CN101759843A - 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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- CN101759843A CN101759843A CN201010000634A CN201010000634A CN101759843A CN 101759843 A CN101759843 A CN 101759843A CN 201010000634 A CN201010000634 A CN 201010000634A CN 201010000634 A CN201010000634 A CN 201010000634A CN 101759843 A CN101759843 A CN 101759843A
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 53
- 239000004814 polyurethane Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000000839 emulsion Substances 0.000 claims abstract description 42
- 229920000642 polymer Polymers 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 26
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000002009 diols Chemical class 0.000 claims abstract description 14
- 239000004970 Chain extender Substances 0.000 claims abstract description 11
- 125000004427 diamine group Chemical group 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- ARSRBNBHOADGJU-UHFFFAOYSA-N 7,12-dimethyltetraphene Chemical compound C1=CC2=CC=CC=C2C2=C1C(C)=C(C=CC=C1)C1=C2C ARSRBNBHOADGJU-UHFFFAOYSA-N 0.000 claims description 35
- VFZRZRDOXPRTSC-UHFFFAOYSA-N DMBA Natural products COC1=CC(OC)=CC(C=O)=C1 VFZRZRDOXPRTSC-UHFFFAOYSA-N 0.000 claims description 35
- 239000007787 solid Substances 0.000 claims description 18
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 15
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 15
- 229920000570 polyether Polymers 0.000 claims description 15
- 241000935974 Paralichthys dentatus Species 0.000 claims description 14
- -1 polypropylene adipate Polymers 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 229920000728 polyester Polymers 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 238000004945 emulsification Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 claims description 8
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- 229920001610 polycaprolactone Polymers 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 5
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 claims description 4
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 4
- 229920003232 aliphatic polyester Polymers 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- 150000002334 glycols Chemical class 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 2
- NIHJEJFQQFQLTK-UHFFFAOYSA-N butanedioic acid;hexanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCCCC(O)=O NIHJEJFQQFQLTK-UHFFFAOYSA-N 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003960 organic solvent Substances 0.000 abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 4
- 230000036541 health Effects 0.000 abstract description 4
- 230000001804 emulsifying effect Effects 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 abstract 1
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 abstract 1
- 125000005442 diisocyanate group Chemical group 0.000 abstract 1
- 239000004816 latex Substances 0.000 abstract 1
- 229920000126 latex Polymers 0.000 abstract 1
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 13
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 238000009835 boiling Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000009775 high-speed stirring Methods 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 239000012948 isocyanate Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 description 7
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000010257 thawing Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- 231100000331 toxic Toxicity 0.000 description 5
- 230000002588 toxic effect Effects 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 150000004982 aromatic amines Chemical class 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000711 cancerogenic effect Effects 0.000 description 3
- 231100000315 carcinogenic Toxicity 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000001684 chronic effect Effects 0.000 description 1
- 231100000762 chronic effect Toxicity 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000004064 dysfunction Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000007170 pathology Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002792 vascular Effects 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
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 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 dibasic 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 central nervous system dysfunction, causes the pathology of respiratory organs, kidney and vascular system, and N-Methyl pyrrolidone boiling point height, finally is difficult for removing and is 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 vapour pressure height, volatile such as one side HDI, IPDI and TDI, easily human and environment is worked the mischief in process of production, and be the polyurethane material of raw material with aromatic isocyanate TDI or MDI, in use may decompose and produce carcinogenic aromatic amine material.This shows, though the organic solvent in the aqueous polyurethane commonly used etc. has reduced greatly to human body, environmentally hazardous substance, 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, by 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 by powerful in performed polymer simultaneously, perhaps under the condition of having used DMPA, do not use solubility promoter and be directly used in 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, emulsion is unstable and easy precipitation, layering.
Summary of the invention
At above technological deficiency, the invention provides a kind of preparation method of innoxious negative ion aqueous polyurethane emulsion.
The preparation method of innoxious negative ion aqueous polyurethane of the present invention comprises the steps:
A) dicyclohexyl methane diisocyanate is mixed with aliphatics polymerization dibasic 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 homogenizer, 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 be
A) dicyclohexyl methane diisocyanate and aliphatics polymerization dibasic 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 homogenizer, 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, described dicyclohexyl methane diisocyanate and aliphatics polymerization dibasic 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 dibasic 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 part 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.
Described 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), compare with dimethylol propionic acid, the solubleness of DMBA in the oligopolymer dibasic alcohol is higher, fusing point is lower, therefore when DMBA is introduced prepolymerization reaction system, can be less with or dissolve DMBA without N-Methyl pyrrolidone (NMP) solubility promoter, reduce the use of toxic organic substance, and the water tolerance that is made aqueous polyurethane by DMBA has an improvement than what DMPA made, has the characteristic of high-modulus, high strength, low modulus simultaneously.
In the aqueous polyurethane preparation, dicyclohexyl methane diisocyanate and aliphatic polyether dibasic alcohol or polyester diol, hydrophilic monomer chainextender DMBA mixed once afterreaction can 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 dibasic 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 of the present 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, described aliphatics polymerization dibasic alcohol is the aliphatic polyether dibasic alcohol or the polyester diol of 600-3000 molecular weight; Or the aliphatic polyether dibasic alcohol of 600-3000 molecular weight or polyester diol and molecular weight are lower than the mixture of 400 dibasic alcohol;
More preferably described aliphatics polymerization dibasic alcohol is the aliphatic polyether dibasic alcohol or the polyester diol of 1000-2000 molecular weight; Or the aliphatic polyether dibasic alcohol of 1000-2000 molecular weight or polyester diol and molecular weight are lower than the mixture of 400 dibasic alcohol;
Wherein, in the described aliphatic polyester binary alcohol polycaprolactone dibasic alcohol that is the 600-3000 molecular weight, PCDL, the polyester adipate one or more; Described aliphatic polyether dibasic alcohol is the PTMG of 600-3000 molecular weight; The polycaprolactone dibasic alcohol that further preferred described aliphatic polyester binary alcohol is the 1000-2000 molecular weight, PCDL, poly-adipate glycol, polypropylene adipate (PPA) dibasic alcohol or poly adipate succinic acid ester dibasic alcohol; Described polyether Glycols is the PTMG of 1000-2000 molecular weight.
In the inventive method, it is ethylene glycol, propylene glycol, 1 that described molecular weight is lower than 400 dibasic alcohol, 4-butyleneglycol, 1,6-hexylene glycol, 1,5-pentanediol, hexylene glycol, glycol ether or neopentyl glycol.
Diamine chain stretching agent of the present invention is hydrazine, quadrol, butanediamine, hexanediamine or isophorone diamine, and they have soluble in water, and speed of response is fast, can finish the chain extending reaction of performed polymer very soon, residual little characteristics.
Catalyzer of the present 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 described 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 may 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 dibasic 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 not decompose to produce carcinogenic aromatic amine material in the preparation of emulsion and goods, storage, use.
Compare with previous patent, the art of this patent 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, simultaneously it is compared with aliphatic isocyanates IPDI that another is usually used in aqueous polyurethane, 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, introduces hydrophilic radical in molecular chain.Compare with DMPA, the fusing point of DMBA solubleness low, in the oligopolymer dibasic 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
Implement the present invention for better, the present invention will be further described but be not limited to these embodiment by following examples, to some nonessential improvement and adjustment that the present invention did, still belongs to protection domain of the present invention according to content of the present invention.
Main raw material source related among the embodiment is 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;
Polypropylene glycol (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 company limited of Tianjin section, reagent.
Chainextender: 1,4-butyleneglycol (BDO), hexanediamine, quadrol, close europeanized reagent company limited 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, centrifugation is 15 minutes under 3000rpm/min, does not illustrate that then stability in storage is more than 6 months if there is the precipitation generation.
Embodiment 1
In the 3000ml four-hole boiling flask that agitator, 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 aqueous solution 1388 grams that restrain KOH at FLUKE emulsify at a high speed dispersion machine and add in the performed polymers, 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 agitator, 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, to contain 10.2 aqueous solution 1180 grams that restrain KOH and add performed polymers, and disperse to add after 20 minutes quadrol 9.9 gram continuation stirring reactions and obtained 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 agitator, 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 adds 35 gram thawings in performed polymer 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 ℃, under the 10000r/min high-speed stirring, will contain 14.6 aqueous solution 1673 grams that restrain KOH at FLUKE emulsify at a high speed dispersion machine and add performed polymers, and disperse to add after 20 minutes quadrol 4.15 gram continuation stirring reactions and obtained 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 agitator, 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 agitator, 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, adds 19.65 gram BDO reactions 2 hours under 80 ℃ 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 agitator, 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, adds 11.25 gram BDO reactions 2.5 hours under 80 ℃ 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 agitator, 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, adds 10.6 gram BDO reactions 2 hours under 80 ℃ 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 agitator, 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, adds 12.5 gram BDO reactions 2.5 hours under 80 ℃ 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 agitator, 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 (10)
1. the preparation method of an innoxious negative ion aqueous polyurethane is characterized in that, described method comprises:
A) dicyclohexyl methane diisocyanate is mixed with aliphatics polymerization dibasic 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 homogenizer to stir and add the deionized water that contains neutralizing agent simultaneously, 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 be
A) dicyclohexyl methane diisocyanate and aliphatics polymerization dibasic 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 the deionized water that adding simultaneously contains neutralizing agent at the FLUKE homogenizer, 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, described dicyclohexyl methane diisocyanate and aliphatics polymerization dibasic alcohol mol ratio 2.5-4: 1, the mol ratio of polymeric dihydric alcohol, dimethylolpropionic acid is 0.5-2.5: 1, the mol ratio of dicyclohexyl methane diisocyanate and dibasic alcohol, dimethylolpropionic acid, aliphatie diamine chainextender total amount is 1.0-1.1, the dimethylolpropionic acid consumption is the 2.5-8% of solid part quality, 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, described neutralizing agent is NaHCO
3, KHCO
3Or KOH.
3. preparation method according to claim 2 is characterized in that, described aliphatics polymerization dibasic alcohol is the aliphatic polyether dibasic alcohol or the polyester diol of 600-3000 molecular weight; Or the aliphatic polyether dibasic alcohol of 600-3000 molecular weight or polyester diol and molecular weight are lower than the mixture of 400 dibasic alcohol.
4. preparation method according to claim 3 is characterized in that, described aliphatics polymerization dibasic alcohol is the aliphatic polyether dibasic alcohol or the polyester diol of 1000-2000 molecular weight; Or the aliphatic polyether dibasic alcohol of 1000-2000 molecular weight or polyester diol and molecular weight are lower than the mixture of 400 dibasic alcohol.
5. preparation method according to claim 3 is characterized in that, in the polycaprolactone dibasic alcohol that described aliphatic polyester binary alcohol is the 600-3000 molecular weight, PCDL, the polyester adipate one or more; Described aliphatic polyether dibasic alcohol is the PTMG of 600-3000 molecular weight.
6. preparation method according to claim 5, it is characterized in that the polycaprolactone dibasic alcohol that described aliphatic polyester binary alcohol is the 1000-2000 molecular weight, PCDL, poly-adipate glycol, polypropylene adipate (PPA) dibasic alcohol or poly adipate succinic acid ester dibasic alcohol; Described polyether Glycols is the PTMG of 1000-2000 molecular weight.
7. preparation method according to claim 6 is characterized in that, it is ethylene glycol, propylene glycol, 1 that described molecular weight is lower than 400 dibasic alcohol, 4-butyleneglycol, 1,6-hexylene glycol, 1,5-pentanediol, hexylene glycol, glycol ether or neopentyl glycol.
8. preparation method according to claim 7 is characterized in that, described diamine chain stretching agent is hydrazine, quadrol, butanediamine, hexanediamine or isophorone diamine.
9. preparation method according to claim 8 is characterized in that, described catalyzer is a dibutyl tin laurate; The consumption of preferred dibutyl tin laurate is 100-300PPm.
10. the anion aqueous polyurethane of the arbitrary described method preparation of a claim 1-9.
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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 |
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