CN102432797A - Hydroxyl-terminated alkyd resin-modified waterborne polyurethane and preparation method thereof - Google Patents
Hydroxyl-terminated alkyd resin-modified waterborne polyurethane and preparation method thereof Download PDFInfo
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- CN102432797A CN102432797A CN2011102376650A CN201110237665A CN102432797A CN 102432797 A CN102432797 A CN 102432797A CN 2011102376650 A CN2011102376650 A CN 2011102376650A CN 201110237665 A CN201110237665 A CN 201110237665A CN 102432797 A CN102432797 A CN 102432797A
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Abstract
The invention relates to hydroxyl-terminated alkyd resin-modified waterborne polyurethane and a preparation method thereof. The hydroxyl-terminated alkyd resin-modified waterborne polyurethane has a structural formula shown in the description and is prepared by replacing general polyalcohol by hydroxyl-terminated alkyd resin. According to the preparation method, an esterification, condensation and stepwise polymerization process is adopted. The preparation method comprises the following steps of: firstly, preparing the hydroxyl-terminated alkyd resin from fatty acid, polybasic acid and polyalcohol by adopting a fatty acid method; secondly, reacting the hydroxyl-terminated alkyd resin, polyhydroxyl carboxylic acid and polyisocyanates to prepare an isocyanate-terminated prepolymer containing a hydrophilic group; thirdly, adding a salt forming agent in the prepolymer for neutralizing carboxylic acid to form salts; fourthly, dispersing the product in ice water and adding polyamine to extend a chain at the same time; and fifthly, after reaction, removing a solvent by distilling to obtain an alkyd resin-modified high-performance polyurethane aqueous dispersion. The hydroxyl-terminated alkyd resin-modified waterborne polyurethane has the advantages of high oil resistance, high chemical product resistance, high water resistance as well as excellent hardness, fullness, lustrousness, storage stability, mechanical properties and integrated performances.
Description
Technical field
The present invention relates to aqueous polyurethane and preparation method thereof field, particularly a kind of terminal hydroxy group Synolac modified aqueous polyurethane and preparation method thereof.
Background technology
Aqueous polyurethane has and advantage such as does not fire, nontoxic, free from environmental pollution, energy-conservation, has HS, excellent properties such as wear-resistant, safe in utilization simultaneously, has therefore obtained to use widely, has become an important development direction of domestic and international field of new.Up to the present, the industrialized aqueous polyurethane kind of China is few, output is little, is difficult to satisfy present diversified demand, and the film-forming properties of product, snappiness, weathering resistance and water tolerance poor-performing are mainly handled and fabric treating as the leather of general property.Performance defect has seriously limited the promotion and application of aqueous polyurethane in paint field; Aqueous polyurethane adopts step-reaction polymerization; Contain a plurality of reactive groups on the molecular chain; Thereby available multiple material carries out the performance that modification improves aqueous polyurethane, and products such as acrylic acid modified in the last few years, epoxy modified aqueous urethane have obtained development fast.
Along with skyrocketing of oil price, be that the application of the Synolac of main raw material has obtained attention day by day with the vegetables oil.Synolac is the synthetic resins that China develops the earliest, output is maximum, and the component of Synolac and performance can be adjusted in wide range, adopt different polyvalent alcohols and polyprotonic acid just can obtain the different resin of performance; And the variation may command degree of branching of the ratio of functionality between the pure and mild acid; Carbonatoms in the resin raw material between the carboxyl or between the hydroxyl can be adjusted the flexibility of resin etc.; These characteristics make Synolac can be applied to more field, are the materials that one type of ideal is used for modified aqueous polyurethane.Synolac has following characteristics aspect modification: 1. contain poly-hydroxy in the Synolac, can react with making isocyanic ester, improve resin's crosslinkage.2. the Synolac of modification can make it contain terminal hydroxy group, can replace the reaction of polyvalent alcohol and POLYMETHYLENE POLYPHENYLISOCYANATE.3. contain unsaturated link(age) in the dry alkyd resin mostly, crosslinking reaction can take place in modified aqueous polyurethane under the effect of oxygen or catalyzer.
Adopt alkyd modified one side can improve polyurethane film physicals and feel, can also reduce cost in addition, so Synolac highlights its meliority day by day aspect modified aqueous polyurethane.
Summary of the invention
The object of the invention aims to provide a kind of advantage that has urethane resin, two kinds of resins of Synolac concurrently, can be applicable to terminal hydroxy group Synolac modified aqueous polyurethane of purposes such as industrial coating, terrace lacquer, wood lacquer, leather surface processing and preparation method thereof.
The modified aqueous polyurethane that the present invention relates to replaces common polyvalent alcohol the terminal hydroxy group Synolac and is prepared from.The structural formula of this polymkeric substance is:
R is the isocyanic ester segment in the structural formula, R
1Be terminal hydroxy group alkyd polyester segment, n is an integer, n>=1.
The preparation method that the present invention is is following: it is characterized in that, may further comprise the steps,
1. polyvalent alcohol, lipid acid, polyprotonic acid are mixed, do reflux solvent with YLENE, 150 ℃ ~ 220 ℃ are reacted to acid number 5 ~ 15mgKOH.g
-1After, steam YLENE, make the terminal hydroxy group Synolac;
2. add POLYMETHYLENE POLYPHENYLISOCYANATE to above-mentioned terminal hydroxy group Synolac, insulation reaction is 1 ~ 2 hour under 85 ℃ ~ 95 ℃ conditions; Add the wetting ability chainextender again, reacted 1 ~ 2 hour under 70 ℃ ~ 90 ℃ conditions; Add then oxy-compound and solvent, 60 ℃ ~ 65 ℃ isothermal reactions are 4 of add-on ~ 8% o'clock to recording NCO content, are cooled to 5 ℃ ~ 10 ℃ dischargings at last, make terminal hydroxy group Synolac modified polyurethane prepolymer;
3. terminal hydroxy group Synolac modified polyurethane prepolymer is carried out dispersed with stirring; Add salt forming agent, acetone below 10 ℃, in the carboxyl salify, add entry then and carry out dispersion and emulsion; Add the polyamine chainextender afterwards and carry out chain extension, make terminal hydroxy group Synolac modified polyurethane aqueous dispersions;
4. with terminal hydroxy group Synolac modified polyurethane aqueous dispersions precipitation, underpressure distillation removes solvent and makes terminal hydroxy group Synolac modified aqueous polyurethane.
Said polyvalent alcohol is a kind of or its any mixture in the binary, ternary, quaternary or the hexa-atomic fatty alcohol that contain 2 ~ 6 carbon atoms; Said lipid acid is a kind of or its mixture in the unsaturated unary fatty acid that contains 10 ~ 20 carbon atoms; Said polyprotonic acid is that binary, ternary contain 2 ~ 6 fat of carbon atom families or aromatic acid a kind of or its mixture wherein.
Said polyvalent alcohol further is preferably a kind of or its any mixture in terepthaloyl moietie, butyleneglycol, TriMethylolPropane(TMP), NSC 6366, the tetramethylolmethane; Said lipid acid further is preferably a kind of or its any mixture in oleic acid, linolic acid, the dehydrated castor oleic acid; Described polyprotonic acid further is preferably a kind of or its any mixture in hexanodioic acid, fumaric acid, Tetra hydro Phthalic anhydride, MALEIC ANHYDRIDE, the m-phthalic acid.
Said POLYMETHYLENE POLYPHENYLISOCYANATE is tolylene diisocyanate, isophorone diisocyanate or diphenylmethanediisocyanate, and said step 2. solvent is acetone, methylethylketone or N.
Said wetting ability chainextender is dimethylol propionic acid or dimethylolpropionic acid; Said is terepthaloyl moietie, 1 to oxy-compound, 4-butyleneglycol or glycol ether.
Said cold water is 0 ℃ deionized water, accounts for 40 ~ 65% of 2. ~ 3. total charging capacity of step; Said salt forming agent is a triethylamine.
Said polyamine chainextender is isophorone diamine, diethylenetriamine or TEPA.
Said step 1. in polyvalent alcohol, lipid acid, polyprotonic acid weight ratio=5 ~ 25:40 ~ 60:20 ~ 45 that feed intake; Step 2. ~ 3. in, each material weight ratio that feeds intake is the terminal hydroxy group Synolac: POLYMETHYLENE POLYPHENYLISOCYANATE: wetting ability chainextender: to oxy-compound: solvent: triethylamine: polyamine chainextender=10 ~ 26:6 ~ 30:4 ~ 8:1 ~ 10:8 ~ 20:1 ~ 6:2 ~ 5.
The preparation method of described terminal hydroxy group Synolac modified aqueous polyurethane further is preferably, said terminal hydroxy group Synolac, POLYMETHYLENE POLYPHENYLISOCYANATE, wetting ability chainextender, to oxy-compound, solvent, triethylamine, polyamine chainextender charging capacity account for respectively step 2. ~ 3. total charging capacity 10 ~ 26%, 6 ~ 30%, 4 ~ 8%, 1 ~ 10%, 8 ~ 20%, 1 ~ 6%, 2 ~ 5%; Described step 1. preferred version is: polyvalent alcohol, lipid acid, polyprotonic acid are mixed according to 5 ~ 25%, 40 ~ 60%, 20 ~ 45% of total charging capacity; Do reflux solvent with YLENE; 150 ℃ ~ 160 ℃ insulation reaction 1.5 ~ 2.5 hours; 175 ~ 185 ℃ of insulation reaction 2 ~ 3 hours are warming up to 200 ~ 220 ℃, and insulation reaction is to acid number 5 ~ 15mgKOH.g
-1, stop heating, steam YLENE, make the terminal hydroxy group Synolac; Said step 3. preferred version is: terminal hydroxy group Synolac modified polyurethane prepolymer is added disperse cylinder, rotating speed is controlled at 500 ~ 1000 rev/mins and carries out dispersed with stirring, adds triethylamine, acetone below 10 ℃; In with the carboxyl salify; After 5 ~ 6 minutes rotating speed is carried to 1000 ~ 2000 rev/mins, the deionized water that adds 0 ℃ then carries out dispersion and emulsion, adds the polyamine chainextender after 9 ~ 11 minutes and carries out chain extension; High speed dispersion 9 ~ 11 minutes; Speed drop is low to moderate 450 ~ 500 rev/mins, disperseed 0.5 ~ 1.5 hour, make terminal hydroxy group Synolac modified polyurethane aqueous dispersions; Said step 4. preferred version is: terminal hydroxy group Synolac modified polyurethane aqueous dispersions is added precipitation still precipitation, and 55 ~ 65 ℃ of temperature, vacuum tightness-0.08Mpa ~-remove solvent under the 0.09Mpa to make terminal hydroxy group Synolac modified aqueous polyurethane.
The present invention compared with prior art has following advantage:
1, the product that the present invention produced has high-weatherability, chemical-resistant, water tolerance, also has excellent hardness, bonding strength, glossiness, stability in storage and over-all properties simultaneously.One big advantage of Synolac is that it does not rely on petroleum products basically, and its raw material sources are extensive, and prescription is easy to give its various characteristics through various modifications flexibly, almost can be applied among all types coating.And contain poly-hydroxy and insatiable hunger key in the Synolac, and can replace linking agent to make urethane produce cross-linked network, both reduced cost, improve this product each item technical feature again.
2, product of the present invention produce and use in three-waste free discharge, be nontoxic, do not fire, free from environmental pollution, save energy, solve environmental pollution from root, the able-bodied environmental protection of protection people, resource-conserving product.
3, product cost of the present invention is lower, has high-performance, and excellent combination property can be widely used in fields such as aqueous industrial coating, terrace lacquer, wood lacquer, hard floor paint, PVC plastic lousing lac varnish, high-performance hide finishes.Along with the enhancing of sound and people's environmental consciousness of Environmental Protection in China rules, will obtain great development with the high-performance multipurpose aqueous polyurethane of water replace solvents, and the alternative import of product, 60% outlet, market outlook are wide.
Embodiment
Embodiment 1: in the stainless steel cauldron of the 100L that whisking appliance, TM, condensing surface, oily-water seperating equipment are housed, once add the 25Kg LAURIC ACID 99 MIN; 10Kg terepthaloyl moietie and 20Kg hexanodioic acid, heat temperature raising is done reflux solvent with YLENE 110kg simultaneously; 150～160 ℃ of insulation reaction 2 hours; 180 ℃ of insulation reaction 2～3 hours are warming up to 210 ℃, and insulation reaction to acid number is to 6mgKOH.g
-1, stop heating, steam YLENE, it is subsequent use to make the discharging of terminal hydroxy group Synolac.
Get above-mentioned 38Kg terminal hydroxy group Synolac and place the 250L stainless steel cauldron that whisking appliance, TM, condensing surface are housed, heat temperature raising, 90 ℃ drip 25Kg tolylene diisocyanate (TDI); Drip off back insulation reaction 1 hour, be cooled to 85 ℃ and add dimethylol propionic acid 3.5kg, reacted 2 hours; Be cooled to 65 ℃ again and add 4Kg 1; 4-butyleneglycol and 50kg acetone insulation reaction 4～5 hours, surveying NCO content is 5% of add-on, makes modified polyurethane resin performed polymer (structural formula I).Be cooled to 5 ℃, the modified polyurethane resin performed polymer added disperse cylinder, rotating speed carries out dispersed with stirring for 500 rev/mins; Add 4Kg triethylamine and proper amount of acetone reaction 3～4min; Then rotating speed is increased to 1500 rev/mins, the powerful stirring adds frozen water, 3Kg diethylenetriamine, high speed dispersion 15 minutes down successively; Then rotating speed is transferred to 500 rev/mins and stirred 30 minutes, make terminal hydroxy group Synolac modified aqueous polyurethane dispersion liquid.The modified polyurethane aqueous dispersions is added the precipitation still, 55 ℃ ~ 65 ℃, slough solvent under vacuum tightness-0.085Mpa condition and both got terminal hydroxy group Synolac modified aqueous polyurethane (structural formula II).The concrete structure formula is following:
The structural formula I:
The structural formula II:
In structural formula I, the II in the structural formula R be tolylene diisocyanate (TDI) segment, R
1Be terminal hydroxy group alkyd polyester (is raw material with LAURIC ACID 99 MIN, terepthaloyl moietie, hexanodioic acid) segment, n is an integer, n>=1.
Embodiment 2: in the stainless steel cauldron of the 100L that whisking appliance, TM, condensing surface, oily-water seperating equipment are housed, once add 30Kg dehydrated castor oleic acid; 15Kg TriMethylolPropane(TMP) and 24Kg Tetra hydro Phthalic anhydride heat temperature raising; Do reflux solvent with YLENE 100kg simultaneously, 150～160 ℃ of insulation reaction 2 hours, 180 ℃ of insulation reaction 2～3 hours; Be warming up to 210 ℃, insulation reaction to acid number to 8 mgKOH.g
-1, stop heating, steam YLENE, it is subsequent use to make the discharging of terminal hydroxy group Synolac.
Get above-mentioned 45Kg terminal hydroxy group Synolac and place the 250L stainless steel cauldron that whisking appliance, TM, condensing surface are housed, heat temperature raising, 90 ℃ drip 32KgMDI; Drip off back insulation reaction 1 hour, be cooled to 85 ℃ and add dimethylol propionic acid 6.5Kg, reacted 2 hours; Be cooled to 65 ℃ of adding 8Kg terepthaloyl moietie and 55kg acetone insulation reaction again 4～5 hours; Surveying NCO content is 6% of add-on, is cooled to 5 ℃, makes the modified polyurethane resin performed polymer.The modified polyurethane resin performed polymer is added the dispersion cylinder, and rotating speed carries out dispersed with stirring for 500 rev/mins, adds 9Kg triethylamine and proper amount of acetone reaction 3～4min; Then rotating speed is increased to 1500 rev/mins, the powerful stirring adds frozen water, 2.5Kg diethylenetriamine down successively; High speed dispersion 15 minutes; Then rotating speed is transferred to 500 rev/mins and stir 30min, make terminal hydroxy group Synolac modified aqueous polyurethane dispersion liquid, the modified polyurethane aqueous dispersions is added the precipitation still; 55 ℃ ~ 65 ℃, slough solvent under the vacuum tightness-0.085 Mpa condition and both got terminal hydroxy group Synolac modified aqueous polyurethane.
Product hardness (pencil hardness) H, gloss (gloss 60o) 110, water tolerance (filming 25 ℃, 100 hours) is non-foaming, nothing comes off; Do not whiten sticking power (cross-hatching)≤1, chemical-resistant (5% acid solution; 8% alkaline solution, 100% ethanolic soln is filmed and was soaked 24 hours) no change.Be suitable as aqueous woodware paint, hard floor paint and terrace lacquer.
The structure formation of modified polyurethane resin, modified polyurethane aqueous dispersions is basically with embodiment 1 in the present embodiment, and difference is that the R in structural formula I, the II is ditan two isocyanide ester ester segments (MDI), R
1For polyester segment (with lipid acid is dehydrated castor oleic acid, and polyvalent alcohol is a TriMethylolPropane(TMP), and polyprotonic acid is that Tetra hydro Phthalic anhydride is starting material), be terepthaloyl moietie to oxy-compound.
Embodiment 3: in the 100L stainless steel cauldron of whisking appliance, TM, condensing surface, oily-water seperating equipment is housed, once add 35Kg oleic acid; 17Kg TriMethylolPropane(TMP) and 26Kg fumaric acid, heat temperature raising is done reflux solvent with YLENE 105Kg simultaneously; 150～160 ℃ of insulation reaction 2 hours; 180 ℃ of insulation reaction 2～3 hours are warming up to 210 ℃, and insulation reaction to acid number was to 9mgKOH hour .g
-1, stop heating, steam YLENE, it is subsequent use to make the discharging of terminal hydroxy group Synolac.
Get above-mentioned 56Kg terminal hydroxy group Synolac and place the 250L stainless steel cauldron that whisking appliance, TM, condensing surface are housed, heat temperature raising, 90 ℃ drip 45KgIPDI; Drip off back insulation reaction 1 hour; Be cooled to 85 ℃ and add dimethylolpropionic acid 7.5Kg, reacted 2 hours, be cooled to 65 ℃ of adding 10Kg glycol ethers and 60kg acetone insulation reaction again 4～5 hours; Surveying NCO content is 4% of add-on, is cooled to 30 ℃ and makes the modified polyurethane resin performed polymer.The modified polyurethane resin performed polymer is added the dispersion cylinder, and rotating speed carries out dispersed with stirring for 500 rev/mins, adds 7.8Kg triethylamine and proper amount of acetone reaction 18～20min; Then rotating speed is increased to 1500 rev/mins, the powerful stirring adds cold water, 2.0Kg isophorone diamine down successively; High speed dispersion 15 minutes; Then rotating speed is transferred to 500 rev/mins and stir 30min, make terminal hydroxy group Synolac modified aqueous polyurethane dispersion liquid, the modified polyurethane aqueous dispersions is added the precipitation still; 55 ℃ ~ 65 ℃, slough solvent under vacuum tightness-0.085Mpa condition and both got terminal hydroxy group Synolac modified aqueous polyurethane.
Shock-resistance 50kg.cm after this product film forming, thermotolerance (120 ℃ of steel plates, 1 hour) no change, xanthochromia property is good, and weathering resistance (30 ℃ ~ 80 ℃, cold cycling 120 times) nothing comes off, no peeling.Can be used for the automobile primary coat, in industrial coating such as be coated with.
The structure formation of modified polyurethane resin, modified polyurethane aqueous dispersions is basically with embodiment 1 in the present embodiment, and difference is that the R in structural formula I, the II is isoflurane chalcone diisocyanate (IPDI) segment, R
1Be polyester (with lipid acid is oleic acid, and polyvalent alcohol is a TriMethylolPropane(TMP), and polyprotonic acid is that fumaric acid is starting material) that polyol is a glycol ether, the wetting ability chainextender is a dimethylolpropionic acid, and the polyamine chainextender is an isophorone diamine.
The above embodiment that lifts can both realize the present invention, the bound value of each raw material of the present invention with and interval value all can realize the present invention, do not enumerate other embodiment one by one at this; The bound value of processing parameter of the present invention with and interval value all can realize the present invention, do not enumerate other embodiment one by one at this.
Claims (10)
1. terminal hydroxy group Synolac modified aqueous polyurethane is characterized in that the structural formula of this polymkeric substance is:
R is the isocyanic ester segment in the structural formula, R
1Be terminal hydroxy group alkyd polyester segment, n is an integer, n>=1.
2. the preparation method of the described terminal hydroxy group Synolac of claim 1 modified aqueous polyurethane is characterized in that: may further comprise the steps,
1. polyvalent alcohol, lipid acid, polyprotonic acid are mixed, do reflux solvent with YLENE, 150 ℃ ~ 220 ℃ are reacted to acid number 5 ~ 15mgKOH.g
-1After, steam YLENE, make the terminal hydroxy group Synolac;
2. add POLYMETHYLENE POLYPHENYLISOCYANATE to above-mentioned terminal hydroxy group Synolac, insulation reaction is 1 ~ 2 hour under 85 ℃ ~ 95 ℃ conditions; Add the wetting ability chainextender again, reacted 1 ~ 2 hour under 70 ℃ ~ 90 ℃ conditions; Add then oxy-compound and solvent, 60 ℃ ~ 65 ℃ isothermal reactions are 4 of add-on ~ 8% o'clock to recording NCO content, are cooled to 5 ℃ ~ 10 ℃ dischargings at last, make terminal hydroxy group Synolac modified polyurethane prepolymer;
3. terminal hydroxy group Synolac modified polyurethane prepolymer is carried out dispersed with stirring; Add salt forming agent, acetone below 10 ℃, in the carboxyl salify, add entry then and carry out dispersion and emulsion; Add the polyamine chainextender afterwards and carry out chain extension, make terminal hydroxy group Synolac modified polyurethane aqueous dispersions;
4. with terminal hydroxy group Synolac modified polyurethane aqueous dispersions precipitation, underpressure distillation removes solvent and makes terminal hydroxy group Synolac modified aqueous polyurethane.
3. the preparation method of terminal hydroxy group Synolac modified aqueous polyurethane according to claim 2 is characterized in that said polyvalent alcohol is a kind of or its any mixture in the binary, ternary, quaternary or the hexa-atomic fatty alcohol that contain 2 ~ 6 carbon atoms; Said lipid acid is a kind of or its mixture in the unsaturated unary fatty acid that contains 10 ~ 20 carbon atoms; Said polyprotonic acid is that binary, ternary contain 2 ~ 6 fat of carbon atom families or aromatic acid a kind of or its mixture wherein.
4. the preparation method of terminal hydroxy group Synolac modified aqueous polyurethane according to claim 3 is characterized in that said polyvalent alcohol is a kind of or its any mixture in terepthaloyl moietie, butyleneglycol, TriMethylolPropane(TMP), NSC 6366, the tetramethylolmethane; Said lipid acid is a kind of or its any mixture in oleic acid, linolic acid, the dehydrated castor oleic acid; Described polyprotonic acid is a kind of or its any mixture in hexanodioic acid, fumaric acid, Tetra hydro Phthalic anhydride, MALEIC ANHYDRIDE, the m-phthalic acid.
5. according to the preparation method of the described terminal hydroxy group Synolac of the arbitrary claim of 2-4 modified aqueous polyurethane; It is characterized in that said POLYMETHYLENE POLYPHENYLISOCYANATE is tolylene diisocyanate, isophorone diisocyanate or diphenylmethanediisocyanate, said step 2. solvent is acetone, methylethylketone or N.
6. the preparation method of terminal hydroxy group Synolac modified aqueous polyurethane according to claim 5 is characterized in that said wetting ability chainextender is dimethylol propionic acid or dimethylolpropionic acid; Said is terepthaloyl moietie, 1 to oxy-compound, 4-butyleneglycol or glycol ether.
7. the preparation method of terminal hydroxy group Synolac modified aqueous polyurethane according to claim 6 is characterized in that said cold water is 0 ℃ deionized water; Said salt forming agent is a triethylamine.
8. the preparation method of terminal hydroxy group Synolac modified aqueous polyurethane according to claim 7 is characterized in that said polyamine chainextender is isophorone diamine, diethylenetriamine or TEPA.
9. the preparation method of terminal hydroxy group Synolac modified aqueous polyurethane according to claim 8 is characterized in that: step 1. in polyvalent alcohol, lipid acid, polyprotonic acid weight ratio=5 ~ 25:40 ~ 60:20 ~ 45 that feed intake; Step 2. ~ 3. in, each material weight ratio that feeds intake is the terminal hydroxy group Synolac: POLYMETHYLENE POLYPHENYLISOCYANATE: wetting ability chainextender: to oxy-compound: solvent: triethylamine: polyamine chainextender=10 ~ 26:6 ~ 30:4 ~ 8:1 ~ 10:8 ~ 20:1 ~ 6:2 ~ 5.
10. the preparation method of terminal hydroxy group Synolac modified aqueous polyurethane according to claim 9; It is characterized by, said terminal hydroxy group Synolac, POLYMETHYLENE POLYPHENYLISOCYANATE, wetting ability chainextender, to oxy-compound, solvent, triethylamine, polyamine chainextender charging capacity account for respectively step 2. ~ 3. total charging capacity 10 ~ 26%, 6 ~ 30%, 4 ~ 8%, 1 ~ 10%, 8 ~ 20%, 1 ~ 6%, 2 ~ 5%; Described step 1. preferred version is: polyvalent alcohol, lipid acid, polyprotonic acid are mixed according to 5 ~ 25%, 40 ~ 60%, 20 ~ 45% of total charging capacity; Do reflux solvent with YLENE; 150 ℃ ~ 160 ℃ insulation reaction 1.5 ~ 2.5 hours; 175 ~ 185 ℃ of insulation reaction 2 ~ 3 hours are warming up to 200 ~ 220 ℃, and insulation reaction is to acid number 5 ~ 15mgKOH.g
-1, stop heating, steam YLENE, make the terminal hydroxy group Synolac; Said step 3. preferred version is: terminal hydroxy group Synolac modified polyurethane prepolymer is added disperse cylinder, rotating speed is controlled at 500 ~ 1000 rev/mins and carries out dispersed with stirring, adds triethylamine, acetone below 10 ℃; In with the carboxyl salify; After 5 ~ 6 minutes rotating speed is carried to 1000 ~ 2000 rev/mins, the deionized water that adds 0 ℃ then carries out dispersion and emulsion, adds the polyamine chainextender after 9 ~ 11 minutes and carries out chain extension; High speed dispersion 9 ~ 11 minutes; Speed drop is low to moderate 450 ~ 500 rev/mins, disperseed 0.5 ~ 1.5 hour, make terminal hydroxy group Synolac modified polyurethane aqueous dispersions; Said step 4. preferred version is: terminal hydroxy group Synolac modified polyurethane aqueous dispersions is added precipitation still precipitation, and 55 ~ 65 ℃ of temperature, vacuum tightness-0.08Mpa ~-remove solvent under the 0.09Mpa to make terminal hydroxy group Synolac modified aqueous polyurethane.
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| CN114395822A (en) * | 2021-09-01 | 2022-04-26 | 长春工业大学 | Preparation method of physical and chemical synergetic super-hydrophobic waterborne polyurethane film |
| CN114751828A (en) * | 2022-04-20 | 2022-07-15 | 江苏恒力化纤股份有限公司 | Hydroxyl-terminated oleate, environment-friendly hydrophobic polyurethane and preparation method and application thereof |
| CN115044013A (en) * | 2022-07-08 | 2022-09-13 | 江苏富琪森新材料有限公司 | Bio-based air-curing type waterborne polyurethane urea resin and preparation method thereof |
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