CN1227284C - Process for preparation of high strength polyurethane aqueous dispersion - Google Patents
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Abstract
The present invention relates to a method for preparing high-strength polyurethane aqueous dispersion, which has the steps: carrying out the reaction of prepolymerization of aliphatic or aromatic diisocyanate and polyester or polyether diatomic alcohol by the molar ratio of 1.5 to 2.1: 1 for one to six hours at the temperature of 40 to 90 DEG C; adding vinyl monomer which accounts for 20 to 80% of the total amount of the polymer into the polymer after the reaction of prepolymerization as diluting agents; adding low-molecule diatomic alcohol or diamine chain extender with the molar ratio of 0.5 to 0.9: 1 to the residual isocyanato for the reaction of chain extension for one to four hours; cooling the system to 28 to 35 DEG C after the reaction of chain extension is finished; adding deflocculant which accounts for 2 to 8% of the total amount of the polymer into the polymer; carrying out aqueous dispersion in the existence of surface active agents which account for 0.5 to 3% of the total amount of the polymer; polymerizing vinyl monomer by a conventional method after the emulsion is stabilized.
Description
The present invention relates to the preparation method of macromolecular compound, specifically is a kind of preparation method of high strength polyurethane aqueous dispersion.
Water dispersible polyurethane all fails to reach the level of solvent borne polyurethane in mechanical properties such as tensile strength, moisture-proof wipings.In the synthesis technique of traditional polyurethane aqueous dispersion body, in water, disperse smoothly, use a large amount of organic solvents to make thinner in order to ensure high-molecular weight urethane.Used the acetone of 40%-80% to help the dispersive thinner in the patent (U.S.Pat.4,870,129) as Beyer Co., Ltd.This method has significantly improved production cost, if acetone must be distillated after the emulsification, has increased the difficulty of environmental protection simultaneously again, and this is that many industrial production are undesirable.
In order to improve the performance of water dispersible polyurethane, widen its range of application, the bi-component polyurethane ester aqueous dispersion has appearred, in the hope of making it reach the requirement of some application by blending, compounding process.People have made number of research projects, as U.S.Pat.5, the water dispersible polyurethane synthetic method of self-vulcanizing in 389,718 be with in the molecular chain with the water dispersion of the water dispersion of the hydroxy-terminated polymer component of carbamate groups, anionic group and polyisocyanates by a certain percentage hybrid reaction form.The functionality of hydroxyl and isocyanic ester when synthesizing each component, the content of carbamate groups, anionic group are all wanted strict control, otherwise very big to the performance impact of synthetic water dispersible polyurethane.And two-pack in process for preparation owing to be subjected to the chemical property, thermodynamical coordinate of material and the influence that colloid power is learned, dispersion particle size is increased, generation is separated, even causes cohesion, makes blending process become complexity and effect not as people's will.
The third method is that inside and outside linking agent by adding polyfunctionality is to improve the water dispersible polyurethane film strength.As: use small molecules TriMethylolPropane(TMP), trolamine to participate in prepolymerization reaction, or use the chainextender of polyfunctionality to come the cross-linked polyurethane chain, these addings of inline dose make the excessive gel that causes of polymer viscosity, cause the emulsification difficulty.And outside cross-linking agents such as epoxy compounds, polynary amine, aziridine add dispersion before use, can cause the emulsion particle alligatoring, and producing precipitation influences stability of emulsion, makes polyurethane film lose snappiness and flexibility simultaneously.Have the researchist on the polyurethane molecular chain, introduce the two keys of insatiable hunger carry out crosslinked, as: use the polyethers that contains unsaturated double-bond or polyester polyol to prepare vinyl monomer urethane among the patent CN.1136054 and be used for making condom.But its film forming matter must carry out crosslinking reaction under the high temperature more than 80 ℃ just has higher intensity, and the range of application of water miscible liquid is restricted.
Avoiding another kind of method with an organic solvent is that base polyurethane prepolymer for use as is dissolved in the vinyl monomer, after water-dispersion, carry out the vinyl polyaddition reaction, form interpenetrating polymer (CN1185454) still, the resulting water dispersion intensity of this method is lower, can be used as binding agent, fabric finishing agent etc. can not satisfy the requirement (as: making condom) of some special application.
The objective of the invention is for the public provide a kind of with low cost, the preparation method of the simple high strength polyurethane aqueous dispersion of technology.
The objective of the invention is to realize by following proposal.
Technical scheme of the present invention is: with aliphatics or aromatic vulcabond and polyester diol or polyether Glycols with 1.5-2.1: 1 mol ratio was carried out prepolymerization reaction 1～6 hour at 40～90 ℃, use in the reaction process or without tin class catalyzer, after pre-polymerization finishes, add 20～80% the vinyl monomer account for the polymkeric substance total amount and make thinner, and add with residue isocyano mol ratio be that 0.5～0.9: 1 low molecular dibasic alcohol or binary amine chainextender carried out chain extending reaction 1～4 hour, with the molecular weight of increase polymkeric substance; After chain extension finishes, system is cooled to 28～35 ℃, add 2～8% deflocculants that account for the polymkeric substance total amount, in the presence of 0.5～3% tensio-active agent that accounts for the polymkeric substance total amount, carry out water-dispersion, treat to carry out according to a conventional method behind the emulsion-stabilizing polymerization of vinyl monomer, obtain the interpenetrating polymer water dispersion of high-strength polyurethane.
In the such scheme: (1) be used to prepare dispersion the polyfunctionality isocyanic ester can according to the needs of system film select aliphatics or aromatic vulcabond as: 4,4`-phenylbenzene-methane diisocyanate, 1, hexamethylene-diisocyanate, isophorone diisocyanate, tolylene diisocyanate, phenylenedimethylidyne isocyanic ester, polyphenyl polyisocyanate, 4, compounds such as 4`-dicyclohexyl methane diisocyanate, cyclohexyl diisocyanate.
(2) oxy-compound of synthesis of polyurethane can use polyester diol or polyether Glycols, its number-average molecular weight scope is 300-5000, average hydroxyl value scope 30-150, suitable polyester diol be select oneself diacid, phthalic acid, terephthalic acid, toxilic acid acid be selected from ethylene glycol, 1,2-propylene glycol, 1, the alcohol preparation of 4-butyleneglycol, hexylene glycol, neopentyl glycol.Polyether Glycols is (as ethylene glycol, 1 by propylene oxide or tetrahydrofuran (THF) and polyvalent alcohol, 2`-propylene glycol and 1, the 4`-butyleneglycol) condensation product, as PTMG, propylene oxide oxyethane copolyether dibasic alcohol, poly-hexanodioic acid 1,4-butanediol ester glycol, polyethylene glycol adipate dibasic alcohol, polyoxypropyleneglycol, poly-hexanodioic acid glycol ether esterdiol etc.
(3) chainextender: chainextender is low molecular dibasic alcohol or binary amine, can be non-ionic, as: 1,4-butyleneglycol, glycol ether, 1,6-hexylene glycol, quadrol, hexamethylene-diamine, piperazine; Also can be anion-containing, as: (used alcohols is generally micromolecular triol or oligopolymer triol to the half ester that dimethylol propionic acid, 2-sodium sulfonate-1,4 butyleneglycol and dibasic acid anhydride reaction generate, as glycerine, low molecular polyether triol; Used acid anhydrides has MALEIC ANHYDRIDE, Tetra hydro Phthalic anhydride.Succinic anhydried, Pyroglutaric acid etc.); Also can use the chainextender of Sulfonates, as: second diamino ethyl sulfonic acid sodium, 1,4-butyleneglycol-2-sodium sulfonate and derivative thereof all can be made the chainextender of sulfonic acid type polyurethane aqueous dispersion body.Cationic chainextender is less, generally is the dihydroxy compound that contains tertiary amine groups as N methyldiethanol amine, trolamine etc.
(4) catalyzer: the suitable reactive hydrogen atom and the catalyzer of isocyanate reaction comprise: dibutyl tin laurate, the inferior tin of lauric acid, the inferior tin of stearic acid, stannous octoate etc.Also can use tertiary amine such as triethylene diamine, triethylamine etc.These catalyzer both can use separately also and can several mixing use.
(5) dispersing auxiliary: the dispersion of urethane generally need be carried out in the presence of dispersing auxiliary among the present invention, and the selection of dispersing auxiliary and the collocation of consumption are very important, and the dispersing auxiliary here can be tensio-active agent, emulsifying agent or colloid.Suitable tensio-active agent can be negatively charged ion, positively charged ion or non-ionic compound or mixture.Generally wherein a class or a few class are mixed use.Preferably hydrophobic relatively and relative hydrophilic emulsifying agent is used in combination, its consumption is generally 0.5～3% of polymkeric substance total amount, as tween-80, polyoxyethylene ester etc., also can add deflocculant: as gelatin Walocel MT 20.000PV, polyvinyl alcohol, Sudan Gum-arabic etc., add-on is 2～8% of a polymkeric substance total amount.
(6) in the prior art, the polymerization of vinyl monomer: the catalyzer of the radical addition polymerization of olefin monomer has water miscible free radical organizer, as: Potassium Persulphate, Sodium Persulfate, Ammonium Persulfate 98.5 etc., general consumption is 00.1～2% of a total solid content, or use with reductive agent (sodium thionyl, Sulfothiorine), as the redox catalysis system, the consumption of reductive agent is 00.1～2% of a total solid content.The vinyl addition polymerization generally carried out under 60-110 ℃ 4-10 hour, until residual monomer content be lower than total scale of construction 0.1% till.
Vinyl monomer mainly contains two purposes in the present invention: 1, action-reaction thinner, work when urethane chain extension and dispersion; 2, monomer can carry out radical polymerization, not only can strengthen the thin polyurethane film strength, can also give polyurethane aqueous dispersion body some special performances, as: the sense of touch comfortableness of the self lubricity of film article, polyamine ester film, the compactness of film etc.Performance requriements according to film article can be selected different monomers.
Hydrophobic monomer has the vinyl acetate of paraffinic acid, as: vinyl formate, propionate, isopropylformic acid vinyl acetate, vinyl laurate etc.; Alkyl acrylate, as: methyl acrylate, ethyl ester, positive butyl ester, lauryl etc.; Alkyl methacrylate, as: methacrylic ester acid methyl esters, ethyl ester, positive butyl ester, lauryl etc.; The monomer of diene class, as: divinyl, isoprene and derivative thereof; Aromatic vinyl monomer is as: vinylbenzene, Vinyl toluene, to chloro-styrene, a-vinyl toluene etc.
Hydrophilic monomer has undersaturated monocarboxylic acid, as: vinylformic acid, methacrylic acid; The ester class of unsaturated acid, as: dibutyl maleinate, dibutyl fumarate bulletin; The acid amides of unsaturated acid, as: acrylamide, N-carboxymethyl acrylamide etc.; The heterocycle vinyl monomer is as vinyl pyridine, N-vinyl pyrrolidone etc.
If the film article requirement is soft, tactile feel is good, can use the dibasic alcohol of the bigger polyether-type of molecular weight, as oxyethane Ethylene Oxide copolyether dibasic alcohol, tetrahydrofuran (THF) propylene oxide copolyether dibasic alcohol etc.; Vulcabond can adopt aliphatic different Buddhist and ketone vulcabond, hexamethylene diisocyanate etc.; Vinyl monomer can adopt the compound of film forming than the softish esters of acrylic acid.
The film article high to some requirement of strength then can use crystalline polyester diol, as poly-hexanodioic acid-1,4-butyleneglycol; Vulcabond adopts aromatic tolylene diisocyanate, 4,4`-diphenylmethanediisocyanate etc.; Acrylic Acid Monomer adopts the harder methyl acrylic ester of film forming.
Will use hydrophobic polyethers dibasic alcohol fully if film requires to have excellent water-resistance, chainextender uses dibasic alcohol or the diamine that does not contain ionic group, and vinyl monomer also adopts the compound of hydrophobic methacrylic ester or esters of acrylic acid.
The present invention is the molecular weight that base polyurethane prepolymer for use as chain extension in the presence of olefin monomer is increased polymkeric substance, in the presence of dispersing auxiliary high-molecular weight urethane is dispersed in the water, and the addition polymerization of carrying out alkene then is to improve polymer properties.The present invention has overcome the defective of prior art, and can give the performance of the various excellences of goods according to the needs of thin-film material, in the reaction process, do not use thinners such as acetone, do not have crosslinking reaction to take place yet, needn't add other components in the use, with low cost, technology is simpler, and stability of emulsion, becomes the film toughness height.
Following examples are used for further illustrating technological process of the present invention:
Embodiment 1:
By PTMG (Mw=1000) and ditan-4, the prepolymer and 1 of 4`-vulcabond preparation, the 4-butanols is chain extension in the presence of the vinyl monomer Jia Jibingxisuanyizhi, then in the presence of a small amount of deflocculant, disperse with distilled water, behind the emulsion-stabilizing, carry out the polyreaction of methyl-prop diluted acid ethyl ester, finally obtain the high-strength polyurethane water dispersion.Concrete steps are as follows; in the 2000ml three-necked bottle, add average mark through processed in the PTMG 150g (hydroxyl 0.3mol) of amount 1000; add ditan-4 under nitrogen protection, 4`-vulcabond 75g (isocyanic ester 0.6mol) was in 50 ℃ of pre-polymerizations 1 hour.With 100g ethyl propenoate monomer dilution prepolymer, add 1,4-butyleneglycol 12.6g (hydroxyl 0.28mol) was 50 ℃ of following chain extensions 1 hour.After treating the isocyanic ester complete reaction, system is cooled to 30 ℃, adds the 16.9g Natvosol, add the emulsification of 660g distilled water behind the stirring homogeneous phase.Continue to stir half an hour, treat behind the emulsion-stabilizing temperature to be risen to 50 ℃, add the 0.1g persulfate aqueous solution and the 0.1g sodium pyrosulfate aqueous solution and cause vinyl polymerization, be warming up to 75-80 ℃, back flow reaction 5 hours, be warming up to 90 ℃ residual monomer reaction is finished, remove the stink of acrylate, promptly get high strength water dispersion 840g after the cooling with nitrogen purging.
The solid content 33% of this dispersion, wherein urethane accounts for 70% of total solids level, and Jia Jibingxisuanyizhi accounts for 30% of total solids.Thin-film material tensile strength with this dispersion preparation can reach 35Mpa.
Embodiment 2:
By propylene oxide oxyethane copolyether dibasic alcohol (Mw=1500) 225g (hydroxyl 0.3mol), tolylene diisocyanate 54.9g (isocyanate group 0.63mol) is in the presence of a small amount of dibutyl tin laurate, in 75 ℃ of pre-polymerizations 2 hours.295g makes thinner with Jia Jibingxisuanyizhi, adds 1, and 6-hexylene glycol 17.7g (hydroxyl 0.3mol) was 76 ℃ of following chain extending reactions 2 hours.After question response finishes, system is cooled to 32 ℃, add deflocculant 30g, add the distilled water 1000g emulsification that is dissolved with the tween-80 that accounts for polymers total amount 2%, stirring rises to 50 ℃ with temperature after half an hour, add the 0.3g Ammonium Persulfate 98.5 aqueous solution and 0.3g aqueous potassium hydrogen sulfate and cause vinyl polymerization, be warming up to 80 ℃, back flow reaction 6 hours is warming up to 90 ℃ the residual monomer reaction is finished, remove the stink of acrylic acid ester with nitrogen purging, promptly get high strength water dispersion 1600g after the cooling.
With above-mentioned polyurethane water dispersion pour into glass or tetrafluoroethylene framed in drying at room temperature promptly get film sample.Survey its tensile strength 30Mpa.
Embodiment 3:
Poly-hexanodioic acid 1,4-butanediol ester dibasic alcohol (Mw=2000) 200g (hydroxyl 0.2mol), phenylenedimethylidyne isocyanic ester 47.05g (isocyanate group 0.5mol) is in the presence of a small amount of stannous octoate, in 55 ℃ of pre-polymerizations 2 hours, 164g makes thinner with n-BMA, adds glycol ether 14.8g (hydroxyl 0.28mol) 52 ℃ of following chain extending reactions 2 hours.After question response finishes, system is cooled to 28 ℃, add deflocculant hydroxyethylamyle 23g and add distilled water 800g emulsification, after stirring half an hour temperature is risen to 50 ℃, add the 0.16g Ammonium Persulfate 98.5 aqueous solution and 0.16g aqueous potassium hydrogen sulfate and cause vinyl polymerization, be warming up to 75 ℃, back flow reaction 6.5 hours promptly gets the high strength water dispersion after the cooling.
This dispersion solid content 35%, the therein ethylene based polyalcohol accounts for 40%, becomes film toughness up to 30Mpa.
Embodiment 4:
By polyethylene glycol adipate dibasic alcohol (Mw=1500) 225g (hydroxyl 0.3mol) and 4,4`-dicyclohexyl methane diisocyanate 78.6g (isocyanate group 0.6mol) is in the presence of a small amount of stannous octoate, in 75 ℃ of pre-polymerizations 3 hours, 100g makes thinner with methacrylic acid, adds dimethylol propionic acid 18.7g (hydroxyl 0.28mol) 80 ℃ of following chain extending reactions 2 hours.After question response finishes, system is cooled to 32 ℃, add salt forming agent triethylamine 20g,, stir and after 40 minutes temperature is risen to 55 ℃ with tensio-active agent distilled water 500g emulsification, add the 0.1g Ammonium Persulfate 98.5 aqueous solution and 0.15g aqueous potassium hydrogen sulfate and cause vinyl polymerization, be warming up to 80 ℃, back flow reaction 5.2 hours is warming up to 95 ℃ the residual monomer reaction is finished, remove the stink of acrylate with nitrogen purging, promptly get the high strength water dispersion after the cooling.
This dispersion is pale blue, deposit good stability, film forming possess hydrophilic property.
Embodiment 5:
By polyoxypropyleneglycol (Mw=1500) 225g (hydroxyl 0.3mol) and hexamethylene diisocyanate 53g (isocyanate group 0.63mol) in the presence of a small amount of stearic acid tin, in 70 ℃ of pre-polymerizations 3 hours.77g makes thinner with butyl acrylate, adds piperazine 29.1 (hydroxyl 0.3mol) 65 ℃ of following chain extending reactions 2 hours.After question response finishes, system is cooled to 35 ℃, add polyvinyl alcohol 20g,, stir and after 35 minutes temperature is risen to 50 ℃ with distilled water 500g emulsification, add the 0.12g Ammonium Persulfate 98.5 aqueous solution and 0.1g aqueous potassium hydrogen sulfate and cause vinyl polymerization, be warming up to 65 ℃, back flow reaction 7 hours is warming up to 90 ℃ the residual monomer reaction is finished, remove the stink of acrylic acid ester with nitrogen purging, promptly get high strength water dispersion 1000g after the cooling.Its solid content 50%, film forming is inhibited from yellowing, tensile strength 25Mpa.
Embodiment 6:
By poly-hexanodioic acid one diethyl acetal esterdiol (Mw=1500) 225g (hydroxyl 0.3mol) and different Buddhist and ketone vulcabond 70g (isocyanate group 0.63mol) in the presence of a small amount of dibutyl tin laurate and diethylenetriamine, in 80 ℃ of pre-polymerizations 1 hour.150g makes thinner with methacrylic acid, adds quadrol 8.4 (hydroxyl 0.28mol) 60 ℃ of following chain extending reactions 1 hour.After question response finishes, system is cooled to 30 ℃, add polyvinyl alcohol 20g, with distilled water 600g emulsification, stirring rises to 55 ℃ with temperature after half an hour, add the 0.15g Ammonium Persulfate 98.5 aqueous solution and 0.15g aqueous potassium hydrogen sulfate and cause vinyl polymerization, be warming up to 85 ℃, back flow reaction 5.5 hours is warming up to 88 ℃ the residual monomer reaction is finished, remove the stink of acrylate with nitrogen purging, promptly get high strength water dispersion 900g after the cooling.Its content 30%, film forming softness, tensile strength 25Mpa.
Embodiment 7:
By poly-hexanodioic acid 1,4-butanediol ester glycol (Mw=1500) 225g (hydroxyl 0.3mol) and different Buddhist and ketone vulcabond 70g (isocyanic ester 0.63mol) were in 75 ℃ of pre-polymerizations 4 hours.100g makes thinner with methacrylic acid, adds 1, and 4-butyleneglycol 8.1g (hydroxyl 0.18mol) dimethylol propionic acid 6.7g (hydroxyl 0.1mol) was 75 ℃ of following chain extending reactions 3 hours.After question response finishes, system is cooled to 32 ℃, with distilled water 800g emulsification, stir and after 40 minutes temperature is risen to 48 ℃, add the 0.15g Ammonium Persulfate 98.5 aqueous solution and 0.15g aqueous potassium hydrogen sulfate and cause vinyl polymerization, be warming up to 80 ℃, back flow reaction 5.2 hours, be warming up to 92 ℃ residual monomer reaction is finished, remove the stink of acrylate, promptly get high strength water dispersion 1200g after the cooling with nitrogen purging.
Embodiment 8:
By polyoxypropyleneglycol (Mw=1500) 225g (hydroxyl 0.3mol) and tolylene diisocyanate 54g (isocyanate group 0.63mol) in the presence of a small amount of stearic acid tin, in 80 ℃ of pre-polymerizations 3 hours.180g makes thinner with butyl acrylate, adds 1, and 6-hexylene glycol 17.7 (hydroxyl 0.3mol) was 60-70 ℃ of following chain extending reaction 2 hours.After question response finishes, system is cooled to 31 ℃, add gelatin 20g, with distilled water 500g emulsification, stirring rises to 50 ℃ with temperature after half an hour, add the 0.1g Ammonium Persulfate 98.5 aqueous solution and 0.12g aqueous potassium hydrogen sulfate and cause vinyl polymerization, be warming up to 75 ℃, back flow reaction 6 hours is warming up to 95 ℃ the residual monomer reaction is finished, remove the stink of acrylic acid ester with nitrogen purging, promptly get high strength water dispersion 1000g after the cooling.Its solid content 50%, film forming is inhibited from yellowing, tensile strength 25Mpa.
Claims (8)
1, the preparation method of high strength polyurethane aqueous dispersion, be with aliphatics or aromatic vulcabond and polyester diol or polyether Glycols with 1.5-2.1: 1 mol ratio was carried out prepolymerization reaction 1～6 hour at 40～90 ℃, use in the reaction process or without tin class catalyzer, after it is characterized in that pre-polymerization finishes, add 20～80% the vinyl monomer account for the polymkeric substance total amount and make thinner, and to add with remaining the isocyano mol ratio be that 0.5～0.9: 1 low molecular dibasic alcohol or binary amine chainextender carried out chain extending reaction 1～4 hour, after chain extension finishes, system is cooled to 28～35 ℃, add 2～8% deflocculants that account for the polymkeric substance total amount, in the presence of 0.5～3% tensio-active agent that accounts for the polymkeric substance total amount, carry out water-dispersion, treat to carry out according to a conventional method behind the emulsion-stabilizing polymerization of vinyl monomer.
2, the preparation method of high strength polyurethane aqueous dispersion according to claim 1, it is characterized in that described aliphatics or aromatic diisocyanate, be selected from: 4,4`-phenylbenzene-methane diisocyanate, 1, hexamethylene-diisocyanate, isophorone diisocyanate, tolylene diisocyanate, phenylenedimethylidyne isocyanic ester, 4,4`-dicyclohexyl methane diisocyanate, cyclohexyl diisocyanate.
3, the preparation method of high strength polyurethane aqueous dispersion according to claim 1, it is characterized in that a small amount of triisocyanate and more the polyisocyanates of high functionality participate in prepolymerization reaction.
4, the preparation method of high strength polyurethane aqueous dispersion according to claim 1, it is characterized in that described polyester diol or polyether Glycols, its number-average molecular weight scope is 300-5000, average hydroxyl value scope 30-150, suitable polyester diol is the diacid of selecting oneself, phthalic acid, terephthalic acid, the acid of toxilic acid be selected from ethylene glycol, 1, the 2`-propylene glycol, 1, the 4-butyleneglycol, hexylene glycol, the alcohol preparation of neopentyl glycol, polyether Glycols is the condensation product of propylene oxide or tetrahydrofuran (THF) and dibasic alcohol, dibasic alcohol is selected from ethylene glycol, 1, the 2`-propylene glycol, 1, the 4`-butyleneglycol.
5, the preparation method of high strength polyurethane aqueous dispersion according to claim 4, it is characterized in that described polyester diol or polyether Glycols are selected from PTMG, propylene oxide oxyethane copolyether dibasic alcohol, poly-hexanodioic acid 1,4-butanediol ester glycol, polyethylene glycol adipate dibasic alcohol, polyoxygenated third rare glycol, poly-hexanodioic acid glycol ether esterdiol.
6, the preparation method of high strength polyurethane aqueous dispersion according to claim 1, it is characterized in that described chainextender is low molecular dibasic alcohol or binary amine, be selected from 1,4-butyleneglycol, glycol ether, 1,6-hexylene glycol, quadrol, hexamethylene-diamine, piperazine, dimethylol propionic acid, 2-sodium sulfonate-1,4 butyleneglycol, N methyldiethanol amine.
7, the preparation method of high strength polyurethane aqueous dispersion according to claim 1 is characterized in that described tensio-active agent is tween-80, polyoxyethylene ester.
8, the preparation method of high strength polyurethane aqueous dispersion according to claim 1 is characterized in that described deflocculant is gelatin Walocel MT 20.000PV, polyvinyl alcohol, Sudan Gum-arabic.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101070370B (en) * | 2007-05-25 | 2010-04-14 | 张勇 | Process for polyurethane crosslinking agent for melting spandex fiber |
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| CN102107473A (en) * | 2010-12-10 | 2011-06-29 | 中国化工橡胶株洲研究设计院 | Die for producing water-base polyurethane condom |
| CN103113817B (en) * | 2013-02-06 | 2015-08-19 | 东莞市三基音响科技有限公司 | Outdoor type Polyurethanes coating and spraying coating process thereof |
| TWI577707B (en) * | 2015-10-19 | 2017-04-11 | Nanya Plastics Corp | A method for producing solventless aqueous polyurethane dispersions |
| CN108821726A (en) * | 2018-05-19 | 2018-11-16 | 邵俊轩 | A kind of aqueous polyurethane mortar floor material of organic inorganic hybridization |
| CN109270646B (en) * | 2018-11-29 | 2020-04-03 | 安徽牡东通讯光缆有限公司 | Self-repairing reinforcing material for optical cable and preparation method thereof |
| CN113774522B (en) * | 2021-10-15 | 2023-05-23 | 华峰化学股份有限公司 | Polyurethane elastic fiber with high elongation and high strength and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101070370B (en) * | 2007-05-25 | 2010-04-14 | 张勇 | Process for polyurethane crosslinking agent for melting spandex fiber |
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