CN102093517A - Aqueous polyurethane-acrylate resin for synthetic leather fabrics and preparation method thereof - Google Patents
Aqueous polyurethane-acrylate resin for synthetic leather fabrics and preparation method thereof Download PDFInfo
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Abstract
The invention discloses aqueous polyurethane-acrylate resin for synthetic leather fabrics and preparation method thereof. The aqueous polyurethane-acrylate resin is characterized in that: the main chains of polyurethane molecules contain organic fluorine and organic silicon elements; the side chains of the polyurethane molecules contain double bond groups, which can be crosslinked, and hydrophilic groups. The preparation method is characterized in that: chemically embedding organic fluorine and organic silicon in polyurethane chain segments by using fluoroether-terminated siloxane diol as a macromolecular polyalcohol; performing crosslinking of an acrylate monomer serving as a diluent with the polyurethane having double bonds through radiation polymerization to improve the compatibility of the two kinds of resins; and synchronously improving the solid content of emulsion and the molecular weight of polyurethane by using polyamine as a delayed chain extending agent. The aqueous polyurethane-acrylate resin prepared by the invention is safe, environmentally-friendly and stable in emulsion performance, and the polymer material has high mechanical performance and waterproof and chemical-resistance performance and can be widely used in synthetic leather finishing coat.
Description
Technical field
The invention belongs to the aqueous polyurethane technical field of synthetic leather, particularly a kind of aqueous polyurethane-acrylate resin that is used for synthetic leather fabric and preparation method thereof.
Background technology
Adopt urethane resin to produce the surface layer and the base material of synthetic leather, make synthetic leather have soft natural, soft, the characteristics that kishke feel is strong of gloss.The corium matte polyurethane leather that China utility model patent ZL200720110550.4 proposes scribbles one deck urethane surface layer on the corium fabric layer in front, make product reach the effect of high emulation skin.Because the water-base resin industrialization meets current internationalization chemical product developing direction and trend, it is the important development strategy that substitutes import, competition world market, therefore, the aqueous polyurethane synthetic leather has become one of synthetic leather kind at present with fastest developing speed, and market potential is very huge.
The characteristics advantage of water-based use for synthetic leather urethane is: economic environmental protection, and safety nuisance free, and unanimous on the whole with traditional solvent borne use for synthetic leather urethane on over-all properties, wherein some index is also more superior.Yet general aqueous polyurethane emulsion poor from thickening property, solid content is low, the poor water resistance of latex film, glossiness are lower, the over-all properties of filming is relatively poor, in order to improve the over-all properties of waterborne polyurethane resin better, the broadened application scope needs aqueous polyurethane emulsion is carried out suitable modification.The synthetic method of the Chinese patent application number 200810037699.3 organosilicon polyurethane-acrylic ester ternary composite ionomer emulsions that propose, this method is used organic-silicon-modified PUA polymkeric substance, comprehensive three's excellent properties, can be applied to fields such as textiles, automobile, household electrical appliances, but noxious solvent (comprising acetone, butanone, toluene etc.) and metal ion (sodium ion, potassium ion etc.) in the base polyurethane prepolymer for use as building-up process, have been used, these compounds are contaminate environment not only, and partly remain in the goods, can influence the quality and the performance of product.The organosilicon-modified acrylic urethane heterozygosis water dispersion that Chinese patent ZL03146960.4 proposes, be on the urethane side chain, to introduce the activity double key group, use function organic silicon oxygen alkane monomer and modified with acrylate monomers simultaneously, the dispersion that obtains has good thermotolerance and solvent resistance, but under chemical initiator causes, the transformation efficiency of organo-siloxane monomer and acrylate monomer is not high, the poor water resistance of waterborne polyurethane resin.
Summary of the invention
The objective of the invention is to propose a kind of aqueous polyurethane-acrylate resin that is used for synthetic leather fabric and preparation method thereof, characteristics such as this resin has VOC free, technology is simple, cost is low, water-fast solvent resistance is good.
Its technical scheme is: a kind of aqueous polyurethane-acrylate resin that is used for synthetic leather fabric is characterized in that: the quality with the general reaction thing is a benchmark, contains organic fluorine and organosilicon element on the polyurethane molecular main chain, and content is 3～7%; Contain crosslinkable pair of key group on the polyurethane molecular side chain, content is 2～7.5%; Contain hydrophilic radical on the urethane side chain, content is 1-3.5%; Polyethers and/or polyester and/or polybutadiene segments, content are 20～42%, and polyacrylic ester segment, content are 40～70%.
Described crosslinkable pair of key is meant the two keys in the acrylate group.
A kind of preparation method who is used for the aqueous polyurethane-acrylate resin of synthetic leather fabric, it is characterized in that: the quality with non-aqueous component in the aqueous polyurethane-acrylate is a benchmark, silicone glycols that 2.5～15% fluorine is ether capped and 10～50% macromolecular polyol were 100～120 ℃ of dehydrations 0.5～1.5 hour, the polyisocyanates of adding 10～25% was 80～100 ℃ of reactions 2～4 hours; The hydrophilic compounds of adding 2～7% and 0～3% small molecule chain extender 60～90 ℃ of reactions 1～4 hour, obtain the polyurethane prepolymer that end group is the NCO group, and the apparent viscosity size adds 20～65% acrylate monomer dilution in the reaction process; Change polyurethane prepolymer over to the high speed shear dispersion machine, under 800～4000 rev/mins of high speed shear and 0～20 ℃ of condition, added 2～6% triethylamine reaction 1～3 minute, add again and remove 150～250% ionized waters, obtain the polyaminoester emulsion that end group is the NCO group after 1～5 minute; Under 0～20 ℃, 800～4000 rev/mins high-speed stirring conditions, slowly add 0～5% polyamine and carry out the back chain extension, stir after 1～10 minute, obtain containing the aqueous polyurethane emulsion of acrylate monomer; The aqueous polyurethane emulsion that will contain acrylate monomer places radiant bottles, utilizes
60The Co-gamma-rays is to shine under 90～120Gy/min 4～6 hours at radiation dose, finally obtains the no-solvent type aqueous polyurethane-acrylate resin.
The silicone glycols that described fluorine is ether capped, structural formula is as follows:
Wherein n is 3～20 integer.
Described macromolecular polyol is polycaprolactone polyol (PJ), polycarbonate polyol (PCD), polytetrahydrofuran ethoxylated polyhydric alcohol (PTMG), polyethylene oxide polyvalent alcohol (PEG), poly(propylene oxide) polyvalent alcohol (PPG) and/or hydroxy-terminated polybutadienes (HTTP).
Described polyisocyanates is tolylene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethanediisocyanate (MDI), 1, hexamethylene-diisocyanate (HDI), xylylene diisocyanate (XDI), naphthalene-1,5-vulcabond (NDI), polymethylene multi-phenenyl isocyanate (PAPI), tetramethylxylylene diisocyanate (TMXDI), Methylcyclohexyl diisocyanate (HTDI) and/or dicyclohexyl methane diisocyanate (HMDI).
Described hydrophilic compounds is that dimethylol propionic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid and/or dihydroxymethyl are sad.
Described small molecule chain extender is ethylene glycol, glycol ether, 1,4-butyleneglycol, 2,3-butyleneglycol, 1,6-hexylene glycol, neopentyl glycol, glycol ether, glycerine, sorbyl alcohol, TriMethylolPropane(TMP), hydroxymethyl-cyclohexane, pentaerythritol diacrylate (PEDA), dipentaerythrityl ether tetraacrylate (DPETA) and/or TriMethylolPropane(TMP) mono acrylic ester (TMPMA).
Described acrylate monomer is a methyl methacrylate, methyl acrylate, butyl acrylate, butyl methacrylate, Jia Jibingxisuanyizhi, ethyl propenoate, vinylformic acid, methacrylic acid, methacrylic acid-beta-hydroxy ethyl ester, Hydroxyethyl acrylate, methacrylic acid-β-hydroxypropyl acrylate, Propylene glycol monoacrylate, vinyl cyanide, methacrylonitrile, glycidyl acrylate, glycidyl methacrylate, methacrylic acid ten difluoro heptyl esters, dodecafluorhe-ptylacrylate, methacrylic acid hexafluoro butyl ester and/or vinylformic acid hexafluoro butyl ester.
Described polyamine is quadrol, propylene diamine, hexanediamine, 2-methyl isophthalic acid, 5-pentamethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine and/or different fluorine that ketone diamines.
A kind of aqueous polyurethane-acrylate resin that is used for synthetic leather fabric of the present invention, quality with non-aqueous component in the aqueous polyurethane-acrylate emulsion is a benchmark, mode with macromolecular polyol is keyed in organic fluorine and organosilicon chemistry in the polyurethane chain section, and organic fluorine and organosilyl introducing make polyurethane material have good mechanical property and water-fast chemical resistance; With the acrylate monomer is thinner at last by radio polymerization, not only improve the consistency with urethane resin, and reduced the content of VOC, reduce cost; With the polyamine is the back chainextender, improves the solid content of emulsion and the molecular weight of urethane simultaneously.Use the aqueous polyurethane-acrylate resin of the inventive method preparation, safety and environmental protection, emulsion property is stable, and polymer materials has excellent mechanical property and water-fast chemical resistance, can be widely used in the synthetic leather surface layer.
Description of drawings
Fig. 1 is the infrared absorpting light spectra of the aqueous polyurethane-acrylate resin of the inventive method preparation.
Embodiment
Embodiment 1
The silicone glycols (Mn=2000) that the fluorine of 26 grams is ether capped and the poly(propylene oxide) polyvalent alcohol (Mn=2000) of 64 grams added the Methylcyclohexyl diisocyanate of 23.5 grams 120 ℃ of dehydrations 1 hour, 90 ℃ of reactions 4 hours; Add the dimethylol propionic acid of 6.8 grams and the pentaerythritol diacrylate of 1.7 grams,, add the vinyl cyanide dilution of the methyl acrylate and 30 grams of 30 grams in the reaction process, obtain the polyurethane prepolymer that end group is the NCO group 80 ℃ of reactions 3 hours; Change polyurethane prepolymer over to the high speed shear dispersion machine, under 800 rev/mins of high speed shear and 20 ℃ of conditions, add the 5.2 triethylamine reactions that restrain 2 minutes, add the water of 340 grams again, obtain the polyaminoester emulsion that end group is the NCO group after 5 minutes; Be lower than under 20 ℃, the 4000 rev/mins high-speed stirring conditions, the quadrol that slowly adds 1.86 grams carries out the back chain extension, stirs after 5 minutes, obtains aqueous polyurethane emulsion; The aqueous polyurethane emulsion that will contain acrylate monomer places radiant bottles, utilizes
60The Co-gamma-rays is to shine 4 hours under the 120Gy/min at radiation dose, finally obtains the no-solvent type aqueous polyurethane-acrylate resin.
Accompanying drawing 1 has provided the Fourier transform infrared spectroscopy figure of present embodiment final product.As seen from the figure, urethane charateristic avsorption band (N-H:3330cm has appearred in the spectrogram
-1C=O:1705cm
-1And C-N:1540cm
-1), siloxanes charateristic avsorption band (Si-O-Si:1110cm
-1), the charateristic avsorption band (Si-CH of silicon methyl
3: 805cm
-1), the absorption peak (C-F:1290cm of carbon-fluorine bond
-1And 690cm
-1C-H (CF
2H): 970cm
-1) and the charateristic avsorption band (C-O-C:1150cm of polyacrylic ester
-1And C-H:1450cm
-1), and the charateristic avsorption band of isocyanic ester and carbon-carbon double bond does not occur, and illustrates that the ether capped polysiloxane polyhydric alcohol of fluorine is access in the urethane, acrylate monomer also inserts in the segment of polymkeric substance by radiation polymerization.
Analytical results by above-mentioned infrared spectrogram proves that the present invention has successfully prepared the aqueous polyurethane-acrylate resin that is used for synthetic leather fabric.
Embodiment 2
The silicone glycols (Mn=2000) that the fluorine of 10 grams is ether capped and the hydroxy-terminated polybutadienes (Mn=2000) of 80 grams added the isophorone diisocyanate of 30 grams 120 ℃ of dehydrations 1 hour, 90 ℃ of reactions 4 hours; The dipentaerythrityl ether tetraacrylate that adds the dimethylolpropionic acid and 3.4 grams of 6.8 grams, 80 ℃ of reactions 3 hours, add methyl methacrylate and the glycidyl acrylate of 25 grams and the methacrylic acid dilution of 5 grams of 30 grams in the reaction process, obtain the polyurethane prepolymer that end group is the NCO group; Change polyurethane prepolymer over to the high speed shear dispersion machine, under 800 rev/mins of high speed shear and 20 ℃ of conditions, add the 5.2 triethylamine reactions that restrain 2 minutes, add the water of 340 grams again, obtain the polyaminoester emulsion that end group is the NCO group after 5 minutes; Be lower than under 20 ℃, the 4000 rev/mins high-speed stirring conditions, the propylene diamine that slowly adds 1.86 grams carries out the back chain extension, stirs after 5 minutes, obtains aqueous polyurethane emulsion; The aqueous polyurethane emulsion that will contain acrylate monomer places radiant bottles, utilizes
60The Co-gamma-rays is to shine 4 hours under the 106Gy/min at radiation dose, finally obtains the no-solvent type aqueous polyurethane-acrylate resin.
The infrared spectrum of gained final product is with accompanying drawing 1.
Embodiment 3
The silicone glycols (Mn=2000) that the fluorine of 26 grams is ether capped and the polyethylene oxide polyvalent alcohol (Mn=2000) of 64 grams added the tolylene diisocyanate of 23.5 grams 120 ℃ of dehydrations 1 hour, 90 ℃ of reactions 4 hours; Add the dihydroxymethyl valeric acid of 6.8 grams and the hydroxymethyl-cyclohexane of 1.7 grams, 80 ℃ of reactions 3 hours, add methyl acrylate and the butyl methacrylate of 20 grams and the dodecafluorhe-ptylacrylate dilution of 10 grams of 30 grams in the reaction process, obtain the polyurethane prepolymer that end group is the NCO group; Change polyurethane prepolymer over to the high speed shear dispersion machine, under 800 rev/mins of high speed shear and 20 ℃ of conditions, add the 5.2 triethylamine reactions that restrain 2 minutes, add the water of 340 grams again, obtain the polyaminoester emulsion that end group is the NCO group after 5 minutes; Be lower than under 20 ℃, the 4000 rev/mins high-speed stirring conditions, your the ketone diamines of different fluorine that slowly adds 1.2 grams carries out the back chain extension, stirs after 5 minutes, obtains aqueous polyurethane emulsion; The aqueous polyurethane emulsion that will contain acrylate monomer places radiant bottles, utilizes
60The Co-gamma-rays is to shine 6 hours under the 90Gy/min at radiation dose, finally obtains the no-solvent type aqueous polyurethane-acrylate resin.
The infrared spectrum of gained final product is with accompanying drawing 1.
Embodiment 4
The silicone glycols (Mn=2000) that the fluorine of 26 grams is ether capped and the polycaprolactone polyol (Mn=2000) of 64 grams add the naphthalene-1 of 23.5 grams 120 ℃ of dehydrations 1 hour, and the 5-vulcabond was 90 ℃ of reactions 4 hours; Add the dihydroxymethyls of 6.8 grams sad and 1.7 restrain 1, the 4-butyleneglycol, 80 ℃ of reactions 3 hours, add the methyl acrylate of 10 grams, the methacrylonitrile of 20 grams and the butyl acrylate dilution of 30 grams in the reaction process, obtain the polyurethane prepolymer that end group is the NCO group; Change polyurethane prepolymer over to the high speed shear dispersion machine, under 800 rev/mins of high speed shear and 20 ℃ of conditions, add the 5.2 triethylamine reactions that restrain 2 minutes, add the water of 340 grams again, obtain the polyaminoester emulsion that end group is the NCO group after 5 minutes; Be lower than under 20 ℃, the 4000 rev/mins high-speed stirring conditions, the triethylene tetramine that slowly adds 0.6 gram carries out the back chain extension, stirs after 5 minutes, obtains aqueous polyurethane emulsion; The aqueous polyurethane emulsion that will contain acrylate monomer places radiant bottles, utilizes
60The Co-gamma-rays is to shine 6 hours under the 95Gy/min at radiation dose, finally obtains the no-solvent type aqueous polyurethane-acrylate resin.
The infrared spectrum of gained final product is with accompanying drawing 1.
Performance embodiment
Aqueous polyurethane-acrylate needs to improve its water resistance owing to contain hydrophilic radical in the molecule segment.The silicone glycols that fluorine among the embodiment 1 is ether capped is changed to PTMG, and the note sample is that the surface property of PUA0 and 4 embodiment gained aqueous polyurethane-acrylate resins is compared, and the result is as shown in table 1:
Table 1
By table 1 data as seen, adopt the water tolerance and the alcohol resistance of the no-solvent type aqueous polyurethane-acrylate resin that the inventive method makes all obviously to be better than the general not aqueous polyurethane-acrylate resin of fluorine silicon.
Claims (10)
1. aqueous polyurethane-acrylate resin that is used for synthetic leather fabric, it is characterized in that: the quality with the general reaction thing is a benchmark, contains organic fluorine and organosilicon element on the polyurethane molecular main chain, and content is 3～7%; Contain crosslinkable pair of key group on the polyurethane molecular side chain, content is 2～7.5%; Contain hydrophilic radical on the urethane side chain, content is 1-3.5%; Polyethers and/or polyester and/or polybutadiene segments, content are 20～42%, and polyacrylic ester segment, content are 40～70%.
2. preparation method who is used for the aqueous polyurethane-acrylate resin of synthetic leather fabric, it is characterized in that: the quality with non-aqueous component in the aqueous polyurethane-acrylate is a benchmark, silicone glycols that 2.5～15% fluorine is ether capped and 10～50% macromolecular polyol were 100～120 ℃ of dehydrations 0.5～1.5 hour, the polyisocyanates of adding 10～25% was 80～100 ℃ of reactions 2～4 hours; The hydrophilic compounds of adding 2～7% and 0～3% small molecule chain extender 60～90 ℃ of reactions 1～4 hour, obtain the polyurethane prepolymer that end group is the NCO group, and the apparent viscosity size adds 20～65% acrylate monomer dilution in the reaction process; Change polyurethane prepolymer over to the high speed shear dispersion machine, under 800～4000 rev/mins of high speed shear and 0～20 ℃ of condition, added 2～6% triethylamine reaction 1～3 minute, add 150～250% water again, obtain the polyaminoester emulsion that end group is the NCO group after 1～5 minute; Under 0～20 ℃, 800～4000 rev/mins high-speed stirring conditions, slowly add 0～5% polyamine and carry out the back chain extension, stir after 1～10 minute, obtain containing the aqueous polyurethane emulsion of acrylate monomer; The aqueous polyurethane emulsion that will contain acrylate monomer places radiant bottles, utilizes
60The Co-gamma-rays is to shine under 90～120Gy/min 4～6 hours at radiation dose, finally obtains the no-solvent type aqueous polyurethane-acrylate resin.
3. the preparation method who is used for the aqueous polyurethane-acrylate resin of synthetic leather fabric according to claim 2 is characterized in that: the silicone glycols that described fluorine is ether capped, and structural formula is as follows:
Wherein n is 3～20 integer.
4. the preparation method who is used for the aqueous polyurethane-acrylate resin of synthetic leather fabric according to claim 2 is characterized in that: described macromolecular polyol is polycaprolactone polyol, polycarbonate polyol, polytetrahydrofuran ethoxylated polyhydric alcohol, polyethylene oxide polyvalent alcohol, poly(propylene oxide) polyvalent alcohol or hydroxy-terminated polybutadienes.
5. the preparation method who is used for the aqueous polyurethane-acrylate resin of synthetic leather fabric according to claim 2, it is characterized in that: described polyisocyanates is tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, 1, hexamethylene-diisocyanate, xylylene diisocyanate, naphthalene-1,5-vulcabond, polymethylene multi-phenenyl isocyanate, tetramethylxylylene diisocyanate, Methylcyclohexyl diisocyanate or dicyclohexyl methane diisocyanate.
6. the preparation method who is used for the aqueous polyurethane-acrylate resin of synthetic leather fabric according to claim 2 is characterized in that: described hydrophilic compounds is that dimethylol propionic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid or dihydroxymethyl are sad.
7. the preparation method who is used for the aqueous polyurethane-acrylate resin of synthetic leather fabric according to claim 2, it is characterized in that: described small molecule chain extender is ethylene glycol, glycol ether, 1,4-butyleneglycol, 2,3-butyleneglycol, 1,6-hexylene glycol, neopentyl glycol, glycol ether, glycerine, sorbyl alcohol, TriMethylolPropane(TMP) and/or hydroxymethyl-cyclohexane.
8. the preparation method who is used for the aqueous polyurethane-acrylate resin of synthetic leather fabric according to claim 2 is characterized in that: described acrylate monomer is a methyl methacrylate, methyl acrylate, butyl acrylate, butyl methacrylate, Jia Jibingxisuanyizhi, ethyl propenoate, vinylformic acid, methacrylic acid, vinyl cyanide, methacrylonitrile, glycidyl methacrylate, glycidyl acrylate, methacrylic acid ten difluoro heptyl esters, dodecafluorhe-ptylacrylate, in methacrylic acid hexafluoro butyl ester and the vinylformic acid hexafluoro butyl ester one or more.
9. the preparation method who is used for the aqueous polyurethane-acrylate resin of synthetic leather fabric according to claim 2, it is characterized in that: described polyamine is quadrol, propylene diamine, hexanediamine, 2-methyl isophthalic acid, 5-pentamethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine or isophorone diamine.
10. the aqueous polyurethane-acrylate resin that is used for synthetic leather fabric according to claim 1 is characterized in that: the described compound that contains crosslinkable pair of key group is pentaerythritol diacrylate, dipentaerythrityl ether tetraacrylate or TriMethylolPropane(TMP) mono acrylic ester.
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