 1 year or more.
Complicated operation when solving the problems, such as that Water-resistance of Waterborne Polyurethane is bad for above-mentioned background technique, increases production Difficulty；And when preparing aqueous polyurethane, required raw material is more, higher cost；In addition, some method of modifying are resistance to for improving Aqueous effect is limited, and water-fast efficiency is lower.Therefore, how the water resistance of the raising aqueous polyurethane of high-efficient simple becomes ability Field technique personnel's urgent problem to be solved.
Summary of the invention
It is of the invention for deficiency of the water-base polyurethane material in terms of water-fast or solvent resistant based on the above-mentioned prior art Purpose is to provide a kind of easy to operate, at low cost, water resistance and the good water-fast or solvent resistance aqueous polyurethane of solvent resistance Preparation method.
The present invention provides a kind of water-fast or solvent resistance aqueous polyurethane preparation methods, comprising the following steps:
(1) cyclic carbonate ester and aminated compounds are subjected to aminolysis reaction and alcoholamine chain extender is made；
(2) 1,4- fourth will be added after polymer polyatomic alcohol, isocyanate compound, the hydrophilic agent prepolymerization reaction containing carboxyl The reaction was continued for glycol and solvent；
(3) salt forming agent is added into above-mentioned reaction product after reaction to be reacted, obtains performed polymer；
(4) chain extension after adding the chain extender that preparation is added after water emulsification to carry out performed polymer, obtains the aqueous poly- ammonia of water-fast/solvent Ester；
(5) gained aqueous polyurethane emulsion is poured into Teflon mould after air drying 20-48h under infrared lamp It toasts or is placed in baking oven and evaporate solvent, aqueous polyurethane is made.
Cyclic carbonate compound in the aminolysis reaction of step (1) as described above: diamine compounds molar ratio is 1: 2.5-10, temperature are 50-120 DEG C, reaction time 3-15h.
If the amine class compound in above-mentioned steps (1) includes hexamethylene diamine, propane diamine, butanediamine, ethylenediamine, pentanediamine Deng.
Cyclic carbonate ester in step (1) as described above is prepared by the following method:
By CO2Cycloaddition reaction is carried out with epoxide and obtains cyclic carbonate compound, and cycloaddition reaction temperature is 90- 150 DEG C, time 25-45h, pressure 0.5-4MPa, catalyst charge is the 1-20% of epoxide weight；
Epoxide includes ethylene oxide, propylene oxide, ethylene glycol diglycidylether, butanediol 2-glycidyl One of ether, hexanediol diglycidyl ether, neopentylglycol diglycidyl ether, diethylene glycol diglycidyl ether etc. Or it is several.
Catalyst as described above is base exchange resin D296.
If the polymer polyatomic alcohol of above-mentioned steps (2) carries out pre-treatment, pre-treating method is to take out very at 100-140 DEG C Sky dehydration 2-4h.
As the dosage of above-mentioned steps (2) polymerization ofathe reactants object polyalcohol and isocyanates be NCO/OH ratio 1.2-1.6 it Between, wherein NCO/OH refers to the ratio between isocyanate equivalent number and equivalents of hydroxyl of synthetic prepolymer before the dispersing, containing carboxyl parent The dosage of aqua is the 3.0%-5.0% of all total mass of raw materiales, and the dosage of small molecule dihydric alcohol is between 2.0%-3.5%； Prepolymerization reaction temperature is 70-95 DEG C, time 2-5h, and the reaction temperature that small molecule dihydric alcohol is added is 30-60 DEG C, the reaction time For 1-3h.
Polymer polyatomic alcohol in step (2) includes one or more of polyetherdiol, polyester-diol, specifically are as follows: Polyester-diol includes polyadipate esters (such as polyethylene glycol adipate, poly adipate succinic acid ester, polyadipate ethylene glycol- Propylene glycol ester, polyadipate ethylene glycol-butanediol ester, polyadipate hexylene glycol ester, in polyadipate ethylene glycol-neopentyl glycol ester It is one or more of), poly-epsilon-caprolactone glycol, polycarbonate glycol, poly (propylene carbonate) glycol；Polyetherdiol is polytetramethylene Ether glycol, polyoxypropyleneglycol, Polyoxyethylene glycol, polybutadiene polyol etc..Polymer polyatomic alcohol used can be Single variety is also possible to the polyalcohol mixing of several different cultivars and different molecular weight, preferred molecular weight range 1000- 2000 polymer polyatomic alcohol.
Diisocyanate cpd in above-mentioned steps (2) is aromatic diisocyanate compounds, two isocyanide of aliphatic One or more of ester compound or the diisocyanate cpd of modification.Aromatic includes toluene di-isocyanate(TDI) (TDI), methyl diphenylene diisocyanate (MDI) etc.；Aliphatic includes 1, hexamethylene-diisocyanate (HDI), dimethyl connection Phenylene diisocyanate (TODI), isophorone diisocyanate (IPDI), 4,4'-Dicyclohexylmethane diisocyanate (H12MDI) etc..Preferably toluene di-isocyanate(TDI) (TDI), isophorone diisocyanate (IPDI).
The hydrophilic agent containing carboxyl in above-mentioned steps (2) includes 2,2- dihydromethyl propionic acid, dihydroxy half ester and diamino One or more of yl benzoic acid.
Solvent in above-mentioned steps (2) includes acetone, n,N-Dimethylformamide or N-Methyl pyrrolidone etc., solvent Additional amount is performed polymer: solvent quality ratio is 1:0.8-1.6.
The dosage of the salt forming agent of above-mentioned steps (3) is carboxyl: the ratio between amount of salt forming agent substance is 1:1, reaction temperature 10- 40 DEG C, reaction time 5-30min.
Salt forming agent in step (3) includes one of triethylamine, tripropyl amine (TPA), tri-n-butylamine, sodium hydroxide and ammonium hydroxide or several Kind.
The dosage of the chain extender of above-mentioned steps (4) is calculated between 0.9-1.0 by chain extension coefficient, and chain extension coefficient refers to pre-polymerization In body in the amount of the substance of isocyanate groups and chain extender amido the ratio between the amount of substance, emulsifying temperature is room temperature, emulsification speed Degree is 1000-5000r/min, emulsification times 10-40min；Chain extension temperature is 10-50 DEG C afterwards, time 20-50min.
Gained polyurethane material is tested according to following standards.
Performance test standard:
(1) water-fast, solvent resistance test
The polyurethane material prepared is soaked in deionized water and is placed simultaneously at 25 DEG C in solvent toluene accordingly Sample quality situation of change is weighed, until the swellbility of sample is calculated as follows when constant weight:
S indicates swellbility, m0Indicate initial mass, m1It is the weight for reaching constant weight after being swollen.
(2) mechanical performance
It is tested according to the sample that the regulation in standard GB1039-92 prepares dumbbell shape, tensile strength executes GB/ T528-1998 standard, elongation at break execute GB528-82 standard, test condition are as follows: and 25 DEG C of room temperature, humidity 55%.
(3) mechanical performance conservation rate
It prepares according to the regulation in standard GB1039-92 and sample is immersed in water and selected solvent after sample, is spaced It takes out to dry after a certain period of time and its mechanical performance is tested by respective standard.
(4) heat resistance
Heat resistance is measured using thermogravimetry (TGA): the sample of 5-7mg being measured in nitrogen with thermogravimetric analyzer, is heated up Speed is 10 DEG C/min, and temperature elevating range is 30-600 DEG C.
One kind of the present invention is water-fast/preparation method of solvent aqueous polyurethane, the advantage is that:
1, it is set out using carbon dioxide as raw material and prepares chain extender, the effective chemistry for realizing carbon dioxide is fixed, for sky The reduction of carbon dioxide content has certain help in gas；
2, preparation process is simple, easy to operate, and it is identical to prepare the technique of aqueous polyurethane with tradition；
3, gained aqueous polyurethane it is water-fast/solvent borne significantly improves, swellbility in water is less than 13.0%, in solvent first There was only 34.6-40.3% in benzene, and tensile strength performance conservation rate can reach 87.3% in water, stretch in solvent toluene strong Property retention rate is spent up to 87.9%；The better mechanical property of the aqueous polyurethane, tensile strength between 24.8-31.5MPa, Thermal stability is basically unchanged compared with prior art, originates thermal decomposition temperature at 200 DEG C or so.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments to the present invention It is further elaborated.It should be appreciated that described herein, specific examples are only used to explain the present invention, is not used to limit The fixed present invention.
Embodiment 1
1) by mass fraction be 100 parts 1,4- fourth diglycidyl ether and mass fraction be the exchange of 15 parts of catalyst alkalinity Resin D296 is added in autoclave, is passed through CO after being warming up to 140 DEG C2, pressure is maintained at 2MPa, filters after reacting 30h Catalyst obtains cyclic carbonate compound.The cyclic carbonate compound for weighing 100 parts of synthesis later, is added 82.8 parts of second two Amine is heated to 100 DEG C of insulation reaction 6h, vacuumizes vacuum distillation 5h after reaction at 90 DEG C and removes excessive ethylenediamine, obtains alcohol Amine chainextender.
2) poly- (adipate glycol propylene glycol) polyalcohol (M for being 10 parts by mass fractionn=2000) reactor is added In, 140 DEG C are warming up to, dehydration 2h is vacuumized；After being cooled to 50 DEG C later, 1.5 parts of 2,2- hydroxymethyl propionic acids and 4.61 parts are added Isophorone diisocyanate compound, then it is warming up to 75 DEG C of reaction 2h；It is cooled to 50 DEG C of additions, 0.6 part of 1,4- after reaction Butanediol and 8.53 parts of solvent acetone back flow reaction 3h.
3) reaction system is cooled to 30 DEG C, 1.11 parts and 8.53 parts acetone of salt forming agent triethylamine is added into reaction product Reaction 10min obtains Waterborne Polyurethane Prepolymer；
4) 37 parts of distilled water are added in hydrotropism's base polyurethane prepolymer for use as to emulsify at normal temperature, revolving speed 4000r/min, Emulsify 20min.The expanding chain pharmaceutical solution that 10.21 parts of mass fractions are 18% is finally added dropwise into polyaminoester emulsion at 20 DEG C to continue Stir chain extension after 30min is carried out.
5) it is toasted under infrared lamp after gained aqueous polyurethane emulsion being poured into Teflon mould air drying for 24 hours Solvent is evaporated, it is spare that aqueous polyurethane elastic film is made.
Embodiment 2
1) by mass fraction be 100 parts diethylene glycol diglycidyl ether and mass fraction be 5 parts of catalyst alkali Property exchanger resin D296 is added in autoclave, is passed through CO after being warming up to 140 DEG C2, pressure is maintained at 4MPa, reacts 45h Filtration catalytic agent afterwards obtains cyclic carbonate compound.The cyclic carbonate compound for weighing 100 parts of synthesis later, is added 120.1 Part hexamethylene diamine is heated to 70 DEG C of insulation reaction 10h, vacuumized at 200 DEG C after reaction vacuum distillation 5h remove it is excessive oneself two Amine obtains alcoholamine chain extender.
2) polycarbonate glycol (M for being 10 parts by mass fractionn=2000) it is added in reactor, is warming up to 100 DEG C, take out Vacuum dehydration 4h；After being cooled to 50 DEG C later, 0.75 part of 2,2- hydroxymethyl propionic acid and 3.04 parts of hexa-methylene diisocyanates are added Ester compounds, then it is warming up to 90 DEG C of reaction 2h；It is cooled to 60 DEG C of 0.24 part of 1,4- butanediols of addition and 10.52 parts after reaction Solvent N-methyl pyrilidone back flow reaction 2h.
3) reaction system is cooled to 25 DEG C, 1.04 parts and 10.52 parts of salt forming agent tri-n-butylamine of addition is molten into reaction product Agent N-Methyl pyrrolidone reaction 10min obtains Waterborne Polyurethane Prepolymer；
4) 42 parts of distilled water are added in hydrotropism's base polyurethane prepolymer for use as to emulsify at normal temperature, revolving speed 5000r/min, Emulsify 35min.The expanding chain pharmaceutical solution that 10.12 parts of mass fractions are 18% is finally added dropwise into polyaminoester emulsion persistently to stir Chain extension after 35min is carried out.
5) gained aqueous polyurethane emulsion is poured into Teflon mould and is toasted under infrared lamp after air drying 30h Solvent is evaporated, it is spare that aqueous polyurethane elastic film is made.
Embodiment 3
1) by mass fraction be 100 parts ethylene glycol diglycidylether and mass fraction be the exchange of 15 parts of catalyst alkalinity Resin D296 is added in autoclave, is passed through CO after being warming up to 130 DEG C2, pressure is maintained at 2MPa, filters after reacting 30h Catalyst obtains cyclic carbonate compound.Later weigh 100 parts synthesis cyclic carbonate compounds, be added 52.4 parts oneself two Amine is heated to 70 DEG C of insulation reaction 10h, vacuumizes vacuum distillation 5h after reaction at 90 DEG C and removes excessive hexamethylene diamine, obtains alcohol Amine chainextender.
2) polycarbonate glycol (M for being 10 parts by mass fractionn=1000) it is added in reactor, is warming up to 120 DEG C, take out Vacuum dehydration 3h；After being cooled to 50 DEG C later, 1 part of 2,2- hydroxymethyl propionic acid and 2.26 parts of methyl diphenylene diisocyanates are added With 2.01 parts of isophorone diisocyanate, then it is warming up to 90 DEG C of reaction 2h；It is cooled to 60 DEG C after reaction and is added 0.3 part 1, 4- butanediol and 6.70 parts of solvent acetone back flow reaction 2h.
3) reaction system is cooled to 25 DEG C, 1.39 parts and 6.70 parts acetone of salt forming agent tri-n-butylamine is added into reaction product Reaction 25min obtains Waterborne Polyurethane Prepolymer；
4) 37 parts of distilled water are added in hydrotropism's base polyurethane prepolymer for use as to emulsify at normal temperature, revolving speed 3000r/min, Emulsify 30min.The expanding chain pharmaceutical solution that 19.37 parts of mass fractions are 18% is finally added dropwise into polyaminoester emulsion persistently to stir Chain extension after 30min is carried out.
5) it is toasted under infrared lamp after gained aqueous polyurethane emulsion being poured into Teflon mould air drying for 24 hours Solvent is evaporated, it is spare that aqueous polyurethane elastic film is made.
Embodiment 4
1) by mass fraction be 50 parts ethylene glycol diglycidylether and mass fraction be 50 parts 1,4- butanediol two Glycidol ether and mass fraction are that 15 parts of catalyst base exchange resin D296 are added in autoclave, are warming up to 130 CO is passed through after DEG C2, pressure is maintained at 2MPa, reacts filtration catalytic agent after 30h, obtain cyclic carbonate compound.100 are weighed later The cyclic carbonate compound of part synthesis, is added 82.8 parts of ethylenediamines and is heated to 100 DEG C of insulation reaction 6h, after reaction at 90 DEG C It vacuumizes vacuum distillation 5h and removes excessive ethylenediamine, obtain alcoholamine chain extender.
2) polycaprolactone glycol (M for being 10 parts by mass fractionn=1000) it is added in reactor, is warming up to 120 DEG C, take out Vacuum dehydration 3h；After being cooled to 50 DEG C later, 1 part of 2,2- hydroxymethyl propionic acid and 2.84 parts of toluene di-isocyanate(TDI)s and 0.40 are added Part isophorone diisocyanate, then it is warming up to 90 DEG C of reaction 2h；It is cooled to 60 DEG C of additions, 0.3 part of 1,4- fourth two after reaction Alcohol and 9.67 parts of solvent acetone back flow reaction 2h.
3) reaction system is cooled to 25 DEG C, 1.39 parts and 9.67 parts acetone of salt forming agent tri-n-butylamine is added into reaction product Reaction 25min obtains Waterborne Polyurethane Prepolymer；
4) 37 parts of distilled water are added in hydrotropism's base polyurethane prepolymer for use as to emulsify at normal temperature, revolving speed 3000r/min, Emulsify 30min.The expanding chain pharmaceutical solution that 18.35 parts of mass fractions are 18% is finally added dropwise into polyaminoester emulsion persistently to stir Chain extension after 30min is carried out.
5) it is toasted under infrared lamp after gained aqueous polyurethane emulsion being poured into Teflon mould air drying for 24 hours Solvent is evaporated, it is spare that aqueous polyurethane elastic film is made.
Embodiment 5
1) by mass fraction be 50 parts ethylene glycol diglycidylether and mass fraction be 50 parts diglycol Diglycidyl ether and mass fraction are that 15 parts of catalyst base exchange resin D296 are added in autoclave, are warming up to CO is passed through after 130 DEG C2, pressure is maintained at 2MPa, reacts filtration catalytic agent after 30h, obtain cyclic carbonate compound.It weighs later The cyclic carbonate compound of 100 parts of synthesis, is added 45.4 parts of ethylenediamines and is heated to 100 DEG C of insulation reaction 6h, obtains hydramine expansion Chain agent vacuumizes vacuum distillation 5h at 90 DEG C and removes excessive ethylenediamine, obtains alcoholamine chain extender after reaction.
2) polycarbonate glycol (M for being 10 parts by mass fractionn=1000) it is added in reactor, is warming up to 130 DEG C, take out Vacuum dehydration 2.5h；After being cooled to 50 DEG C later, 1 part of 2,2- hydroxymethyl propionic acid and 7.23 parts of toluene di-isocyanate(TDI)s are added, then It is warming up to 90 DEG C of reaction 2h；It is cooled to 60 DEG C of 0.6 part of 1,4- butanediols of addition and 13.01 parts of solvent acetone reflux after reaction React 2h.
3) reaction system is cooled to 25 DEG C, 0.57 part and 10.77 part third of salt forming agent triethylamine is added into reaction product Reactive ketone 25min obtains Waterborne Polyurethane Prepolymer；
4) 37 parts of distilled water are added in hydrotropism's base polyurethane prepolymer for use as to emulsify at normal temperature, revolving speed 3000r/min, Emulsify 30min.The expanding chain pharmaceutical solution that 21.41 parts of mass fractions are 18% is finally added dropwise into polyaminoester emulsion persistently to stir Chain extension after 30min is carried out.
5) it is toasted under infrared lamp after gained aqueous polyurethane emulsion being poured into Teflon mould air drying for 24 hours Solvent is evaporated, it is spare that aqueous polyurethane elastic film is made.
Embodiment 6
1) by mass fraction be 20 parts propylene oxide and mass fraction be 80 parts 1,4- butanediol diglycidyl ether And mass fraction is that 15 parts of catalyst base exchange resin D296 are added in autoclave, is passed through after being warming up to 130 DEG C CO2, pressure is maintained at 2MPa, reacts filtration catalytic agent after 30h, obtain cyclic carbonate compound.100 parts of synthesis are weighed later Cyclic carbonate compound is added 74.5 parts of ethylenediamines and is heated to 100 DEG C of insulation reaction 6h, vacuumizes and subtract at 90 DEG C after reaction Pressure distillation 5h removes excessive ethylenediamine, obtains alcoholamine chain extender.
2) the poly (propylene carbonate) glycol (M for being 2 parts by mass fractionn=1000) it is 8 parts with mass fraction and gathers in oneself Ester (Mn=1000) it is added in reactor, is warming up to 130 DEG C, vacuumize dehydration 2.5h；After being cooled to 50 DEG C later, it is added 1.1 Part diaminobenzoic acid and 7.23 parts of toluene di-isocyanate(TDI)s, then it is warming up to 90 DEG C of reaction 2h；It is cooled to 60 DEG C after reaction 0.6 part of 1,4- butanediol and 13.01 parts of solvent acetone back flow reaction 2h are added.
3) reaction system is cooled to 25 DEG C, 0.57 part and 10.77 part third of salt forming agent triethylamine is added into reaction product Reactive ketone 25min obtains Waterborne Polyurethane Prepolymer；
4) 37 parts of distilled water are added in hydrotropism's base polyurethane prepolymer for use as to emulsify at normal temperature, revolving speed 3000r/min, Emulsify 30min.The expanding chain pharmaceutical solution that 21.41 parts of mass fractions are 18% is finally added dropwise into polyaminoester emulsion persistently to stir Chain extension after 30min is carried out.
5) it is toasted under infrared lamp after gained aqueous polyurethane emulsion being poured into Teflon mould air drying for 24 hours Solvent is evaporated, it is spare that aqueous polyurethane elastic film is made.
Embodiment 7
1) by mass fraction be 50 parts ethylene glycol diglycidylether and mass fraction be 50 parts diglycol Diglycidyl ether and mass fraction are that 15 parts of catalyst base exchange resin D296 are added in autoclave, are warming up to CO is passed through after 140 DEG C2, pressure is maintained at 1.5MPa, reacts filtration catalytic agent after 30h, obtain cyclic carbonate compound.Claim later Measure 100 parts synthesis cyclic carbonate compounds, 91.8 parts of ethylenediamines are added and are heated to 100 DEG C of insulation reaction 6h, after reaction Vacuum distillation 5h is vacuumized at 90 DEG C and removes excessive ethylenediamine, obtains alcoholamine chain extender.
2) polyoxypropyleneglycol (M for being 10 parts by mass fractionn=1000) it is added in reactor, is warming up to 130 DEG C, Vacuumize dehydration 2.5h；After being cooled to 50 DEG C later, 1 part of 2,2- hydroxymethyl propionic acid and 7.23 parts of toluene di-isocyanate(TDI)s are added, It is warming up to 90 DEG C of reaction 2h again；It is cooled to 60 DEG C of 0.6 part of 1,4- butanediols of addition after reaction and 13.01 parts of solvent acetones are returned Stream reaction 2h.
3) reaction system is cooled to 25 DEG C, 0.57 part and 10.77 part third of salt forming agent triethylamine is added into reaction product Reactive ketone 25min obtains Waterborne Polyurethane Prepolymer；
4) 37 parts of distilled water are added in hydrotropism's base polyurethane prepolymer for use as to emulsify at normal temperature, revolving speed 3000r/min, Emulsify 30min.The expanding chain pharmaceutical solution that 21.41 parts of mass fractions are 18% is finally added dropwise into polyaminoester emulsion persistently to stir Chain extension after 30min is carried out.
5) it is toasted under infrared lamp after gained aqueous polyurethane emulsion being poured into Teflon mould air drying for 24 hours Solvent is evaporated, it is spare that aqueous polyurethane elastic film is made.
Embodiment 8
1) by mass fraction be 30 parts diethylene glycol diglycidyl ether and mass fraction be 70 parts 1,4- fourth Hexanediol diglycidyl ether and mass fraction are that 15 parts of catalyst base exchange resin D296 are added in autoclave, are heated up CO is passed through after to 130 DEG C2, pressure is maintained at 2MPa, reacts filtration catalytic agent after 40h, obtain cyclic carbonate compound.Claim later Measure 100 parts synthesis cyclic carbonate compounds, 144.0 parts of propane diamine are added and are heated to 100 DEG C of insulation reaction 6h, after reaction Vacuum distillation 5h is vacuumized at 90 DEG C and removes excessive propane diamine, obtains alcoholamine chain extender.
2) Polyoxyethylene glycol (M for being 1 part by mass fractionn=1000) and 9 parts of polycarbonate glycol (Mn= 1000) it is added in reactor, is warming up to 130 DEG C, vacuumize dehydration 2.5h；After being cooled to 50 DEG C later, 1 part of 2,2- hydroxyl first is added Base propionic acid and 2.84 parts of toluene di-isocyanate(TDI)s and 0.48 part of dimethyl diphenyl diisocyanate, then it is warming up to 90 DEG C of reaction 2h； It is cooled to 60 DEG C of 0.6 part of 1,4- butanediols of addition and 13.01 parts of solvent acetone back flow reaction 2h after reaction.
3) reaction system is cooled to 25 DEG C, 0.57 part and 10.77 part third of salt forming agent triethylamine is added into reaction product Reactive ketone 25min obtains Waterborne Polyurethane Prepolymer；
4) 37 parts of distilled water are added in hydrotropism's base polyurethane prepolymer for use as to emulsify at normal temperature, revolving speed 3000r/min, Emulsify 30min.The expanding chain pharmaceutical solution that 21.41 parts of mass fractions are 18% is finally added dropwise into polyaminoester emulsion persistently to stir Chain extension after 30min is carried out.
5) it is toasted under infrared lamp after gained aqueous polyurethane emulsion being poured into Teflon mould air drying for 24 hours Solvent is evaporated, it is spare that aqueous polyurethane elastic film is made.
Embodiment 9
1) by mass fraction be 50 parts ethylene glycol diglycidylether and mass fraction be 50 parts 1,4- butanediol two Glycidol ether and mass fraction are that 15 parts of catalyst base exchange resin D296 are added in autoclave, are warming up to 130 CO is passed through after DEG C2, pressure is maintained at 2MPa, reacts filtration catalytic agent after 30h, obtain cyclic carbonate compound.100 are weighed later The cyclic carbonate compound of part synthesis, is added 159.8 parts of ethylenediamines and is heated to 100 DEG C of insulation reaction 6h, at 90 DEG C after reaction Under vacuumize vacuum distillation 5h and remove excessive ethylenediamine, obtain alcoholamine chain extender.
2) polytetramethylene ether diol (M for being 8 parts by mass fractionn=1000) and 2 parts of Polyoxyethylene glycol (Mn= 1000) it is added in reactor, is warming up to 130 DEG C, vacuumize dehydration 2.5h；After being cooled to 50 DEG C later, 0.5 part of 2,2- hydroxyl is added Methylpropanoic acid and 0.56 part of diaminobenzoic acid and 6.98 part 1, hexamethylene-diisocyanate, then it is warming up to 90 DEG C of reaction 2h；Reaction After be cooled to 60 DEG C of 0.6 part of 1,4- butanediols of addition and 13.01 parts of solvent N,N-dimethylformamide back flow reaction 2h.
3) reaction system is cooled to 25 DEG C, 0.57 part and 10.77 parts N of salt forming agent triethylamine is added into reaction product, Dinethylformamide reaction 25min obtains Waterborne Polyurethane Prepolymer；
4) 37 parts of distilled water are added in hydrotropism's base polyurethane prepolymer for use as to emulsify at normal temperature, revolving speed 3000r/min, Emulsify 30min.The expanding chain pharmaceutical solution that 21.41 parts of mass fractions are 18% is finally added dropwise into polyaminoester emulsion persistently to stir Chain extension after 30min is carried out.
5) it is toasted under infrared lamp after gained aqueous polyurethane emulsion being poured into Teflon mould air drying for 24 hours Solvent is evaporated, it is spare that aqueous polyurethane elastic film is made.
Embodiment 10
1) by mass fraction be 100 parts 1,4- fourth diglycidyl ether and mass fraction be the exchange of 15 parts of catalyst alkalinity Resin D296 is added in autoclave, is passed through CO after being warming up to 140 DEG C2, pressure is maintained at 2MPa, filters after reacting 30h Catalyst obtains cyclic carbonate compound.The cyclic carbonate compound for weighing 100 parts of synthesis later, is added 82.8 parts of second two Amine is heated to 100 DEG C of insulation reaction 6h, vacuumizes vacuum distillation 5h after reaction at 90 DEG C and removes excessive ethylenediamine, obtains alcohol Amine chainextender.
2) polycarbonate glycol (M for being 10 parts by mass fractionn=1000) it is added in reactor, is warming up to 130 DEG C, take out Vacuum dehydration 2.5h；After being cooled to 50 DEG C later, 1 part of 2,2- hydroxymethyl propionic acid and 5.44 part 4,4 '-dicyclohexyl methyl hydrides are added Diisocyanate and 3.49 part 1, hexamethylene-diisocyanate, then it is warming up to 90 DEG C of reaction 2h；60 DEG C are cooled to after reaction to add Enter 0.6 part of 1,4- butanediol and 13.01 parts of solvent N,N-dimethylformamide back flow reaction 2h.
3) reaction system is cooled to 25 DEG C, 0.57 part and 10.77 parts N of salt forming agent triethylamine is added into reaction product, Dinethylformamide reaction 25min obtains Waterborne Polyurethane Prepolymer；
4) 37 parts of distilled water are added in hydrotropism's base polyurethane prepolymer for use as to emulsify at normal temperature, revolving speed 3000r/min, Emulsify 30min.The expanding chain pharmaceutical solution that 21.41 parts of mass fractions are 18% is finally added dropwise into polyaminoester emulsion persistently to stir Chain extension after 30min is carried out.
5) it is toasted under infrared lamp after gained aqueous polyurethane emulsion being poured into Teflon mould air drying for 24 hours Solvent is evaporated, it is spare that aqueous polyurethane elastic film is made.
The correlated performance for preparing aqueous polyurethane elastic film is listed in Table 1 below.
The correlated performance of 1. elastic polyurethane film of table

Claims (25)

1. a kind of water-fast or solvent resistance aqueous polyurethane preparation method, it is characterised in that the following steps are included:
(1) cyclic carbonate ester and aminated compounds are subjected to aminolysis reaction and alcoholamine chain extender is made；
(2) 1,4- butanediol will be added after polymer polyatomic alcohol, isocyanate compound, the hydrophilic agent prepolymerization reaction containing carboxyl And the reaction was continued for solvent；
(3) salt forming agent is added into above-mentioned reaction product after reaction to be reacted, obtains performed polymer；
(4) chain extension after adding the chain extender that preparation is added after water emulsification to carry out performed polymer, obtains the aqueous poly- ammonia of water-fast or solvent resistant Ester lotion；
(5) gained aqueous polyurethane emulsion is poured into Teflon mould and is toasted under infrared lamp after air drying 20-48h Or be placed in baking oven and evaporate solvent, aqueous polyurethane is made.
2. a kind of water-fast or solvent resistance aqueous polyurethane preparation method as described in claim 1, it is characterised in that described Cyclic carbonate in the aminolysis reaction of step (1): diamine compounds molar ratio is 1:2-10, and reaction temperature is 50-120 DEG C, Reaction time is 3-15h.
3. a kind of water-fast or solvent resistance aqueous polyurethane preparation method as described in claim 1, it is characterised in that state step Suddenly the amine class compound in (1) is hexamethylene diamine, propane diamine, butanediamine, ethylenediamine or pentanediamine.
4. a kind of water-fast or solvent resistance aqueous polyurethane preparation method as described in claim 1, it is characterised in that described Cyclic carbonate ester in step (1) is prepared by the following method:
By CO2Cycloaddition reaction is carried out with epoxide and obtains cyclic carbonate compound, and cycloaddition reaction temperature is 90-150 DEG C, time 25-45h, pressure 0.5-4MPa, catalyst charge are the 1-20% of epoxide weight.
5. a kind of water-fast or solvent resistance aqueous polyurethane preparation method as claimed in claim 4, it is characterised in that described Epoxide be ethylene carbonate, propene carbonate, ethylene glycol diglycidylether, butanediol diglycidyl ether, oneself two One or more of alcohol diglycidyl ether, neopentylglycol diglycidyl ether, diethylene glycol diglycidyl ether.
6. a kind of water-fast or solvent resistance aqueous polyurethane preparation method as claimed in claim 4, it is characterised in that described Catalyst is base exchange resin D296.
7. a kind of water-fast or solvent resistance aqueous polyurethane preparation method as described in claim 1, it is characterised in that described The polymer polyatomic alcohol of step (2) carries out pre-treatment, and pre-treating method is that dehydration 2-4h is vacuumized at 100-140 DEG C.
8. a kind of water-fast or solvent resistance aqueous polyurethane preparation method as described in claim 1, it is characterised in that step (2) polymer polyatomic alcohol in is one or more of polyetherdiol, polyester-diol, biological material polyalcohol.
9. a kind of water-fast or solvent resistance aqueous polyurethane preparation method as claimed in claim 8, it is characterised in that step (2) polymer polyatomic alcohol used in is the polyalcohol mixing of single variety or several different cultivars and different molecular weight, molecule Measure the polymer polyatomic alcohol of range 1000-2000.
10. a kind of water-fast or solvent resistance aqueous polyurethane preparation method as claimed in claim 8, it is characterised in that polyester Glycol is polyadipate esters, poly-epsilon-caprolactone glycol, polycarbonate glycol or poly (propylene carbonate) glycol.
11. a kind of water-fast or solvent resistance aqueous polyurethane preparation method as claimed in claim 9, it is characterised in that gather oneself Two esters of gallic acid are polyethylene glycol adipate, poly adipate succinic acid ester, polyadipate ethylene glycol and 1,2-propylene glycol ester, polyadipate Ethylene glycol-butanediol ester, polyadipate hexylene glycol ester are one or more of in polyadipate ethylene glycol-neopentyl glycol ester.
12. a kind of water-fast or solvent resistance aqueous polyurethane preparation method as claimed in claim 8, it is characterised in that polyethers Glycol is polytetramethylene ether diol, polyoxypropyleneglycol, Polyoxyethylene glycol or polybutadiene polyol.
13. a kind of water-fast or solvent resistance aqueous polyurethane preparation method as claimed in claim 8, it is characterised in that biology Material is castor oil or vegetable oil.
14. a kind of water-fast or solvent resistance aqueous polyurethane preparation method as described in claim 1, it is characterised in that step (2) diisocyanate cpd in is aromatic diisocyanate compounds, aliphatic diisocyanate compound or changes One or more of the diisocyanate cpd of property.
15. a kind of water-fast or solvent resistance aqueous polyurethane preparation method as claimed in claim 14, it is characterised in that virtue Fragrant (cyclo) aliphatic diisocyanates compound is toluene di-isocyanate(TDI) (TDI), 1,5- naphthalene diisocyanate (NDI) or diphenyl methane two Isocyanates (MDI).
16. a kind of water-fast or solvent resistance aqueous polyurethane preparation method as claimed in claim 14, it is characterised in that rouge Fat (cyclo) aliphatic diisocyanates compound is 1, hexamethylene-diisocyanate (HDI), dimethyl diphenyl diisocyanate (TODI), different Fo Er Ketone diisocyanate (IPDI), 4,4'-Dicyclohexylmethane diisocyanate (H12MDI).
17. a kind of water-fast or solvent resistance aqueous polyurethane preparation method as described in claim 1, it is characterised in that two is different Cyanate esters are toluene di-isocyanate(TDI) (TDI) or isophorone diisocyanate (IPDI).
18. a kind of water-fast or solvent resistance aqueous polyurethane preparation method as described in claim 1, it is characterised in that step (2) hydrophilic agent containing carboxyl in is one of 2,2- dihydromethyl propionic acid, dihydroxy half ester, diaminobenzoic acid or several Kind.
19. a kind of water-fast or solvent resistance aqueous polyurethane preparation method as described in claim 1, it is characterised in that step (2) solvent in is acetone, n,N-Dimethylformamide or N-Methyl pyrrolidone, and the additional amount of solvent is performed polymer: solvent Mass ratio is 1:0.8-1.6.
20. a kind of water-fast or solvent resistance aqueous polyurethane preparation method as described in claim 1, it is characterised in that state step Suddenly the prepolymerization reaction temperature of (2) is 70-95 DEG C, time 2-5h.
21. a kind of water-fast or solvent resistance aqueous polyurethane preparation method as described in claim 1, it is characterised in that state step Suddenly it is 30-60 DEG C that 1,4-butanediol and the solvent reaction temperature that the reaction was continued, which is added, in (2), reaction time 1-3h.
22. a kind of water-fast or solvent resistance aqueous polyurethane preparation method as described in claim 1, it is characterised in that step (3) reaction temperature is 10-40 DEG C, reaction time 5-30min.
23. a kind of water-fast or solvent resistance aqueous polyurethane preparation method as described in claim 1, it is characterised in that step (3) salt forming agent in is one or more of triethylamine, tripropyl amine (TPA), tri-n-butylamine, sodium hydroxide, ammonium hydroxide.
24. a kind of water-fast or solvent resistance aqueous polyurethane preparation method as described in claim 1, it is characterised in that step (4) emulsifying temperature is room temperature, and emulsifying rate is 1000-5000 r/min, emulsification times 10-40min.
25. a kind of water-fast or solvent resistance aqueous polyurethane preparation method as described in claim 1, it is characterised in that step (4) chain extension temperature is 10-50 DEG C afterwards, time 20-50min.
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CN110862336A (en) * 2019-10-29 2020-03-06 中国科学院山西煤炭化学研究所 Alcohol amine chain extender, preparation method and application
CN110894275A (en) * 2019-12-19 2020-03-20 山东一航新材料科技有限公司 Environment-friendly polyurethane chain extender and preparation method and application thereof
CN111138658A (en) * 2020-01-14 2020-05-12 四川大学 Method for preparing two-block nonionic fluorine-containing short-chain surfactant by non-isocyanate route
CN111138658B (en) * 2020-01-14 2021-04-23 四川大学 Method for preparing two-block nonionic fluorine-containing short-chain surfactant by non-isocyanate route
CN111662423A (en) * 2020-06-16 2020-09-15 中国科学院山西煤炭化学研究所 Preparation method of hydroxyl functionalized waterborne polyurethane
CN111848910A (en) * 2020-08-05 2020-10-30 山东华诚高科胶粘剂有限公司 Waterborne polyurethane prepared from sulfonated polycarbonate polyol containing amino ester bonds and preparation method thereof
CN112812262A (en) * 2020-12-31 2021-05-18 泰兴市华盛银洋新材料科技有限公司 Solvent-free hydroxyl waterborne polyurethane for wood lacquer, preparation method thereof and wood lacquer

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