CN101759843B - Innoxious negative ion aqueous polyurethane and preparation method thereof - Google Patents
Innoxious negative ion aqueous polyurethane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of innoxious negative ion aqueous polyurethane, and aqueous polyurethane prepared by the method. The method comprises the following steps: mixing dicyclohexyl methane diisocyanate and aliphatic diol according to a mol ratio of 2.5 to 4; carrying out reaction for 3 to 5 hours at 70 to 90 DEG C to obtain performed polymers; adding dimethylolbutyric acid with hydrophilic groups for taking the reaction for 3 to 5 hours; adding KOH water solution for emulsifying dispersion; and dripping diamine chain extenders for extending chains to obtain aqueous polyurethane latex emulsion. The invention adopts the aliphatic diisocyanate dicyclohexyl methane diisocyanate resin and the aliphatic polymeric diol, does not contain organic solvents such as NMP, acetone and the like often used for preparing the aqueous polyurethane, and does not contain common use neutralizing agents such as triethylamine and the like. The completely innoxious polyurethane material can be prepared, and the invention can be widely used in the fields of medical and health, food and household articles.
Description
Technical field
The present invention relates to a kind of Synthesis of Waterborne Polyurethane method, be specifically related to a kind of preparation method of innoxious negative ion aqueous polyurethane and the urethane that obtains by this method.
Background technology
Aqueous polyurethane is dispersion medium with water, compares with solvent borne polyurethane, have do not fire, smell is little, energy-conservation, advantage such as easy to operate has been widely used as hide finishes, coating and tackiness agent etc.
Although compare with solvent borne polyurethane, the product performance such as the water tolerance of aqueous polyurethane also have gap.In recent years, Along with people's to healthy, environmental protection requirement improves day by day and the promulgation of relevant laws and regulations of the state, research has a lot of reports to Synthesis of Waterborne Polyurethane.
Patent CN101003613A, CN1405196A, CN1930257A, CN1827690A, CN1918251A, CN1510065A, CN1980964A etc. all have report to Synthesis of Waterborne Polyurethane.In these patents and other bibliographical informations, the aqueous polyurethane preparation method who mentions adopts acetone method mostly, with dimethylolpropionic acid (DMPA) for containing the hydrophilic monomer material to introduce hydrophilic carboxyl, to be neutralizing agent with the tertiary amines material.Because the solubleness of DMPA in ketone, oligopolymer divalent alcohol is lower, all be to be solubility promoter usually when adding DMPA in the performed polymer with N-Methyl pyrrolidone (NMP).The N-Methyl pyrrolidone chronic effect can cause the cns dysfunction, causes the pathology of respiratory organs, kidney and vascular system, and the N-Methyl pyrrolidone boiling point high, finally be difficult for removing and be trapped in the material, must bio-toxicity thereby have.Secondly aqueous polyurethane is a neutralizing agent with tertiary amines material such as triethylamine usually; And triethylamine has strong ammonia smelly, and solubleness is little in water, and this type of aqueous polyurethane can give out the stink of amine; Can work the mischief to human and environment in process of production, make goods that certain toxicity is arranged simultaneously.The 3rd; In previous patent, use aromatic isocyanates such as HDI, IPDI aliphatics carbimide or TDI to be raw material mostly; Carbimide vps such as HDI, IPDI and TDI are high, volatile on the one hand; Be prone in process of production human and environment is worked the mischief, and be the polyurethane material of raw material, in use possibly decompose and produce carcinogenic aromatic amine material with aromatic isocyanate TDI or MDI.This shows; Though the organic solvent in the aqueous polyurethane commonly used etc. has reduced human body, environmentally hazardous substance greatly; But in production, the goods use; Still can produce a certain amount of to human body, the deleterious material of environment, thereby limited in some field the particularly application in field such as health care, food.
Patent CN1995086A discloses a kind of method for preparing aqueous nontoxic degradable polyurethane elastomer, this method with KOH, NaOH be in neutralizing agent, the production process not with an organic solvent, through these methods to eliminate toxicity.But this invention is not used for fear of using solubility promoter NMP and is contained the hydrophilic monomer chainextender; Directly adding water during emulsification stirs to realize that emulsification disperses through powerful in performed polymer simultaneously; Perhaps under the condition of having used DMPA, do not use solubility promoter and directly be used for the performed polymer chain extension, because its pure dissolubility is poor, prepolymerization system presents muddy shape; Be unfavorable for chain extending reaction, the shortcoming of this invention is that the emulsion particle diameter of its preparation is big, the unstable and easy deposition of emulsion, layering.
Summary of the invention
To above technological deficiency, the present invention provides a kind of preparation method of innoxious negative ion aqueous polyurethane emulsion.
The preparation method of innoxious negative ion aqueous polyurethane according to the invention comprises the steps:
A) dicyclohexyl methane diisocyanate is mixed with aliphatics polymerization divalent alcohol, adds catalyzer and at 60-90 ℃, preferred 70-90 ℃ down reaction obtained performed polymer in 1-3 hour;
B) in performed polymer, add the DMBA that contains hydrophilic radical, continue reaction 2-4 hour down at 70-90 ℃;
C) reduce the temperature to 25-35 ℃, stir the deionized water that adding simultaneously contains neutralizing agent at the FLUKE impeller, neutralizing agent concentration is 0.1-0.3mol/l, to the about 25-45% of emulsion solid content, and emulsification 0.2-0.5 hour;
D) in emulsion, add two amine chainextenders, continue emulsification, chain extension 0.5-2 and hour obtain aqueous polyurethane;
Or do
A) dicyclohexyl methane diisocyanate and aliphatics polymerization divalent alcohol, the DMBA that contains hydrophilic radical are mixed, and add catalyzer 60-90 ℃ down reaction obtained performed polymer in 2-5 hour;
B) reduce the temperature to 25-35 ℃, stir the deionized water that adding simultaneously contains neutralizing agent at the FLUKE impeller, neutralizing agent concentration is 0.1-0.3mol/l, to the about 25-45% of emulsion solid content, and emulsification 0.2-0.5 hour;
C) in emulsion, add two amine chainextenders, continue emulsification, chain extension 0.5-2 and hour obtain aqueous polyurethane;
Wherein, said dicyclohexyl methane diisocyanate and aliphatics polymerization divalent alcohol mol ratio 2.5-4: 1, be preferably 2.8-3.2: 1; The mol ratio of polymeric dihydric alcohol, DMBA is 0.5-2.5: 1, be preferably 1.2-1.8: and 1, the mol ratio of dicyclohexyl methane diisocyanate and divalent alcohol, DMBA, aliphatie diamine chainextender total amount is 1.0-1.1, is preferably 1.01-1.05: 1; The DMBA consumption is the 2.5-8% of solid quality, is preferably 3-4.5%; The mole number of neutralizing agent is the 100%-110% of DMBA mole number, and emulsion solid content is 25-45%.
It is raw material that the present invention adopts aliphatic isocyanates, compares with aromatic isocyanates such as MDI, TDI, and the aliphatic isocyanates goods in use can not produce the aromatic amine carcinogenic substance.
Said aliphatic isocyanates includes but not limited to dicyclohexyl methane diisocyanate, isophorone diisocyanate or hexamethylene diisocyanate, preferred dicyclohexyl methane diisocyanate; The aqueous polyurethane that dicyclohexyl methane diisocyanate makes has better mechanics, water tolerance, anti-yellowing property; The volatilization of the relative isophorone diisocyanate of dicyclohexyl methyl hydride diisocyanate resin and hexamethylene diisocyanate still less, this in the aqueous polyurethane production process for operator's safety and environmental protection more.
The inventive method adopts dimethylolpropionic acid (DMBA), compares with dimethylol propionic acid, and the solubleness of DMBA in the oligopolymer divalent alcohol is higher; Fusing point is lower; Therefore when DMBA is introduced prepolymerization reaction system, can reduce the use of toxic organic substance less with perhaps dissolving DMBA without N-Methyl pyrrolidone (NMP) solubility promoter; And the water tolerance that is made aqueous polyurethane by DMBA has an improvement than what DMPA made, has the characteristic of high-modulus, HS, low modulus simultaneously.
In the aqueous polyurethane preparation; Can dicyclohexyl methane diisocyanate and aliphatic polyether divalent alcohol or polyester diol, hydrophilic monomer chainextender DMBA mixed once afterreaction be prepared prepolymer; Prepolymer emulsification, neutralization, chain extension are made big, the skewness of hydrophilic radical in molecular weight of aqueous polyurethane performed polymer viscosity of the single stage method preparation of aqueous polyurethane emulsion, emulsifying effectiveness is relatively poor again.
With the reinforced method of substep; Earlier dicyclohexyl methane diisocyanate is reacted with aliphatic polyether divalent alcohol or polyester diol and make performed polymer; Again with performed polymer and the small molecules diol chain-extension agent chain extension that contains hydrophilic monomer; Prepolymer emulsification dispersion, neutralization, chain extension behind the chain extension are obtained aqueous polyurethane emulsion, and hydrophilic monomer distribution uniform in the prepolymer that makes with the substep feed way, emulsifying effectiveness are better.
Neutralizing agent includes but not limited to NaHCO described in the inventive method
3, KHCO
3Or KOH; Neutralizing agent wherein according to the invention is preferably KOH, is that stability of emulsion, the dispersiveness of neutralizing agent is better with KOH, can obtain blueing light, translucent emulsion; Actual finding when neutralizing agent is selected, is that the outward appearance of emulsion of neutralizing agent is relatively poor, particle diameter big, poor stability with NaOH.
In the inventive method, said aliphatics polymerization divalent alcohol is the aliphatic polyether divalent alcohol or the polyester diol of 600-3000 molecular weight; Or the aliphatic polyether divalent alcohol of 600-3000 molecular weight or polyester diol and molecular weight are lower than the mixture of 400 divalent alcohol;
Aliphatic polyether divalent alcohol or polyester diol that further to be preferably said aliphatics polymerization divalent alcohol be the 1000-2000 molecular weight; Or the aliphatic polyether divalent alcohol of 1000-2000 molecular weight or polyester diol and molecular weight are lower than the mixture of 400 divalent alcohol;
Wherein, in the said aliphatic polyester binary alcohol polycaprolactone divalent alcohol that is the 600-3000 molecular weight, PCDL, the polyester adipate one or more; Said aliphatic polyether divalent alcohol is the PTMG of 600-3000 molecular weight; Further preferred described aliphatic polyester binary alcohol for polycaprolactone divalent alcohol, the PCDL of 1000-2000 molecular weight, gather adipate glycol, polypropylene adipate(PPA) divalent alcohol or poly adipate succinic acid ester divalent alcohol; Said polyether Glycols is the PTMG of 1000-2000 molecular weight.
In the inventive method, it is terepthaloyl moietie, Ucar 35,1 that said molecular weight is lower than 400 divalent alcohol, 4-butyleneglycol, 1,6-pinakon, 1,5-pentanediol, pinakon, glycol ether or NSC 6366.
Diamine chain stretching agent according to the invention is hydrazine, quadrol, tetramethylenediamine, hexanediamine or isophorone diamine, and they have soluble in water, and speed of response is fast, can accomplish the chain extending reaction of performed polymer very soon, residual little characteristics.
Catalyzer according to the invention is a dibutyl tin laurate; The consumption of preferred dibutyl tin laurate is 100-300PPm.
It is a kind of by the prepared aqueous polyurethane of aforesaid method that the present invention also provides, and said aqueous polyurethane can be widely used in the higher food of health requirements, medical and health and household goods field.
The inventive method has overcome in the past, and aqueous polyurethane prepares the toxigenous shortcoming of patented technology possibility; The raw material that possibly produce toxic action in the aqueous polyurethane production technique in the past, technology etc. are improved, so that a kind of toxic aqueous polyurethane that do not have fully to be provided.
At first, the DMBA fusing point that adopts in this patent is low, and solubleness is bigger in the oligopolymer divalent alcohol, need be not solvent with NMP, has eliminated the residual of organic solvent NMP;
Secondly, it is neutralizing agent that this patent adopts KOH, has eliminated the volatilization of organic amine material and residual, does not have bio-toxicity.
Once more, this patent adopts dicyclohexyl methane diisocyanate, compares H with TDI with other the two kinds isocyanic ester IPDI that are usually used in aqueous polyurethane
12The steam of MDI forces down, and volatility is little, and is little to the toxic action of environment and producers' generation in process of production.
At last, compare with conventional fragrant family isocyanic ester, with H
12MDI is a raw material, can in the preparation of emulsion and goods, storage, use, not decompose to produce carcinogenic aromatic amine material.
Compare with previous patent, patent art has following advantage:
One. the dicyclohexyl methane diisocyanate that this patent adopts is an aliphatic isocyanates; Can be in the preparation of emulsion and goods, produce carcinogenic aromatic amine material in storing; It is compared with other a kind of aliphatic isocyanates IPDI that is usually used in aqueous polyurethane simultaneously; Its compound with regular structure, rigidity are bigger, have performances such as better mechanics, calorifics.H in addition
12The steam of MDI forces down, volatility is little, compares with raw materials such as TDI, IPDI, and its toxic action to environment is littler.
Two. it is chainextender that this patent adopts carboxylic DMBA, in molecular chain, introduces hydrophilic radical.Compare with DMPA, the fusing point of DMBA solubleness low, in the oligopolymer divalent alcohol is bigger, need not be solubility promoter with NMP, can effectively reduce the use of organic solvent.
Three. it is neutralizing agent that this patent adopts KOH, and goods do not have bio-toxicity, also can effectively eliminate the harm that the organic amine material volatilization in the aqueous polyurethane production process causes environment simultaneously.
Four. this patent has adopted and has fed intake step by step, the preparation technology of self-emulsifying, and the polyaminoester emulsion particle diameter that makes is little, stability in storage, dispersed better.
Embodiment
For better embodiment of the present invention, through following examples the present invention is further specified but be not limited to these embodiment, to some nonessential improvement and adjustment that the present invention did, still belong to protection domain of the present invention according to content of the present invention.
Main raw material related among the embodiment is originated as follows:
Dicyclohexyl methane diisocyanate (H
12MDI), Yantai Wanhua Polyurethane Co., Ltd produces.
Polyether Glycols:
Polytetrahydrofuran diol (PTMEG, molecular weight 600,1000,2000) Korea S PTG produces, industrial goods;
W 166 (molecular weight 1000,2000), Tianjin three petrochemical iy produced, industrial goods.Polyester diol: polycarbonate diol (PCDL, molecular weight 1000,2000), NPU, industrial goods;
Polycaprolactone glycol (PCL, molecular weight 1000,2000), Solvay company, industrial goods.
Dimethylolpropionic acid (DMBA): Sweden Bai Situo company, industrial goods.
Neutralizing agent: KOH, close europeanized reagent ltd of Tianjin section, reagent.
Chainextender: 1,4-butyleneglycol (BDO), hexanediamine, quadrol, close europeanized reagent ltd of Tianjin section, reagent.
FLUKE emulsify at a high speed dispersion machine, Shanghai Frock Fluid Machinery Manufacture Co., Ltd.;
Solid content testing method: according to GB/T 1725-79.
The tensile property test: testing tool adopts the ZWICK Z005 of company type universal testing machine, tests according to ASTM D882 standard.
The emulsion particle diameter test: testing tool is the zatasizer nano ZS of a Ma Erwen instrument company laser nano particle size analyzer, and probe temperature is 25 ℃.
Stability in storage: get emulsion and place separating centrifuge, spinning is 15 minutes under 3000rpm/min, does not explain that then stability in storage is more than 6 months if there is the deposition generation.
Embodiment 1
In the 3000ml four-hole boiling flask that whisking appliance, condensing reflux pipe, thermopair are housed, add H
12The MDI235.8 gram restrains PTMEG1000 with 300, adds 4 T12 catalyzer, and reaction is 1 hour under 70 ℃, and performed polymer is heated to 80 ℃, and the DMBA that adds 28.7 gram thawings reacted 3 hours, adds 9.54 gram BDO reactions 1 hour again.Performed polymer behind the above-mentioned chain extending reaction is cooled to 30 ℃; Under the 10000r/min high-speed stirring, will contain 12 at FLUKE emulsify at a high speed dispersion machine and restrain in the aqueous solution 1388 gram adding performed polymers of KOH, and disperse to add after 20 minutes quadrol 15.4 gram continuation stirring reactions and obtained white aqueous polyurethane emulsion in 20 minutes.Record emulsion solid content and be 30%, DMBA content 4.87%, particle diameter 80-110nm, film tensile strength 28MPa, elongation at break 860%.
Embodiment 2
In the 3000ml four-hole boiling flask that whisking appliance, condensing reflux pipe, thermopair are housed, add H
12MDI 235.8 grams restrain PTMEG600 with 216, add 4 T12 catalyzer, and reaction is 1 hour under 70 ℃, and performed polymer is heated to 80 ℃, and the DMBA that adds 24.6 gram thawings reacted 3 hours, add 14.9 gram BDO reactions 1 hour again.Performed polymer behind the above-mentioned chain extending reaction is cooled to 30 ℃; At FLUKE emulsify at a high speed dispersion machine under the 10000r/min high-speed stirring; The aqueous solution 1180 gram that will contain 10.2 gram KOH adds performed polymers, disperses to add after 20 minutes quadrol 9.9 gram continuation stirring reactions and obtains translucent, the white aqueous polyurethane emulsion of gala in 20 minutes.Record emulsion solid content and be 30.5%, DMBA content 4.9%, particle diameter 80-100nm, film tensile strength 30.4MPa, elongation at break 830%.
Embodiment 3
In the 3000ml four-hole boiling flask that whisking appliance, condensing reflux pipe, thermopair are housed, add H
12The MDI235.8 gram restrains PTMEG2000 with 600, adds 4 T12 catalyzer, and after 1 hour, the DMBA that in performed polymer, adds 35 gram thawings reacted 3.5 hours in reaction under 80 ℃, adds 6.86 gram BDO reactions 1.5 hours again.Performed polymer behind the above-mentioned chain extending reaction is cooled to 30 ℃; The aqueous solution 1673 gram that under the 10000r/min high-speed stirring, will contain 14.6 gram KOH at FLUKE emulsify at a high speed dispersion machine adds performed polymers, disperses to add after 20 minutes quadrol 4.15 gram continuation stirring reactions and obtains translucent, the white aqueous polyurethane emulsion of gala in 20 minutes.Record emulsion solid content and be 35.2%, DMBA content, particle diameter 95-120nm, film tensile strength 24MPa, elongation at break 890%.
Embodiment 4
In the 3000ml four-hole boiling flask that whisking appliance, condensing reflux pipe, thermopair are housed, add H
12MDI 262 gram and 250 gram PPG1000 add 4 T12 catalyzer, 80 ℃ of reactions after 1 hour down, add the DMBA that 28 grams melt down in the performed polymer at 80 ℃ and answer 3.5 hours, add 20.5 again and restrain BDO and reacted 1.5 hours.Performed polymer behind the above-mentioned chain extending reaction is cooled to 30 ℃; At FLUKE emulsify at a high speed dispersion machine under the 10000r/min high-speed stirring; The aqueous solution 1397 grams that will contain 11.6 gram KOH add in the performed polymer; Disperse to add after 20 minutes hexanediamine 33.1 grams and continued stirring reaction 20 minutes, obtain translucent, the white aqueous polyurethane emulsion of gala.Record emulsion solid content and be 30%, DMBA content 4.7%, particle diameter 85-110nm, film tensile strength 25MPa, elongation at break 960%.
Embodiment 5
In the 3000ml four-hole boiling flask that whisking appliance, condensing reflux pipe, thermopair are housed, add H
12The MDI238.4 gram restrains PCDL1000 with 303, adds 3 T12 catalyzer, and reaction is 1 hour under 60 ℃, and performed polymer is warmed up to 70 ℃, and the DMBA that adds 26.49 gram thawings reacted 3 hours, under 80 ℃, adds 19.65 gram BDO reactions 2 hours again.Performed polymer behind the above-mentioned chain extending reaction is cooled to 30 ℃; Under the 10000r/min high-speed stirring, add the aqueous solution 1427 grams that contain 10.6 gram KOH at FLUKE emulsify at a high speed dispersion machine, disperse to add after 20 minutes hexanediamine 19.33 gram continuation stirring reactions and obtained white aqueous polyurethane emulsion in 20 minutes.Record emulsion solid content and be 30%, DMBA content 4.37%, particle diameter 80-110nm, film tensile strength 35MPa, elongation at break 820%.
Embodiment 6
In the 3000ml four-hole boiling flask that whisking appliance, condensing reflux pipe, thermopair are housed, add H
12The MDI238.4 gram restrains PCDL2000 with 606, adds 3 T12 catalyzer, and reaction is 1.5 hours under 60 ℃, and performed polymer is warmed up to 70 ℃, and the DMBA that adds 40.3 gram thawings reacted 3.5 hours, under 80 ℃, adds 11.25 gram BDO reactions 2.5 hours again.Performed polymer behind the above-mentioned chain extending reaction is cooled to 30 ℃; Under the 10000r/min high-speed stirring, add the aqueous solution 1717 grams that contain 16.8 gram KOH at FLUKE emulsify at a high speed dispersion machine, disperse to add after 20 minutes hexanediamine 19.33 gram continuation stirring reactions and obtained white aqueous polyurethane emulsion in 20 minutes.Record emulsion solid content and be 30%, DMBA content 4.4%, particle diameter 80-110nm, film tensile strength 28MPa, elongation at break 860%.
Embodiment 7
In the 3000ml four-hole boiling flask that whisking appliance, condensing reflux pipe, thermopair are housed, add H
12The MDI262 gram restrains PCL1000 with 333, adds 3 T12 catalyzer, and reaction is 1 hour under 60 ℃, and performed polymer is warmed up to 70 ℃, and the DMBA that adds 31.9 gram thawings reacted 3 hours, under 80 ℃, adds 10.6 gram BDO reactions 2 hours again.Performed polymer behind the above-mentioned chain extending reaction is cooled to 30 ℃; Under the 10000r/min high-speed stirring, add the aqueous solution 1540 grams that contain 13.3 gram KOH at FLUKE emulsify at a high speed dispersion machine, disperse to add after 20 minutes quadrol 17.1 gram continuation stirring reactions and obtained white aqueous polyurethane emulsion in 20 minutes.Record emulsion solid content and be 30%, DMBA content 4.4%, particle diameter 80-100nm, film tensile strength 36MPa, elongation at break 820%.
Embodiment 8
In the 3000ml four-hole boiling flask that whisking appliance, condensing reflux pipe, thermopair are housed, add H
12The MDI262 gram restrains PCL2000 with 666, adds 3 T12 catalyzer, and reaction is 1.5 hours under 60 ℃, and performed polymer is warmed up to 70 ℃, and the DMBA that adds 44.7 gram thawings reacted 3.5 hours, under 80 ℃, adds 12.5 gram BDO reactions 2.5 hours again.Performed polymer behind the above-mentioned chain extending reaction is cooled to 30 ℃; Under the 10000r/min high-speed stirring, add the aqueous solution 1780 grams that contain 18.5 gram KOH at FLUKE emulsify at a high speed dispersion machine, disperse to add after 20 minutes hexanediamine 21.6 gram continuation stirring reactions and obtained white aqueous polyurethane emulsion in 20 minutes.Record emulsion solid content and be 34%, DMBA content 4.4%, particle diameter 90-110nm, film tensile strength 29MPa, elongation at break 860%.
Embodiment 9
In the 500ml four-hole boiling flask that whisking appliance, condensing reflux pipe, thermopair are housed, add H
12MDI238.4 gram and 303 gram PCDL1000 add 3 catalyzer T12, the DMBA that adding 26.49 grams melt under 70 ℃, 19.65 gram BDO 2.5 hours.Above-mentioned performed polymer is cooled to 30 ℃; Under the 10000r/min high-speed stirring, add the aqueous solution 1427 grams that contain 10.6 gram KOH at FLUKE emulsify at a high speed dispersion machine, disperse to add after 20 minutes hexanediamine 19.33 gram continuation stirring reactions and obtained white aqueous polyurethane emulsion in 20 minutes.Record emulsion solid content and be 30%, DMBA content 4.37%, particle diameter 90-120nm, film tensile strength 33MPa, elongation at break 840%.
Claims (11)
1. the preparation method of an innoxious negative ion aqueous polyurethane is characterized in that, said method comprises:
A) dicyclohexyl methane diisocyanate is mixed with aliphatics polymerization divalent alcohol, add catalyzer then and, obtain performed polymer 60-90 ℃ of following reaction 1-3 hour;
B) in performed polymer, add dimethylolpropionic acid, continue reaction 2-4 hour down at 70-90 ℃;
C) reduce the temperature to 25-35 ℃, adopt the FLUKE impeller to stir and add the deionized water that contains neutralizing agent simultaneously, neutralizing agent concentration is 0.1-0.3mol/l, to emulsion solid content be 25-45%, emulsification 0.2-0.5 hour;
D) in emulsion, add two amine chainextenders, continue emulsification, chain extension 0.5-2 and hour obtain aqueous polyurethane; Or do
A) dicyclohexyl methane diisocyanate and aliphatics polymerization divalent alcohol, the DMBA mixture that contains hydrophilic radical add catalyzer 60-90 ℃ down reaction obtained performed polymer in 2-5 hour;
B) reduce the temperature to 25-35 ℃, stir simultaneously at the FLUKE impeller and add the deionized water that contains neutralizing agent, neutralizing agent concentration is 0.1-0.3mol/l, to emulsion solid content be 25-45%, emulsification 0.2-0.5 hour;
C) in emulsion, add two amine chainextenders, continue emulsification, chain extension 0.5-2 and hour obtain aqueous polyurethane;
Wherein, Said dicyclohexyl methane diisocyanate and aliphatics polymerization divalent alcohol mol ratio 2.5-4: 1; The mol ratio of said aliphatics polymerization divalent alcohol, dimethylolpropionic acid is 0.5-2.5: 1; The mol ratio of dicyclohexyl methane diisocyanate and said aliphatics polymerization divalent alcohol, dimethylolpropionic acid, aliphatie diamine chainextender total amount is 1.0-1.1; The dimethylolpropionic acid consumption is the 2.5-8% of solid quality, and the mole number of neutralizing agent is the 100%-110% of dimethylolpropionic acid mole number, and emulsion solid content is 25-45%.
2. preparation method according to claim 1 is characterized in that, said neutralizing agent is NaHCO
3, KHCO
3Or KOH.
3. preparation method according to claim 2 is characterized in that, said aliphatics polymerization divalent alcohol is the aliphatic polyether divalent alcohol or the polyester diol of 600-3000 molecular weight; Or the aliphatic polyether divalent alcohol of 600-3000 molecular weight or polyester diol and molecular weight are lower than the mixture of 400 divalent alcohol.
4. preparation method according to claim 3 is characterized in that, said aliphatics polymerization divalent alcohol is the aliphatic polyether divalent alcohol or the polyester diol of 1000-2000 molecular weight; Or the aliphatic polyether divalent alcohol of 1000-2000 molecular weight or polyester diol and molecular weight are lower than the mixture of 400 divalent alcohol.
5. preparation method according to claim 3 is characterized in that, in the polycaprolactone divalent alcohol that described aliphatic polyester binary alcohol is the 600-3000 molecular weight, PCDL, the polyester adipate one or more; Said aliphatic polyether divalent alcohol is the PTMG of 600-3000 molecular weight.
6. preparation method according to claim 5; It is characterized in that, described aliphatic polyester binary alcohol for polycaprolactone divalent alcohol, the PCDL of 1000-2000 molecular weight, gather adipate glycol, polypropylene adipate(PPA) divalent alcohol or poly adipate succinic acid ester divalent alcohol; Said polyether Glycols is the PTMG of 1000-2000 molecular weight.
7. preparation method according to claim 6 is characterized in that, it is terepthaloyl moietie, Ucar 35,1 that said molecular weight is lower than 400 divalent alcohol, 4-butyleneglycol, 1,6-pinakon, 1,5-pentanediol, pinakon, glycol ether or NSC 6366.
8. preparation method according to claim 7 is characterized in that, said diamine chain stretching agent is hydrazine, quadrol, tetramethylenediamine, hexanediamine or isophorone diamine.
9. preparation method according to claim 8 is characterized in that, said catalyzer is a dibutyl tin laurate.
10. preparation method according to claim 9 is characterized in that, the consumption of said dibutyl tin laurate is 100-300PPm.
11. the anion aqueous polyurethane of the arbitrary said method preparation of claim 1-10.
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Owner name: WANHUA CHEMICAL GROUP CO., LTD. Free format text: FORMER NAME: YANTAI WANHUA POLYURETHANE CO., LTD. |
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Address after: Happiness Road Yantai city Shandong province 264002 No. 7 Yantai Wanhua polyurethane Limited by Share Ltd Patentee after: Wanhua Chemical Group Co., Ltd. Address before: Happiness Road Yantai city Shandong province 264002 No. 7 Yantai Wanhua polyurethane Limited by Share Ltd Patentee before: Yantai Wanhua Polyurethane Co., Ltd. |
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Application publication date: 20100630 Assignee: Wanhua Chemical (Ningbo) Co., Ltd. Assignor: Wanhua chemical (Beijing) Co., Ltd.|Wanhua Chemical Group Co., Ltd. Contract record no.: 2017990000328 Denomination of invention: Innoxious negative ion aqueous polyurethane and preparation method thereof Granted publication date: 20120418 License type: Common License Record date: 20170818 |