CN101280051A - Method for preparing aromatic waterborne polyurethane from reproducible polylol - Google Patents
Method for preparing aromatic waterborne polyurethane from reproducible polylol Download PDFInfo
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- CN101280051A CN101280051A CNA2008100249771A CN200810024977A CN101280051A CN 101280051 A CN101280051 A CN 101280051A CN A2008100249771 A CNA2008100249771 A CN A2008100249771A CN 200810024977 A CN200810024977 A CN 200810024977A CN 101280051 A CN101280051 A CN 101280051A
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Abstract
The invention discloses a method which uses renewable polyol to prepare aromatic waterborne polyurethane; the prepared polyurethane has better film forming performance and excellent mechanical properties of glue film. The method comprises the following procedures: (A) renewable polyol and hydrophilic chain extender are added into a reactor which is provided with a blender and a return condensing tube, then the renewable polyol and hydrophilic chain extender are melted at 90 to 100 DEG C and cooled to 60 to 80 DEG C, then aromatic isocyanate is added, followed by catalyst drop by drop; the mixture in the reactor is stirred and reacted for 3 to 6 hours at 60 to 80 DEG C in the presence of acetone to obtain prepolymer; (B) after the prepolymer is cooled to 30 to 60 DEG C, salt forming reagent is added to neutralize salification; (C) the salifiable prepolymer is cut and dispersed into deionized water and emulsified for 10 to 20min at a rotating speed of 2000-6000r/m, and then chain extender is added at -5 to 20 DEG C for chain extending reaction which lasts for 0.5 to 2 hours; after the acetone is removed through decompression and distillation, the aromatic waterborne polyurethane dispersing liquid is obtained.
Description
Technical field
The present invention relates to a kind of method for preparing aqueous polyurethane, more specifically to a kind of method for preparing aromatic waterborne polyurethane by reproducible polylol.
Background technology
Urethane is a kind of high functionality resin, but need a large amount of solvents in traditional solvent borne polyurethane building-up process, also need to add many organic solvents in the construction process, the volatilization of solvent and the solvent that remains in the goods can constitute a serious threat to workmen and human consumer's health.Enhancing along with people's environmental consciousness, various countries begin VOC content is limited, the poly-ammonia of water-based extremely is to substitute organic solvent as dispersion medium with water, has the tangible value of environmental protection, can be applied to aspects such as coating, tackiness agent, water-based hide finishes, fabric finishing agent, more and more be subject to people's attention.
The development of water-based PU is year surplus in the of existing 50 so far, its commercially produced product also has the history more than 20 years, what actual applicable product used is aliphatics or the cycloaliphatic diisocyanates lower with the water reactive behavior, for example: isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4 '-dicyclohexyl methane diisocyanate (H
12MDI) etc.But, the price of these vulcabond is too high, market value as IPDI is about 8.5 ten thousand yuan/ton, and the market value of the normal diphenylmethanediisocyanate (MDI) that uses of solvent-borne type PU is about 2.3 ten thousand yuan/ton, this just makes much higher than solvent-borne type PU of the raw materials cost of water-based PU, therefore downstream manufacturers is unwilling to use expensive water-based PU to replace solvent-borne type PU for the consideration of cost.
The water-based PU that uses aromatic diisocyanate, especially tolylene diisocyanate (TDI) and diphenylmethanediisocyanate (MDI) is that the whole world actively drops into development product.But when adopting aromatic isocyanate to be raw material, the end of polyurethane prepolymer is aromatic isocyanate group, carry out in the water-dispersion process at it, because the speed of reaction of aromatic isocyanate group functional group and water is very high, most isocyanate group functional group can generate amido with the water reaction and consume, make that remaining isocyanate group functional group very little after the water-dispersion, effectively increase chain reaction to promote the molecular weight of resin and can't provide, cause final rerum natura of resin and mechanical property not good, the commercialization of not having is worth.
For addressing the above problem, US5714561, US5852105, US5905113, EP738750, EP682049, CA2132905, US5334690, US5231130 adopt the aliphatic diisocyanate that mixes part in aromatic diisocyanate, with after overcoming water-dispersion-NCO and water effect and the difficulty that die-offs rapidly, as HADI, HDI, two isocyanic acid tetramethylene diformazan phenyl esters (TMXDI), to make water-based PU, but thus, equally still do not reach the purpose that reduced cost originally.In addition, patent DE19719925A1, DE19 719924A1, US5770264, JP08337767A2, JP07 268055A2, JP07165855A2, US5470907A, CA2081414AA, JP65255587A2, JP05051430A2, JP04103614A2 then is to use " acetone method " preparation aromatic waterborne PU that does not conform with economic benefits and environmental requirement, the processing procedure of product is complicated and time consumption very, and remove acetone because of the need decompression, can cause a large amount of organic solvent waste liquids on the contrary and consume big energy.In addition, still there is disclosed other complicated special methods to have: US5714561, US5306764, US4497932A, JP05222139, JP05222139A2, W09847975A1 is because of its processing procedure complexity, and cost of material is expensive more, also do not meet the inexpensive water-based PU that manufacturing can be vied with each other to see who is the better with solvent-borne type PU one.
Polyester (or polyethers) polyvalent alcohol is to produce one of PU resin main raw material, and it all is to take from petroleum resources basically at present.For example, the CN 1621429A[2005.6.1 of Bayer (China) Co., Ltd.], use based on the polyester polyols of aromatic anhydride pure and mild single based on aliphatics, two or the polyethylene oxide/propylene oxide polyether glycol of polyamines, be used for rigid urethane foam.The U.S. receives your Du suburb CN1668668A[2005.9.14 of company of curtain], use the aromatic polyester polyvalent alcohol; The Germany BASF CN1656140A[2005.8.17 of stock company], the CN 1247656C[2006.3.29 of Yantai Wanhua Polyurethane Co., Ltd], the preparation polyester polyol used hexanodioic acid, neighbour (to) phthalic acid.But, problem such as, price increase in short supply increasingly serious along with global petroleum resources, the substitute of seeking suitable petroleum resources has become the big problem that is concerning national economy.Biological resources are because its recyclability is just obtaining the whole world and paying close attention to widely, and a large amount of biomass resources that use also are a kind of inexorable trends of science and technology, production development in every field.In addition, use petroleum resources also can cause problems such as environmental pollution in a large number.Lipid acid is exactly the more a kind of resource of occupancy volume in numerous biomass resources.By being present in long-chain unsaturated fatty acid in the vegetables oil, can obtain dimeracid at the certain condition reactive polymeric.It is a kind of reproducible resource, has suitable molecular weight, is synthesizing polyester polyvalent alcohol good raw material.Dimeracid is carried out the synthetic of polyester polyol as raw material, not only reduce cost, can also reduce present dependence petroleum resources.China Forests Science Academe Forests Chemical Industry Research Institute's report (CN101066920A), by with vegetables oil through the methyl alcohol alcoholysis, after carry out transesterification reaction again and can get fatty polyol dimer, and be applied to rigid urethane foam, can significantly improve resistance to tearing, intensity and the resistance toheat of product.
Summary of the invention
The objective of the invention is to solve deficiency and the problem that exists in the above-mentioned present technology, a kind of method that is prepared aromatic waterborne polyurethane by reproducible polylol is provided, the aqueous polyurethane that makes has film forming properties preferably, the mechanical property excellence of glued membrane after the film forming.
The present invention is achieved by the following technical solutions:
Of the present inventionly prepare the method for aromatic waterborne polyurethane, may further comprise the steps by reproducible polylol:
(A) in the reactor that agitator and reflux condensing tube are housed, add reproducible polylol and hydrophilic chain extender, after fusing under 90～100 ℃, be cooled to 60～80 ℃ and add aromatic isocyanate, drip catalyzer then, 60～80 ℃ of stirring reactions are 3～6 hours in the presence of acetone, obtain performed polymer;
(B) add in the salt-forming reagent after performed polymer is cooled to 30～60 ℃ and salify;
(C) will in and behind the salify prepolymer that obtains be distributed to emulsification 10～20min in the deionized water at the rotating speed down cut of 2000～6000r/m, add chainextender down at-5～20 ℃ then and carried out chain extending reaction 0.5～2 hour, obtain the aromatic waterborne polyurethane dispersion liquid after decompression steams acetone;
The consumption mass percent proportioning of wherein said aromatic isocyanate, reproducible polylol, catalyzer, hydrophilic chain extender, salt-forming reagent and chainextender is as follows:
Aromatic isocyanate 10～40%
Reproducible polylol 30～80%
Catalyzer 0.05～0.2%
Hydrophilic chain extender 1～15%
Salt-forming reagent 2～12%
Chainextender 0.1～6%
Described regeneration type polyvalent alcohol is the fatty polyol dimer that derives from biomass resource.
In the method that is prepared aromatic waterborne polyurethane by reproducible polylol of the present invention, its used fatty polyol dimer preferred structure formula is as follows: (its preparation method is the disclosed method of CN101066920A for the Chinese patent publication number)
Wherein: n1=1～12; N2=1～10; R=
In the method for preparing aromatic waterborne polyurethane by reproducible polylol of the present invention, its described isocyanic ester is preferably tetramethylene diisocyanate, hexamethylene diisocyanate, ten dimethylene diisocyanates, isophorone diisocyanate, trimethyl cyclohexane vulcabond and 4, the mixture of one or both in 4 '-dicyclohexyl methane diisocyanate; Described catalyzer is preferably dibutyl tin laurate, stannous octoate, tetramethyl butane diamine or triethylenediamine; Described hydrophilic chain extender is preferably one or more the mixture in dihydroxymethyl acetate, dimethylol propionic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid, dihydroxyl half ester, diaminobenzoic acid, amino acid, ethylene oxide glycol, second diamino second semi-annular jade pendant acid sodium and two (hydroxyethyl) aminopropane semi-annular jade pendants acid of the 3-sodium; Described salt-forming reagent is preferably triethylamine, ammoniacal liquor or sodium hydroxide; Described chainextender is preferably one or more the mixture in quadrol, Ursol D, diethylenetriamine, triethylene tetramine, hexanediamine, hydrazine and the isophorone diamine; Described thinner acetone accounts for 5～15% of performed polymer total mass.
The invention has the beneficial effects as follows:
The present invention is that initial raw material prepares aromatic waterborne polyurethane with large number of biological matter resource, reduces a large amount of pollutions of using petroleum resources to environment, has solved raw material problem in short supply; Method technology of the present invention is simple, and production cost is low, and economic benefit is good; The aromatic waterborne polyurethane that makes simultaneously has film forming properties preferably, and the mechanical property excellence of glued membrane after the film forming can be widely used in aspects such as coating, tackiness agent, water-based hide finishes, fabric finishing agent.
Embodiment
Embodiment 1
Raw material:
109.4g fatty polyol dimer
33.6g tolylene diisocyanate (TDI)
7.1g dimethylol propionic acid (DMPA)
5.3g triethylamine (TEA)
1.5g quadrol (EDA)
0.06g dibutyl tin laurate (DBTDL)
336.1g deionized water
In the glass reactor that electric mixer, reflux condensing tube, thermocouple thermometer are housed, add fatty polyol dimer, DMPA, after fusing under 90-100 ℃, be cooled to about 70 ℃ and add TDI, drip DBTDL,, obtain performed polymer in 70 ℃ of stirring reactions 4 hours.Add among the TEA after performed polymer is cooled to 50 ℃ and salify.The prepolymer of neutralization back gained is distributed to deionization at the rotating speed down cut of 2000r/m carries out the about 10min of emulsification in going, at 5 ℃ of adding EDA chain extensions 0.5 hour down, obtaining a solid content is the stable milky aqueous polyurethane dispersing liquid of 30.2wt% then.The dry film of gained is a high gloss clear films, and its wiping of anti-toluene can reach 100 times, and tensile strength is 323kg/cm
2, modulus is 88kg/cm
2, elongation at break is 330%.
Embodiment 2
Raw material:
116.8g fatty polyol dimer
35.8g 4,4 '-diphenylmethanediisocyanate (MDI)
7.1g dihydroxymethyl acetate
5.3g ammoniacal liquor
1.9g Ursol D
0.1g stannous octoate
354.9g deionized water
In the glass reactor that electric mixer, reflux condensing tube, thermocouple thermometer are housed, add fatty polyol dimer, dihydroxymethyl acetate, after fusing under 90-100 ℃, be cooled to about 80 ℃ and add MDI, drip stannous octoate,, obtain performed polymer in 80 ℃ of stirring reactions 3 hours.Add in the ammoniacal liquor after performed polymer is cooled to 55 ℃ and salify.The prepolymer of neutralization back gained is distributed to deionization at the rotating speed down cut of 4000r/m carries out the about 10min of emulsification in going, added the Ursol D chain extension 1.5 hours down at-5 ℃ then, obtaining a solid content is the stable milky aqueous polyurethane dispersing liquid of 32.3wt%.The dry film of gained is insoluble to methylethylketone and toluene, and its wiping of anti-toluene can reach 300 times, and tensile strength is 450kg/cm
2, modulus is 60kg/cm
2, elongation at break is 370%.
Embodiment 3
Raw material:
94.8g fatty polyol dimer
14.1g to phenylene vulcabond (PPDI)
6.1g dimethylolpropionic acid (DMBA)
4.7g sodium hydroxide
1.2g diethylenetriamine
0.1g tetramethyl butane diamine
224.7g deionized water
In the glass reactor that electric mixer, reflux condensing tube, thermocouple thermometer are housed, add fatty polyol dimer, DMBA, after fusing under 90-100 ℃, be cooled to about 75 ℃ and add PPDI, drip tetramethyl butane diamine,, obtain performed polymer in 75 ℃ of stirring reactions 3 hours.Add in the sodium hydroxide after performed polymer is cooled to 45 ℃ and salify.The prepolymer of neutralization back gained is distributed to deionization at the rotating speed down cut of 3000r/m carries out the about 10min of emulsification in going, added the diethylenetriamine chain extension 1.5 hours down at 0 ℃ then, obtaining a solid content is the stable milky aqueous polyurethane dispersing liquid of 35.1wt%.The dry film of gained is insoluble to methylethylketone and toluene, and its wiping of anti-toluene can reach 300 times, and tensile strength is 410kg/cm
2, modulus is 60kg/cm
2, elongation at break is 380%.
Embodiment 4
Raw material:
96.7g fatty polyol dimer
34.9g 4,4 '-diphenylmethanediisocyanate (MDI)
8.4g dihydroxymethyl valeric acid
6.4g triethylamine (TEA)
1.4g triethylene tetramine
0.06g triethylenediamine
380.1g deionized water
In the glass reactor that electric mixer, reflux condensing tube, thermocouple thermometer are housed, add fatty polyol dimer, dihydroxymethyl valeric acid, after fusing under 90-100 ℃, be cooled to about 65 ℃ and add MDI, drip triethylenediamine, in 65 ℃ of stirring reactions 3 hours, obtain performed polymer.Add among the TEA after performed polymer is cooled to 45 ℃ and salify.The prepolymer of neutralization back gained is distributed to deionization at the rotating speed down cut of 3000r/m carries out the about 10min of emulsification in going, added the triethylene tetramine chain extension 1.5 hours down at 0 ℃ then, obtaining a solid content is the stable milky aqueous polyurethane dispersing liquid of 27.6wt%.The dry film of gained is insoluble to methylethylketone and toluene, and its wiping of anti-toluene can reach 600 times, and tensile strength is 400kg/cm
2, modulus is 80kg/cm
2, elongation at break is 400%.
Embodiment 5
Raw material:
152.7g fatty polyol dimer
25.1g to phenylene vulcabond (PPDI)
40.6g tolylene diisocyanate (TDI)
6.7g dihydroxyl half ester
5.1g triethylamine (TEA)
2.1g hexanediamine
0.06g stannous octoate
283.9g deionized water
In the glass reactor that electric mixer, reflux condensing tube, thermocouple thermometer are housed, add fatty polyol dimer, dihydroxyl half ester, after fusing under 90-100 ℃, be cooled to and add PPDI and TDI about 80 ℃, drip stannous octoate, in 80 ℃ of stirring reactions 3 hours, obtain performed polymer.Add among the TEA after performed polymer is cooled to 50 ℃ and salify.The prepolymer of neutralization back gained is distributed to deionization at the rotating speed down cut of 5000r/m carries out the about 10min of emulsification in going, added the hexanediamine chain extension 1.5 hours down at 0 ℃ then, obtaining a solid content is the stable milky aqueous polyurethane dispersing liquid of 45.2wt%.The dry film of gained is insoluble to methylethylketone and toluene, and its wiping of anti-toluene can reach 1000 times, and tensile strength is 360kg/cm
2, modulus is 70kg/cm
2, elongation at break is 320%.
Embodiment 6
Raw material:
133.4g fatty polyol dimer
34.3g 4,4 '-diphenylmethanediisocyanate (MDI)
35.8g to phenylene vulcabond (PPDI)
10.6g diaminobenzoic acid
8.2g triethylamine (TEA)
1.5g hydrazine
0.08g tetramethyl butane diamine
495.2g deionized water
In the glass reactor that electric mixer, reflux condensing tube, thermocouple thermometer are housed, add fatty polyol dimer, diaminobenzoic acid, after fusing under 90-100 ℃, be cooled to and add MDI and PPDI about 75 ℃, drip tetramethyl butane diamine, in 75 ℃ of stirring reactions 3 hours, obtain performed polymer.Add among the TEA after performed polymer is cooled to 50 ℃ and salify.The prepolymer of neutralization back gained is distributed to deionization at the rotating speed down cut of 5000r/m carries out the about 10min of emulsification in going, under 20 ℃, add hydrazine chain extension 1.5 hours then, obtaining a solid content is the stable milky aqueous polyurethane dispersing liquid of 20.2wt%, and the dry film of gained is insoluble to methylethylketone and toluene.
Embodiment 7
Raw material:
153.1g fatty polyol dimer
21.5g P, P '-diphenyl diisocyanate (BPDI)
35.8g tolylene diisocyanate (TDI)
3.9g amino acid
3.0g ethylene oxide glycol
5.2g diaminobenzoic acid
9.1g triethylamine (TEA)
1.5g isophorone diamine
0.08g dibutyl tin laurate (DBTDL)
432.9g deionized water
In the glass reactor that electric mixer, reflux condensing tube, thermocouple thermometer are housed, add fatty polyol dimer, amino acid, diaminobenzoic acid and ethylene oxide glycol, after fusing under 90-100 ℃, be cooled to and add BPDI and TDI about 75 ℃, drip DBTDL, in 75 ℃ of stirring reactions 3 hours, obtain performed polymer.Add among the TEA after performed polymer is cooled to 45 ℃ and salify.The prepolymer of neutralization back gained is distributed to deionization at the rotating speed down cut of 2000r/m carries out the about 10min of emulsification in going, added the isophorone diamine chain extension 1.5 hours down at 10 ℃ then, obtaining a solid content is the stable milky aqueous polyurethane dispersing liquid of 35.1wt%.The dry film of gained is insoluble to methylethylketone and toluene, and its wiping of anti-toluene can reach 1000 times.
Embodiment 8
Raw material:
80.6g fatty polyol dimer
40.0g 4,4 '-diphenylmethanediisocyanate (MDI)
27.8g tolylene diisocyanate (TDI)
10.7g second diamino second semi-annular jade pendant acid sodium
9.9g triethylamine (TEA)
2.8g quadrol (EDA)
0.08g dibutyl tin laurate (DBTDL)
687.2g deionized water
In the glass reactor that electric mixer, reflux condensing tube, thermocouple thermometer are housed, add fatty polyol dimer, second diamino second semi-annular jade pendant acid sodium, after fusing under 90-100 ℃, be cooled to and add MDI and TDI about 65 ℃, drip DBTDL, in the presence of 40.0g acetone,, obtain performed polymer in 65 ℃ of stirring reactions 6 hours.Add among the TEA after performed polymer is cooled to 45 ℃ and salify.The prepolymer of neutralization back gained is distributed to deionization at the rotating speed down cut of 2000r/m carries out the about 10min of emulsification in going, added the EDA chain extension 1.5 hours down at 15 ℃ then, obtaining a solid content is the stable milky aqueous polyurethane dispersing liquid of 20.8wt%.The dry film of gained is insoluble to methylethylketone and toluene, and its wiping of anti-toluene can reach 1000 times.
Embodiment 9
Raw material:
50.2g fatty polyol dimer
18.8g 4,4 '-diphenylmethanediisocyanate (MDI)
21.8g P, P '-diphenyl diisocyanate (BPDI)
3.6g two (hydroxyethyl) aminopropane semi-annular jade pendant acid of 3-sodium
5.4g dimethylol propionic acid (DMPA)
6.0g ammoniacal liquor
0.5g quadrol (EDA)
0.3g isophorone diamine
0.08g dibutyl tin laurate (DBTDL)
425.8g deionized water
In the glass reactor that electric mixer, reflux condensing tube, thermocouple thermometer are housed, add two (hydroxyethyl) aminopropane semi-annular jade pendant acid of fatty polyol dimer, DMPA and 3-sodium, after fusing under 90-100 ℃, be cooled to and add MDI and BPDI about 65 ℃, drip DBTDL, in 65 ℃ of stirring reactions 6 hours, obtain performed polymer.Add in the ammoniacal liquor after performed polymer is cooled to 45 ℃ and salify.The prepolymer of neutralization back gained is distributed to deionization at the rotating speed down cut of 2000r/m carries out the about 10min of emulsification in going, added EDA and isophorone diamine chain extension 1.5 hours down at 10 ℃ then, obtaining a solid content is the stable milky aqueous polyurethane dispersing liquid of 20.3wt%.The dry film of gained is insoluble to methylethylketone and toluene, and its wiping of anti-toluene can reach 1000 times.
Embodiment 10
Raw material:
80.0g fatty polyol dimer
40.0g 4,4 '-diphenylmethanediisocyanate (MDI)
27.8g tolylene diisocyanate (TDI)
16.8g dimethylol propionic acid (DMPA)
9.9g sodium hydroxide
2.1 quadrol (EDA)
0.06g dibutyl tin laurate (DBTDL)
706.4g deionized water
In the glass reactor that electric mixer, reflux condensing tube, thermocouple thermometer are housed, add fatty polyol dimer, DMPA, after fusing under 90-100 ℃, be cooled to and add MDI and TDI about 70 ℃, drip DBTDL,, obtain performed polymer in 70 ℃ of stirring reactions 4 hours.Add in the sodium hydroxide after performed polymer is cooled to 50 ℃ and salify.The prepolymer of neutralization back gained is distributed to deionization at the rotating speed down cut of 6000r/m carries out the about 10min of emulsification in going, at 5 ℃ of adding EDA chain extensions 1.5 hours down, obtaining a solid content is the stable milky aqueous polyurethane dispersing liquid of 20.2wt% then.The dry film tensile strength of gained is 400kg/cm
2, modulus is 160kg/cm
2, elongation at break is 330%.
Embodiment 11
Raw material:
100.0g fatty polyol dimer
40.0g 4,4 '-diphenylmethanediisocyanate (MDI)
34.8g tolylene diisocyanate (TDI)
8.4g dimethylol propionic acid (DMPA)
5.2g second diamino second semi-annular jade pendant acid sodium
10.1 triethylamine (TEA)
2.9g quadrol (EDA)
0.03g dibutyl tin laurate (DBTDL)
402.8g deionized water
Preparation method: in the glass reactor that electric mixer, reflux condensing tube, thermocouple thermometer are housed, add polyester diol, DMPA and second diamino second semi-annular jade pendant acid sodium, after fusing under 90-100 ℃, be cooled to and add MDI and TDI about 70 ℃, drip DBTDL, in 70 ℃ of stirring reactions 5 hours, obtain performed polymer.Add among the TEA after performed polymer is cooled to 50 ℃ and salify.The prepolymer of neutralization back gained is distributed to deionization at the rotating speed down cut of 5000r/m carries out the about 10min of emulsification in going, at 0 ℃ of adding EDA chain extension 2 hours down, obtaining a solid content is the stable milky aqueous polyurethane dispersing liquid of 33.6wt% then.The dry film of gained is insoluble to methylethylketone and toluene, and its wiping of anti-toluene can reach 1000 times, and tensile strength is 420kg/cm
2, modulus is 140kg/cm
2, elongation at break is 380%.
Embodiment 12
Raw material:
58.9g fatty polyol dimer
63.6g P, P '-diphenyl diisocyanate (BPDI)
2.6g dimethylol propionic acid (DMPA)
2.1g triethylamine (TEA)
0.9g quadrol (EDA)
0.7g hydrazine
0.6g triethylene tetramine
0.03g dibutyl tin laurate (DBTDL)
517.6g deionized water
In the glass reactor that electric mixer, reflux condensing tube, thermocouple thermometer are housed, add fatty polyol dimer, DMPA, be warming up to about 70 ℃ and add BPDI, drip DBTDL, in 70 ℃ of stirring reactions 5 hours, obtain performed polymer.Add among the TEA after performed polymer is cooled to 50 ℃ and salify.The prepolymer of neutralization back gained is distributed to deionization at the rotating speed down cut of 5000r/m carries out the about 10min of emulsification in going, added down EDA, hydrazine and triethylene tetramine chain extension 2 hours at 10 ℃ then, obtaining a solid content is the stable milky aqueous polyurethane dispersing liquid of 20.6wt%.The dry film of gained is insoluble to methylethylketone and toluene, and its wiping of anti-toluene can reach 1000 times, and tensile strength is 260kg/cm
2, modulus is 60kg/cm
2, elongation at break is 280%.
Claims (8)
1, a kind ofly prepare the method for aromatic waterborne polyurethane, it is characterized in that may further comprise the steps by reproducible polylol:
(A) in the reactor that agitator and reflux condensing tube are housed, add reproducible polylol and hydrophilic chain extender, after fusing under 90～100 ℃, be cooled to 60～80 ℃ and add aromatic isocyanate, drip catalyzer then, 60～80 ℃ of stirring reactions are 3～6 hours in the presence of acetone, obtain performed polymer;
(B) add in the salt-forming reagent after performed polymer is cooled to 30～60 ℃ and salify;
(C) will in and behind the salify prepolymer that obtains be distributed to emulsification 10～20min in the deionized water at the rotating speed down cut of 2000～6000r/m, add chainextender down at-5～20 ℃ then and carried out chain extending reaction 0.5～2 hour, obtain the aromatic waterborne polyurethane dispersion liquid after decompression steams acetone;
The consumption mass percent proportioning of wherein said aromatic isocyanate, reproducible polylol, catalyzer, hydrophilic chain extender, salt-forming reagent and chainextender is as follows:
Aromatic isocyanate 10～40%
Reproducible polylol 30～80%
Catalyzer 0.05～0.2%
Hydrophilic chain extender 1～15%
Salt-forming reagent 2～12%
Chainextender 0.1～6%
Described regeneration type polyvalent alcohol is the fatty polyol dimer that derives from biomass resource.
2, according to claim 1ly prepare the method for aromatic waterborne polyurethane, it is characterized in that described fatty polyol dimer structural formula is as follows by reproducible polylol:
3, the method for preparing aromatic waterborne polyurethane by reproducible polylol according to claim 1, it is characterized in that described aromatic isocyanate be tolylene diisocyanate, to phenylene vulcabond, 4, his P of 4 '-diphenylmethanediisocyanate, the mixture of one or both in P '-diphenyl diisocyanate.
4, according to claim 1ly prepare the method for aromatic waterborne polyurethane, it is characterized in that described catalyzer is dibutyl tin laurate, stannous octoate, tetramethyl butane diamine or triethylenediamine by reproducible polylol.
5, according to claim 1ly prepare the method for aromatic waterborne polyurethane, it is characterized in that described hydrophilic chain extender is one or more the mixture in dihydroxymethyl acetate, dimethylol propionic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid, dihydroxyl half ester, diaminobenzoic acid, amino acid, ethylene oxide glycol, second diamino second semi-annular jade pendant acid sodium and two (hydroxyethyl) aminopropane semi-annular jade pendants acid of the 3-sodium by reproducible polylol.
6, according to claim 1ly prepare the method for aromatic waterborne polyurethane, it is characterized in that described salt-forming reagent is triethylamine, ammoniacal liquor or sodium hydroxide by reproducible polylol.
7, according to claim 1ly prepare the method for aromatic waterborne polyurethane, it is characterized in that described chainextender is one or more the mixture in quadrol, Ursol D, diethylenetriamine, triethylene tetramine, hexanediamine, hydrazine and the isophorone diamine by reproducible polylol.
8, according to claim 1ly prepare the method for aromatic waterborne polyurethane, it is characterized in that described thinner acetone accounts for 5～15% of performed polymer total mass by reproducible polylol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008100249771A CN101280051A (en) | 2008-05-23 | 2008-05-23 | Method for preparing aromatic waterborne polyurethane from reproducible polylol |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127202A (en) * | 2010-11-30 | 2011-07-20 | 中科院广州化学有限公司 | High-hydrolysis-resistance aqueous polyurethane having dimer acid structural unit and preparation method thereof |
| CN103030775A (en) * | 2012-12-14 | 2013-04-10 | 广州宏昌胶粘带厂 | Waterborne polyurethane emulsion for making waterproof strip and preparation method thereof |
| CN103709361A (en) * | 2013-12-19 | 2014-04-09 | 孙启龙 | Waterborne polyurethane as well as preparation method and use thereof |
| CN106884332A (en) * | 2017-03-27 | 2017-06-23 | 浙江鸿辰新材料科技有限公司 | A kind of elastic polyurethane silk fiber and preparation method thereof |
| CN110294828A (en) * | 2019-05-29 | 2019-10-01 | 华南农业大学 | A kind of aqueous polyurethane and the preparation method and application thereof |
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2008
- 2008-05-23 CN CNA2008100249771A patent/CN101280051A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127202A (en) * | 2010-11-30 | 2011-07-20 | 中科院广州化学有限公司 | High-hydrolysis-resistance aqueous polyurethane having dimer acid structural unit and preparation method thereof |
| CN102127202B (en) * | 2010-11-30 | 2013-01-02 | 中科院广州化学有限公司 | High-hydrolysis-resistance aqueous polyurethane having dimer acid structural unit and preparation method thereof |
| CN103030775A (en) * | 2012-12-14 | 2013-04-10 | 广州宏昌胶粘带厂 | Waterborne polyurethane emulsion for making waterproof strip and preparation method thereof |
| CN103030775B (en) * | 2012-12-14 | 2015-08-26 | 广州宏昌胶粘带厂 | For aqueous polyurethane emulsion making water-proof strip and preparation method thereof |
| CN103709361A (en) * | 2013-12-19 | 2014-04-09 | 孙启龙 | Waterborne polyurethane as well as preparation method and use thereof |
| CN103709361B (en) * | 2013-12-19 | 2015-08-26 | 孙启龙 | A kind of aqueous polyurethane and its production and use |
| CN106884332A (en) * | 2017-03-27 | 2017-06-23 | 浙江鸿辰新材料科技有限公司 | A kind of elastic polyurethane silk fiber and preparation method thereof |
| CN110294828A (en) * | 2019-05-29 | 2019-10-01 | 华南农业大学 | A kind of aqueous polyurethane and the preparation method and application thereof |
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