CN104004155B - Poly-(carbonic ester-ether) type polyurethane resin and preparation method thereof and leather slurry - Google Patents
Poly-(carbonic ester-ether) type polyurethane resin and preparation method thereof and leather slurry Download PDFInfo
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- CN104004155B CN104004155B CN201410193127.XA CN201410193127A CN104004155B CN 104004155 B CN104004155 B CN 104004155B CN 201410193127 A CN201410193127 A CN 201410193127A CN 104004155 B CN104004155 B CN 104004155B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/22—Catalysts containing metal compounds
- C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2203/00—Macromolecular materials of the coating layers
- D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06N2203/068—Polyurethanes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2205/00—Condition, form or state of the materials
- D06N2205/02—Dispersion
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1678—Resistive to light or to UV
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Abstract
The invention discloses a kind of poly-(carbonic ester-ether) type polyurethane resin and preparation method thereof and leather slurry, belong to leather slurry technical field.Solve the raw material preparing polyurethane leather slurry in prior art to depend on the catalyst of petroleum chemicals and use and there is the technical problem of potential hazard.The leather slurry of the present invention includes the dimethylformamide of poly-(carbonic ester-ether) type polyurethane resin of 85-120 weight portion, the surfactant of 0.26-0.98 weight portion, the defoamer of 0.42-1.3 weight portion, the levelling agent of 0.13-0.27 weight portion and 128-200 weight portion, wherein, the structural formula of poly-(carbonic ester-ether) type polyurethane resin is shown in formula I.This leather slurry does not rely on petroleum resources, safety and environmental protection, and has hot strength and the elongation at break of excellence, hot strength can up to 60MPa, elongation at break up to 1200%, not yellowing under ultraviolet illumination for a long time.
Description
Technical field
The invention belongs to leather slurry technical field, be specifically related to a kind of poly-(carbonic ester-ether) type polyurethane resin and preparation method thereof and leather slurry.
Background technology
Polyurethane leather slurry is mainly for the production of all kinds of synthetic leather.The good physical properties of the synthetic leather of its production, the index such as intensity, wearability, folding resistance, elongation at break is even better than corium, so being widely applied in fields such as footwear leather, sofa artificial leather, fancy leather and automobile leather.
The production method of polyurethane leather slurry is with polyisocyanates and polyhydric alcohol for raw material, with dimethylformamide (DMF) for solvent, prepares with organotin, Organic leadP, organic mercury or tertiary amine for catalyst reacts at a certain temperature.As patent CN101914285A discloses a kind of polyurethane slurry and preparation method thereof, with organotin or organic amine for catalyst, PEPA, terylene level ethylene glycol, 1.4-butanediol (or 1.3-butanediol), trimethylolpropane and toluene di-isocyanate(TDI) is adopted to be polymerized.For another example patent CN102443131B discloses a kind of non yellowing polyurethane slurry and preparation method thereof, with organotin or organic amine for catalyst, PEPA, terylene level ethylene glycol, 1.4-butanediol (1.3-butanediol or neopentyl glycol), trimethylolpropane and hydrogenation phenyl toluene di-isocyanate(TDI) is adopted to be polymerized.
But, the polyhydric alcohol that above-mentioned preparation method uses is petroleum chemicals, exhaustion day by day along with fossil resources, the preparation making polyurethane leather slurry does not have sustainable development, thus, a kind of synthetic route being independent of or reduce dependence petrochemicals is needed in the preparation in this leather slurry synthesis field badly.nullAnd tertiary amine and organotin、Plumbous、Although the use of the class catalyst such as hydrargyrum greatly facilitate polyurethane slurry production (such as organic tin catalyst be possible not only to improve polyurethane synthetic reaction speed、But also the polyhydric alcohol of different relative molecular mass and the reactivity of isocyanates can be regulated，The polyurethane prepolymer making preparation has narrower molecular weight distribution and relatively low viscosity)，But amine and organotin in synthetic leather、Plumbous、The potential hazard that the residue of hydrargyrum etc. brings to user and Producer，As amines catalyst has potential carcinogenic danger，Organotin、Plumbous、Hydrargyrum class heavy metal catalyst not only results in environmental pollution，Can also result in organism deformity and chronic poisoning，Therefore，Such catalyst is listed in the list prohibitted the use of by developed countries such as European Union，The polyurethane leather export abroad using this type of catalyst is restricted.
Summary of the invention
Present invention aim to address that the raw material preparing polyurethane leather slurry in prior art depends on the catalyst of petroleum chemicals and use and there is the technical problem of potential hazard, it is provided that a kind of poly-(carbonic ester-ether) type polyurethane resin and preparation method thereof and leather slurry.
The structural formula of poly-(carbonic ester-ether) type polyurethane resin of the present invention is shown in formula I:
In formula, m, n is integer, 6≤m≤43,5≤n≤42；
-R1-for the one in following structure:
R2-for the one in following structure:
The preparation method of above-mentioned poly-(carbonic ester-ether) type polyurethane resin of the present invention, comprises the following steps:
(1) in reaction unit, add poly-(carbonic ester-ether) dihydroxylic alcohols of 60-105 weight portion; after decompression distillation; under nitrogen protection; cool to 65-70 DEG C; add the small molecule chain extender of 8.5-14.6 weight portion, be dividedly in some parts the diisocyanate of the dimethylformamide of 168-235 weight, the catalyst of 0.032-0.076 weight portion and 32.4-52.8 weight portion, every batch add after; all react 1-2h, finally obtain the first intermediate product；
The number-average molecular weight of described poly-(carbonic ester-ether) dihydroxylic alcohols is 1500-5000 dalton, and described catalyst is BiCAT4130；
(2) it is warmed up to 80-85 DEG C, in the first intermediate product, add the trimethylolpropane of 3.6-5.3 weight portion, stirring reaction 1-3h, add the methanol of 0.3-0.8 weight portion, continue reaction 0.5-2h, gathered (carbonic ester-ether) type polyurethane resin.
Preferably, described small molecule chain extender is butanediol, ethylene glycol, diglycol or triethylene-glycol.
Preferably, described diisocyanate is 2,4 toluene diisocyanate, dicyclohexyl methyl hydride diisocyanate, methyl diphenylene diisocyanate, isophorone diisocyanate or 1, hexamethylene-diisocyanate.
The present invention also provides for poly-(carbonic ester-ether) the type polyurethane leather slurry containing above-mentioned poly-(carbonic ester-ether) type polyurethane resin, described leather slurry includes poly-(carbonic ester-ether) type polyurethane resin of 85-120 weight portion, the surfactant of 0.26-0.98 weight portion, the defoamer of 0.42-1.3 weight portion, the levelling agent of 0.13-0.27 weight portion and the dimethylformamide of 128-200 weight portion.
Preferably, described surfactant is tween-20, tween-60, tween-80, span-60, span-80 or OP-10.
Preferably, described defoamer is BYK-065, BYK-066, BYK-070, BYK-088, BYK-141, BYK-020 or BYK-080.
Preferably, described levelling agent is BYK-354, BYK-355, BYK-361, BYK-380, BYK-381 or BYK-390.
The preparation method that the present invention also provides for above-mentioned poly-(carbonic ester-ether) type polyurethane leather slurry:
Poly-(carbonic ester-ether) type polyurethane resin of 85-120 weight portion, the surfactant of 0.26-0.98 weight portion, the defoamer of 0.42-1.3 weight portion, the levelling agent of 0.13-0.27 weight portion and the dimethylformamide of 128-200 weight portion are joined in reaction unit, stirring, to thickness, is gathered (carbonic ester-ether) type polyurethane leather slurry.
Preferably, described mixing speed is 1800-2000rpm, and mixing time is 30-45min.
Beneficial effects of the present invention:
(1) present invention uses poly-(carbonic ester-ether) dihydroxylic alcohols and synthesized polyurethane resin as soft section, and then obtain polyurethane leather slurry through formulation optimization, reduce the dependence to fossil resources of the existing polyurethane leather slurry；
(2) preparation method of polyurethane resin of the present invention uses organic zirconium catalyst, do not contain the heavy metal such as stannum, hydrargyrum, make the leather slurry environmental protection more finally given, simultaneously, NCO/OH reaction is had high selectivity by organic zirconium, has efficiently controlled the polymerization of polyurethane resin；
(3) the polyurethane leather slurry that the present invention is soft section of preparation with poly-(carbonic ester-ether) dihydroxylic alcohols, there is hot strength and the elongation at break of excellence, hot strength can up to 60MPa, and elongation at break is up to 1200% and long-term not yellowing in ultraviolet illumination use procedure；
(4) the preparation production technology of polyurethane leather slurry of the present invention is simple, easily operation, hardening time are short.
Accompanying drawing explanation
Fig. 1 is the nuclear magnetic spectrogram of poly-(carbonic ester-ether) type polyurethane resin of the embodiment of the present invention 1 preparation.
Detailed description of the invention
In order to further appreciate that the present invention, below in conjunction with detailed description of the invention, the preferred embodiments of the invention are described, but it is to be understood that these describe simply as further illustrating the features and advantages of the present invention rather than limiting to the claimed invention.
Poly-(carbonic ester-ether) type polyurethane resin structural formula such as Formulas I:
In formula, m, n is integer, 6≤m≤43,5≤n≤42；
-R1-for the one in following structure:
R2-for the one in following structure:
Preferably, the preparation method of above-mentioned poly-(carbonic ester-ether) type polyurethane resin is:
(1) adding poly-(carbonic ester-ether) dihydroxylic alcohols of 60-105 weight portion in reaction unit, be warmed up to 110 DEG C, reduce pressure 1-1.5h；Under nitrogen protection; cool to 65-70 DEG C; add the small molecule chain extender of 8.5-14.6 weight portion; for preventing reaction sudden and violent poly-; (namely dimethylformamide, catalyst and diisocyanate are divided into three parts to add the diisocyanate of the dimethylformamide of 168-235 weight portion, the catalyst of 0.032-0.076 weight portion and 32.4-52.8 weight portion in three batches; every batch adds a dimethylformamide, a catalyst and a diisocyanate); every batch adds; reaction 1-2h; three batches all add and react after, obtain the first intermediate product；
(2) it is warmed up to 80-85 DEG C, continue to obtain the trimethylolpropane of addition 3.6-5.3 weight portion in the reaction unit of the first intermediate product toward step (1), stirring reaction 1-3h, add 0.3-0.8 parts by weight Methanol, continue reaction 0.5-2h, gathered (carbonic ester-ether) type polyurethane resin.
In the present invention, the structural formula of poly-(carbonic ester-ether) dihydroxylic alcohols isIn formula, m, n is integer, 6≤m≤43,5≤n≤42；The number-average molecular weight of poly-(carbonic ester-ether) dihydroxylic alcohols is 1500-5000 dalton, prepares according to CN102432857；Catalyst is BiCAT4130 (leading chemical company of the U.S. produces)；Small molecule chain extender is butanediol, ethylene glycol, diglycol or triethylene-glycol；Diisocyanate is 2,4 toluene diisocyanate, dicyclohexyl methyl hydride diisocyanate, methyl diphenylene diisocyanate, isophorone diisocyanate or 1, hexamethylene-diisocyanate.
Poly-(carbonic ester-ether) the type polyurethane leather slurry of the present invention includes the dimethylformamide of poly-(carbonic ester-ether) type polyurethane resin of 85-120 weight portion, the surfactant of 0.26-0.98 weight portion, the defoamer of 0.42-1.3 weight portion, the levelling agent of 0.13-0.27 weight portion and 128-200 weight portion.Various additives can also be included.
In leather slurry, the structural formula of poly-(carbonic ester-ether) type polyurethane resin is shown in formula I, surfactant, levelling agent and defoamer all can pass through commercially available, the effect of surfactant is the surface tension reducing leather slurry at substrate surface, and surfactant is tween-20, tween-60, tween-80, span-60, span-80 or OP-10；The effect of levelling agent is to make leather slurry have good levelling effect at substrate surface, BYK-354, BYK-355, BYK-361, BYK-380, BYK-381 or BYK-390 that levelling agent can produce for BYK company；The effect of defoamer is to eliminate leather slurry at the bubble used or produce in whipping process, BYK-065, BYK-066, BYK-070, BYK-088, BYK-141, BYK-020 or BYK-080 that defoamer can produce for BYK company.
The preparation method of above-mentioned poly-(carbonic ester-ether) type polyurethane leather slurry is: under room temperature, poly-(carbonic ester-ether) type polyurethane resin of 85-120 weight portion, the surfactant of 0.26-0.98 weight portion, the defoamer of 0.42-1.3 weight portion, the levelling agent of 0.13-0.27 weight portion and the dimethylformamide of 128-200 weight portion are joined in material-compound tank, 1800-2000rpm stirs 30-45min, is gathered (carbonic ester-ether) type polyurethane leather slurry.
Describe the present invention below in conjunction with embodiment and accompanying drawing.
Embodiment 1
The preparation of poly-(carbonic ester-ether) type polyurethane resin (m=10, n=5):
Adding poly-(carbonic ester-ether) dihydroxylic alcohols (number-average molecular weight 1500) of 60g in there-necked flask, be warmed up to 110 DEG C, reduce pressure 1h；Under nitrogen protection, cool to 65 DEG C, add 8.5g butanediol; add the dicyclohexyl methyl hydride diisocyanate of the dimethylformamide of 168g, the BiCAT4130 catalyst of 0.032g and 32.4g in three batches; every batch add after, react 1h, after three batch reactions are complete; it is warmed up to 80 DEG C; continue to add 3.6g trimethylolpropane, stirring reaction 1h in there-necked flask, add 0.3g methanol; continue reaction 0.5h, gathered (carbonic ester-ether) type polyurethane resin.
Fig. 1 is the proton nmr spectra (CDCl of poly-(carbonic ester-ether) type polyurethane resin of embodiment 1 preparation3), it can be seen that HNMR (CDCl3): 1.14ppm, 1.34ppm, 1.51ppm, 1.61ppm, 1.98ppm, 2.19ppm, 2.33ppm, 2.40ppm, 2.90ppm, 2.98ppm, 3.58ppm, 4.05ppm, 4.21ppm, 4.57ppm4.88ppm, 5.02ppm, 7.12ppm, 7.28ppm, 8.04ppm.
Embodiment 2
The preparation of poly-(carbonic ester-ether) type polyurethane resin (m=43, n=9):
Adding poly-(carbonic ester-ether) dihydroxylic alcohols (number-average molecular weight 5000) of 105g in there-necked flask, be warmed up to 110 DEG C, reduce pressure 1.5h；Under nitrogen protection, cool to 70 DEG C, add 14.6g ethylene glycol small molecule chain extender; add the 2,4 toluene diisocyanate of the dimethylformamide of 235g, the BiCAT4130 catalyst of 0.076g and 52.8g in three batches, every batch add after; reaction 2h; after three batch reactions are complete, it is warmed up to 85 DEG C, continues to add 5.3g trimethylolpropane in there-necked flask; stirring reaction 3h; add 0.8g methanol, continue reaction 2h, gathered (carbonic ester-ether) type polyurethane resin.
The proton nmr spectra of poly-(carbonic ester-ether) type polyurethane resin of embodiment 2 preparation, HNMR (CDCl3): 1.16ppm, 1.38ppm, 1.54ppm, 1.67ppm, 2.01ppm, 2.20ppm, 2.31ppm, 2.42ppm, 2.93ppm, 3.01ppm, 3.55ppm, 4.07ppm, 4.23ppm, 4.59ppm4.92ppm, 5.04ppm, 7.15ppm, 7.26ppm, 8.07ppm.
Embodiment 3
The preparation of poly-(carbonic ester-ether) type polyurethane resin (m=6, n=21):
Adding poly-(carbonic ester-ether) dihydroxylic alcohols (number-average molecular weight 2000) of 76g in there-necked flask, be warmed up to 110 DEG C, reduce pressure 1h；Under nitrogen protection, cool to 68 DEG C, add the diglycol small molecule chain extender of 9.7g; add the isophorone diisocyanate of the dimethylformamide of 186g, the BiCAT4130 catalyst of 0.046g and 39.8g in three batches; every batch add after, react 1.5h, after three batch reactions are complete; it is warmed up to 82 DEG C; continue to add 4.1g trimethylolpropane, stirring reaction 2h in there-necked flask, add 0.5g methanol; continue reaction 1h, gathered (carbonic ester-ether) type polyurethane resin.
The proton nmr spectra of poly-(carbonic ester-ether) type polyurethane resin of embodiment 3 preparation, HNMR (CDCl3): 1.10ppm, 1.35ppm, 1.50ppm, 1.62ppm, 1.95ppm, 2.17ppm, 2.30ppm, 2.41ppm, 2.92ppm, 2.96ppm, 3.55ppm, 4.08ppm, 4.23ppm, 4.59ppm4.90ppm, 5.04ppm, 7.10ppm, 7.29ppm, 8.05ppm.
Embodiment 4
The preparation of poly-(carbonic ester-ether) type polyurethane resin (m=15, n=23):
Adding poly-(carbonic ester-ether) dihydroxylic alcohols (number-average molecular weight 3000) of 85g in there-necked flask, be warmed up to 110 DEG C, reduce pressure 1h；Under nitrogen protection, cool to 67 DEG C, add 10.3g triethylene-glycol small molecule chain extender; add the dicyclohexyl methyl hydride diisocyanate of the dimethylformamide of 176g, the BiCAT4130 catalyst of 0.053g and 45.1g in three batches; every batch add after, react 1h, after three batch reactions are complete; it is warmed up to 80 DEG C; continue to add 4.8g trimethylolpropane, stirring reaction 2.5h in there-necked flask, add 0.6g methanol; continue reaction 1.5h, gathered (carbonic ester-ether) type polyurethane resin.
The proton nmr spectra of poly-(carbonic ester-ether) type polyurethane resin of embodiment 4 preparation, HNMR (CDCl3): 1.17ppm, 1.38ppm, 1.54ppm, 1.63ppm, 2.04ppm, 2.23ppm, 2.35ppm, 2.44ppm, 2.94ppm, 2.97ppm, 3.61ppm, 4.08ppm, 4.26ppm, 4.59ppm4.92ppm, 5.04ppm, 7.17ppm, 7.26ppm, 8.09ppm.
Embodiment 5
The preparation of poly-(carbonic ester-ether) type polyurethane resin (m=22, n=19):
Adding poly-(carbonic ester-ether) dihydroxylic alcohols (number-average molecular weight 3500) of 88g in there-necked flask, be warmed up to 110 DEG C, reduce pressure 1.5h；Under nitrogen protection, cool to 70 DEG C, add 11.8g butanediol small molecule chain extender; add in three batches the dimethylformamide of 206g, the BiCAT4130 catalyst of 0.058g and 43.8 methyl diphenylene diisocyanate; every batch add after, react 1.5h, after three batch reactions are complete; it is warmed up to 80 DEG C; continue to add 4.7g trimethylolpropane, stirring reaction 2.5h in there-necked flask, add 0.7g methanol; continue reaction 1h, gathered (carbonic ester-ether) type polyurethane resin.
The proton nmr spectra of poly-(carbonic ester-ether) type polyurethane resin of embodiment 5 preparation, HNMR (CDCl3): 1.10ppm, 1.35ppm, 1.50ppm, 1.64ppm, 1.93ppm, 2.17ppm, 2.35ppm, 2.44ppm, 2.91ppm, 3.02ppm, 3.60ppm, 4.07ppm, 4.24ppm, 4.58ppm4.86ppm, 5.05ppm, 7.14ppm, 7.27ppm, 8.01ppm.
Embodiment 6
The preparation of poly-(carbonic ester-ether) type polyurethane resin (m=20, n=42):
Adding poly-(carbonic ester-ether) dihydroxylic alcohols (number-average molecular weight 4500) of 100g in there-necked flask, be warmed up to 110 DEG C, reduce pressure 1.5h；Under nitrogen protection, cool to 68 DEG C, add 13.5g ethylene glycol small molecule chain extender; add the 1 of the dimethylformamide of 220g, the BiCAT4130 catalyst of 0.065g and 49.8g in three batches, hexamethylene-diisocyanate, every batch add after; reaction 2h; after three batch reactions are complete, it is warmed up to 85 DEG C, continues to add 4.9g trimethylolpropane in there-necked flask; stirring reaction 2h; add 0.6g methanol, continue reaction 1.5h, gathered (carbonic ester-ether) type polyurethane resin.
The proton nmr spectra of poly-(carbonic ester-ether) type polyurethane resin of embodiment 6 preparation, HNMR (CDCl3): 1.12ppm, 1.35ppm, 1.54ppm, 1.67ppm, 2.04ppm, 2.22ppm, 2.35ppm, 2.47ppm, 2.99ppm, 3.61ppm, 4.07ppm, 4.28ppm, 4.63ppm4.90ppm, 5.04ppm, 7.16ppm, 7.26ppm, 8.11ppm.
Embodiment 7
The preparation of poly-(carbonic ester-ether) type polyurethane leather slurry:
Material rate according to table 1, under room temperature, poly-(carbonic ester-ether) type polyurethane resin, surfactant, defoamer, levelling agent and the dimethylformamide that are obtained by embodiment 1-6 join in material-compound tank, stir 30-45min with the speed of 1800-2000rpm, gathered (carbonic ester-ether) type polyurethane leather slurry.It is respectively labeled as PU01, PU02, PU03, PU04, PU05 and PU06.
Material rate prepared by poly-(carbonic ester-ether) the type polyurethane leather slurry of table 1
PU01 that embodiment 7 is obtained, PU02, PU03, PU04, PU05 and PU06 carry out mechanics properties testing and Detection of Stability respectively, and testing result is as shown in table 2.
Poly-(carbonic ester-ether) type polyurethane leather size performance test result of table 2
Hot strength and percentage elongation are tested according to GB GB/T1040-92.
Obviously, the explanation of above example is only intended to help to understand method and the core concept thereof of the present invention.It should be pointed out that, the those of ordinary skill for described technical field, under the premise without departing from the principles of the invention, it is also possible to the present invention carries out some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.
Claims (8)
1. poly-(carbonic ester-ether) type polyurethane resin, it is characterised in that structural formula shown in formula I:
Formulas I
In formula, m, n is integer, 6≤m≤43,5≤n≤42；
-R1-for the one in following structure:
R2-for the one in following structure:
Described poly-(carbonic ester-ether) type polyurethane resin is prepared by the following method:
(1) in reaction unit, add poly-(carbonic ester-ether) dihydroxylic alcohols of 60-105 weight portion; after decompression distillation; under nitrogen protection; cool to 65-70 DEG C; add the small molecule chain extender of 8.5-14.6 weight portion, be dividedly in some parts the diisocyanate of the dimethylformamide of 168-235 weight portion, the catalyst of 0.032-0.076 weight portion and 32.4-52.8 weight portion, every batch add after; all react 1-2h, finally obtain the first intermediate product；
The number-average molecular weight of described poly-(carbonic ester-ether) dihydroxylic alcohols is 1500-5000 dalton, and described catalyst is BiCAT4130；
Described small molecule chain extender is butanediol, ethylene glycol, diglycol or triethylene-glycol；
Described diisocyanate is 2,4 toluene diisocyanate, dicyclohexyl methyl hydride diisocyanate, methyl diphenylene diisocyanate, isophorone diisocyanate or 1, hexamethylene-diisocyanate；
(2) it is warmed up to 80-85 DEG C, in the first intermediate product, add the trimethylolpropane of 3.6-5.3 weight portion, stirring reaction 1-3h, add the methanol of 0.3-0.8 weight portion, continue reaction 0.5-2h, gathered (carbonic ester-ether) type polyurethane resin.
2. the preparation method of poly-(carbonic ester-ether) type polyurethane resin described in claim 1, it is characterised in that comprise the following steps:
(1) in reaction unit, add poly-(carbonic ester-ether) dihydroxylic alcohols of 60-105 weight portion; after decompression distillation; under nitrogen protection; cool to 65-70 DEG C; add the small molecule chain extender of 8.5-14.6 weight portion, be dividedly in some parts the diisocyanate of the dimethylformamide of 168-235 weight portion, the catalyst of 0.032-0.076 weight portion and 32.4-52.8 weight portion, every batch add after; all react 1-2h, finally obtain the first intermediate product；
The number-average molecular weight of described poly-(carbonic ester-ether) dihydroxylic alcohols is 1500-5000 dalton, and described catalyst is BiCAT4130；
Described small molecule chain extender is butanediol, ethylene glycol, diglycol or triethylene-glycol；
Described diisocyanate is 2,4 toluene diisocyanate, dicyclohexyl methyl hydride diisocyanate, methyl diphenylene diisocyanate, isophorone diisocyanate or 1, hexamethylene-diisocyanate；
(2) it is warmed up to 80-85 DEG C, in the first intermediate product, add the trimethylolpropane of 3.6-5.3 weight portion, stirring reaction 1-3h, add the methanol of 0.3-0.8 weight portion, continue reaction 0.5-2h, gathered (carbonic ester-ether) type polyurethane resin.
3. contain poly-(carbonic ester-ether) type polyurethane leather slurry of poly-(carbonic ester-ether) type polyurethane resin of claim 1, it is characterised in that this leather slurry includes:
。
4. poly-(carbonic ester-ether) type polyurethane leather slurry according to claim 3, it is characterised in that described surfactant is tween-20, tween-60, tween-80, span-60, span-80 or OP-10.
5. poly-(carbonic ester-ether) type polyurethane leather slurry according to claim 3, it is characterised in that described defoamer is BYK-065, BYK-066, BYK-070, BYK-088, BYK-141, BYK-020 or BYK-080.
6. poly-(carbonic ester-ether) type polyurethane leather slurry according to claim 3, it is characterised in that described levelling agent is BYK-354, BYK-355, BYK-361, BYK-380, BYK-381 or BYK-390.
7. the preparation method of poly-(carbonic ester-ether) the type polyurethane leather slurry described in claim 3-6 any one, it is characterized in that, poly-(carbonic ester-ether) type polyurethane resin of 85-120 weight portion, the surfactant of 0.26-0.98 weight portion, the defoamer of 0.42-1.3 weight portion, the levelling agent of 0.13-0.27 weight portion and the dimethylformamide of 128-200 weight portion are joined in reaction unit, stirring, to thickness, is gathered (carbonic ester-ether) type polyurethane leather slurry.
8. the preparation method of poly-(carbonic ester-ether) type polyurethane leather slurry according to claim 7, it is characterised in that described mixing speed is 1800-2000rpm, and mixing time is 30-45min.
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| CN109438655B (en) * | 2018-11-21 | 2021-04-02 | 上海华峰新材料研发科技有限公司 | Carbon dioxide-based polycarbonate ether polyol polyurethane and preparation method and application thereof |
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| CN1865311A (en) * | 2006-04-27 | 2006-11-22 | 中国科学院广州化学研究所 | Polymerized thylene carbonate urethane elastomer and its preparation method |
| WO2012135625A1 (en) * | 2011-03-31 | 2012-10-04 | Dow Global Technologies Llc | Hydrophobic polyester polycarbonate polyols for use in polyurethane applications |
| CN103408715A (en) * | 2013-08-09 | 2013-11-27 | 中科院广州化学有限公司 | Internal crosslinking polypropylene carbonate waterborne polyurethane emulsion and preparation method and application thereof |
| CN103665308A (en) * | 2013-12-11 | 2014-03-26 | 中国科学院长春应用化学研究所 | Elastomer and carbon dioxide-propylene oxide copolymer foamed plastics |
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| CN1865311A (en) * | 2006-04-27 | 2006-11-22 | 中国科学院广州化学研究所 | Polymerized thylene carbonate urethane elastomer and its preparation method |
| WO2012135625A1 (en) * | 2011-03-31 | 2012-10-04 | Dow Global Technologies Llc | Hydrophobic polyester polycarbonate polyols for use in polyurethane applications |
| CN103408715A (en) * | 2013-08-09 | 2013-11-27 | 中科院广州化学有限公司 | Internal crosslinking polypropylene carbonate waterborne polyurethane emulsion and preparation method and application thereof |
| CN103665308A (en) * | 2013-12-11 | 2014-03-26 | 中国科学院长春应用化学研究所 | Elastomer and carbon dioxide-propylene oxide copolymer foamed plastics |
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