CN104140515A - Preparation method of high-folding-resistance polyurethane resin for synthetic leather - Google Patents
Preparation method of high-folding-resistance polyurethane resin for synthetic leather Download PDFInfo
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- CN104140515A CN104140515A CN201410298333.7A CN201410298333A CN104140515A CN 104140515 A CN104140515 A CN 104140515A CN 201410298333 A CN201410298333 A CN 201410298333A CN 104140515 A CN104140515 A CN 104140515A
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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
- C08G18/28—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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
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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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- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a preparation method of high-folding-resistance polyurethane resin for synthetic leather. The preparation method of the high-folding-resistance polyurethane resin for the synthetic leather comprises the following steps: firstly, heating polycarbonate glycol, diisocyanate, water, a diamine chain extender, an antioxidant and a catalyst in a solvent for preparing a prepolymer A, wherein diisocyanate is excessive; secondly, heating polyether glycol, diisocyanate, a glycol chain extender, an antioxidant and a catalyst in a solvent for preparing a prepolymer B, wherein polyether glycol is excessive; thirdly, adding the prepolymer B into the prepolymer A, and carrying out polymerization reaction, so that a final product is obtained, wherein ratio of the total mole number of isocyanate groups in the prepolymer A to the total mole number of hydroxyls in the prepolymer B is (1.01-1.015) to 1. The two macromolecular prepolymers are alternately combined by adopting a chemical method, and an alternately arranged 'hard (A)-soft (B)-hard (A)' 'damping' structure is formed, so that the prepared synthetic leather has high folding resistance.
Description
Technical field
The invention belongs to synthetic leather field, relate to the preparation method of the high folding urethane resin of a kind of use for synthetic leather.
Background technology
Instantly, Synthetic Leather is used in the every aspect of people's life due to features such as its unique emulation, weathering resistance, soft adaptive, from furniture to clothes, footwear are to case and bag, automotive trim to outdoor goods, we almost can see Synthetic Leather everywhere.Although yet constantly upgrading and improvement of currently available products, high physical property synthetic leather emerges in an endless stream, but still is difficult to meet the requirement that some specific area is used.Such as automobile hand brake, manual gear parcel leather, stationery outer packaging leather, sports shoes upper leather etc. has to synthetic leather folding quality the harsh requirement of being close to.In life, be not difficult to find, several articles for use that have high requirement for synthetic leather folding resistance of more than enumerating, after using for some time (1-3), surface there will be the cracking phenomena that degree is different, makes people have to its replacing or abandon; As everyone knows, Synthetic Leather present stage is not also recycled means, and therefore discarded synthetic leather is burned or abandon, and environment and people's life are caused to great effect.
Synthetic Leather is repeatedly ftractureing in folding process, its essence is the phenomenon that material ruptures or lost efficacy under cyclic stress effect, and this kind of phenomenon is in use common collapse mode of material.Under the effect of the cyclic stress lower than yielding stress or rupture stress, material internal or the surface stress place of concentrating causes crackle and impels crack propagation, thereby causes final destruction.And the positions such as constraint place that has hole, breach and have a rigidity at material internal and its neighborhood the most easily cause and the phenomenon that stress strengthens make material because stress concentration produces fatigue cracking.Chinese patent CN201210376021.4 has introduced a kind of preparation method of high elongation at tear urethane resin, the method is prepared Resin A by poly-dihydric alcohol and di-isocyanate reaction, chainextender and di-isocyanate reaction are prepared to resin B, again A, B resin are carried out to physical mixed, obtain the finished product of high elongation at tear.Yet, the physical blending of Resin A, B in A resin, has also increased focal point of stress and rigid constraint place and neighborhood thereof by the B resin dispersion of utmost point rigidity in the time of the lifting of elongation at break, the risk that material ftractures under cyclic stress effect is increased, be that folding resistance is still inadequate, easy to crack.
Summary of the invention
The object of the invention is to propose the preparation method of the high folding urethane resin of a kind of new use for synthetic leather, improve the folding quality of existing synthetic leather, give its longer duration of service under the working conditions of bending repeatedly.
The preparation method of the high folding urethane resin of this use for synthetic leather comprises the following steps:
(I) adds hot preparation performed polymer A by PCDL, vulcabond, water, binary amine chainextender, oxidation inhibitor, catalyzer in solvent, and wherein vulcabond is excessive;
(II) adds hot preparation performed polymer B by polyether Glycols, vulcabond, di-alcohols chainextender, oxidation inhibitor, catalyzer in solvent, and wherein polyether Glycols is excessive;
In the performed polymer A that the performed polymer B that (III) obtains II step adds I step to obtain, carry out polyreaction, the ratio of performed polymer A and B is: in A in isocyanate groups total mole number and B hydroxyl total mole number than being (1.01-1.015): 1; After reaction certain hour, it is predetermined while finally requiring that reactant viscosity reaches, and adds appropriate small molecules monohydroxy-alcohol termination reaction, obtains final product.
Method of the present invention is based on " compound nested-Soft hard segment structure " this model, be in polyurethane molecular structure, itself to have microphase-separated Soft hard segment structure, and the macromole performed polymer " hard section block " that can prepare on this basis relative rigidity (A) with the macromole performed polymer " soft section of block " of relative flexibility (B), A block is mainly by the PCDL of relative rigidity, vulcabond, water, binary amine chainextender forms, water, the introducing of binary amine chainextender has further promoted the existence of " rigid structure " in block structure, B block is mainly by the polyether Glycols of relative flexibility, vulcabond, di-alcohols chainextender forms, full polyether Glycols is as soft section of part in block, give B block flexible preferably.Two kinds of macromole performed polymers are carried out to alternate combinations by chemical process, the final molecular chain forming is only comprised of the large block of [A-B-A] form, formed " damping type " structure of " hard (A)-soft (B)-hard (A) " alternative arrangement, and possess equally " Soft hard segment structure " in A, B block, the final molecular chain that forms " compound nested-Soft hard segment structure ", the soft section of flexible group of conduct, can carry out the conduction of power to a certain extent, hard section, as rigid radical, can play the carrying effect of power; The countless a plurality of Soft hard segment structure actings in conjunction that exist in countless many molecular chains make the Synthetic Leather goods in macroscopic view possess elastic stretching and nerve, can be comparatively desirable complete extraneous stressed carrying and conduction, make the synthetic leather of making there is good folding quality.
Embodiment
The preparation method of the high folding urethane resin of this use for synthetic leather comprises the following steps:
(I) adds hot preparation performed polymer A by PCDL, vulcabond, water, binary amine chainextender, oxidation inhibitor, catalyzer in solvent, and wherein vulcabond is excessive;
(II) adds hot preparation performed polymer B by polyether Glycols, vulcabond, di-alcohols chainextender, oxidation inhibitor, catalyzer in solvent, and wherein polyether Glycols is excessive;
In the performed polymer A that the performed polymer B that (III) obtains II step adds I step to obtain, carry out polyreaction, the ratio of performed polymer A and B is: in A in isocyanate groups total mole number and B hydroxyl total mole number than being (1.01-1.015): 1; After reaction certain hour, it is predetermined while finally requiring that reactant viscosity reaches, and adds appropriate small molecules monohydroxy-alcohol termination reaction, obtains final product.
In the preparation method of the high folding urethane resin of this use for synthetic leather, the amount of the vulcabond adding during the synthetic performed polymer A of I step can be comprised of two portions: the mole number of the mole number+chainextender of the mole number=water of first part's vulcabond, in second section vulcabond, in the mole number of isocyanate group and PCDL, the ratio of the mole number of hydroxyl is 1:(0.50～0.65), the add-on of water is 0.5% of PCDL total mass, the mole number of the addition of chainextender be water add-on mole number 50%, temperature of reaction is controlled at 70～75 ℃, the amount of the vulcabond adding while synthesizing performed polymer B in II step is comprised of two portions: the mole number of first part's vulcabond equates with the mole number of chainextender, in the mole number of the isocyanate group in second section vulcabond and polyether Glycols, the ratio of hydroxyl mole number is (0.50～0.65): 1, the chainextender total mole number that the addition of chainextender adds during with synthetic performed polymer A is identical, and temperature of reaction is controlled at 75～80 ℃, III step performed polymer A, the mixed temperature of reaction of B are controlled at 75～80 ℃, and final product viscosity controller is 4.0 * 10
4～6.0 * 10
4mPa.S/25 ℃, in mole number=performed polymer A of described small molecules monohydroxy-alcohol add-on 1%～1.5% of total isocyanate group mole number.
In the preparation method of the high folding urethane resin of this use for synthetic leather, the PCDL described in I step can be one or more of the molecular weight PCDL that is 1000～5000; Described water is deionized water (water is also for preparing the reactant of performed polymer A); Described vulcabond can be one or more in aromatics vulcabond, for example, and 4,4'-diphenylmethanediisocyanate or tolylene diisocyanate a kind of or two kinds; Described binary amine chainextender can be one or more in straight chain small molecules diamine, for example, and one or more in quadrol, Putriscine or Ursol D; Polyether Glycols described in II step can be one or more in PTMG (polybutylene ether glycol) or PPG (epoxypropane polymer) class polyether Glycols, and molecular weight is 1000～4000; Described vulcabond can be one or more in non-aromatic class vulcabond, for example, and a kind of in hexamethylene-diisocyanate or isophorone diisocyanate or two kinds; Described di-alcohols chainextender can be one or more in conventional small molecules di-alcohols chainextender, for example, and one or more in BDO, glycol ether or 1,6-hexylene glycol.
In the preparation method of the high folding urethane resin of this use for synthetic leather, oxidation inhibitor described in I, II step can be 2,6-di-tert-butyl-4-methy phenol, described catalyzer can be the organo-bismuth class catalyzer such as isocaprylic acid bismuth, two lauric acid bismuths, neodecanoic acid bismuth, and described solvent can be one or more in dimethyl formamide, toluene, butanone or ethyl acetate.
The preparation method's of the high folding urethane resin of this use for synthetic leather specific operation process is as follows:
(1) PCDL used, polyether Glycols are dewatered under the vacuum condition of 90～110 ℃, to reduce the generation of side reaction, dewatering time is no less than 5h, and the polyvalent alcohol after dehydration is no more than 3h apart from the time of preparation feedback.
(2) prepare performed polymer A:(a) in reactor A, add 30% solvent and PCDL, water, amine chain extender, catalyzer, the oxidation inhibitor of preset blending ratio, heat up, reach 65 ℃, insulation 20min to temperature.(b) vulcabond is divided into and adds in reactor for 2 times, temperature of reaction kettle is controlled at 70～75 ℃, and adding for the first time the reaction times after vulcabond is 3～4h, adds 30% solvent after having reacted; Adding for the second time the reaction times after vulcabond is 4～5h, adds remaining solvent (i.e. 40% solvent) after having reacted, and the final solid content of product is controlled at 30%.
(3) prepare performed polymer B:(a) in reactor B, add 30% solvent and polyether Glycols, alcohols chainextender, catalyzer, the oxidation inhibitor of preset blending ratio, heat up, reach 65 ℃, insulation 20min to temperature.(b) vulcabond is divided into and adds in reactor for 2 times, temperature of reaction kettle is controlled at 75～80 ℃, and adding for the first time the reaction times after vulcabond is 3～4h, adds 30% solvent after having reacted; Adding for the second time the reaction times after vulcabond is 4～5h, adds remaining solvent (i.e. 40% solvent) after having reacted, and the final solid content of product is controlled at 30%.
(4) according to the proportioning designing, after being weighed, the performed polymer in reactor B adds in reactor A, and temperature of reaction is controlled at 75～80 ℃, and final product viscosity controller is 4.0 * 10
4～6.0 * 10
4mPa.S/25 ℃, the reaction times determines according to the final viscosity of reaction product, and small molecules monohydroxy-alcohol addition is no more than 6.25 * 10
-3mol, the solid content of final product is controlled at 30%.
(5) cooling, obtain final product.
Final product polyurethane molecular of the present invention, its structure can be represented by the formula:
R-O-(A-B-A······A-B-A)-O-R
In formula, R-O-is small molecules monohydroxy-alcohol, and A is that structural unit, the B of performed polymer A is the structural unit of performed polymer B.
The present invention is by preparing respectively relative rigidity, the performed polymer of flexible two types, and by chemical means, performed polymer is linked, the molecular chain forming is only by " large block type damping type " structure of " hard (A)-soft (B)-hard (A) " alternative arrangement, and in hard soft section of block, possess equally microcosmic " Soft hard segment structure ", make final urethane form the molecular chain of countless many " compound nested-Soft hard segment structures ".Selection is simple, process stabilizing easy handling, can realize like a cork suitability for industrialized production, the Synthetic Leather goods of making can be resisted the effect that puts on polyurethane material external force preferably, external force is able to effectively carrying and conduction in molecular chain, saboteur's chain structure not, material can be used for a long time under folding condition and be unlikely to break, final synthetic leather life cycle under the folding condition of high request is increased.
To the present invention, be described further by specific embodiment below.
Embodiment 1
A component :-OH/-NCO=0.5/1
| Material name | Rank | Quality |
| PCDL PCG | Technical grade molecular weight 1000 | 1000g |
| PCDL PCG | Technical grade molecular weight 2000 | 1000g |
| Deionized water | Analytical pure | 10g |
| Oxidation inhibitor-2,6 di tert butyl 4 methyl phenol | Technical grade | 2g |
| Catalyzer-isocaprylic acid bismuth | Technical grade | 1g |
| Quadrol | Technical grade | 16.70g |
| MDI (4,4 '-diphenylmethanediisocyanate) | Technical grade | 959.27g |
| Solvent: dimethyl formamide, butanone (mass ratio 70/30) | Technical grade | 6967.26g |
B component :-NCO/-OH=0.5/1
| Material name | Rank | Quality |
| Polyether Glycols PTMG | Technical grade molecular weight 1000 | 3000g |
| Polyether Glycols PPG | Technical grade molecular weight 2000 | 3000g |
| BDO | Technical grade | 75.12g |
| Oxidation inhibitor-2,6 di tert butyl 4 methyl phenol | Technical grade | 6g |
| Catalyzer-isocaprylic acid bismuth | Technical grade | 3g |
| HDI (hexamethylene-diisocyanate) | Technical grade | 518.02g |
| Solvent: dimethyl formamide, butanone (mass ratio 70/30) | Technical grade | 15384g |
Ratio when performed polymer A and B polyreaction, according to isocyanate group and hydroxyl mol ratio 1.01:1, adds 14506.38g performed polymer B in the reactor of synthetic performed polymer A.
Operating process:
(1) poly-dihydric alcohol used is dewatered under the vacuum condition of 100 ℃, to reduce the generation of side reaction, dewatering time 5h.
(2) in reactor A, add PCG (f=2, molecular weight 1000), PCG (f=2, molecular weight 2000) two kinds of each 1000g of poly-dihydric alcohol and oxidation inhibitor 2g, catalyzer 1g, and add deionized water 10g, quadrol 16.70g, add solvent dimethyl formamide, butanone (dimethyl formamide and butanone add according to mass ratio 70/30) 2090.18g, temperature of reaction kettle is risen to 65 ℃, insulation 30min.
(3) MDI479.64g (50% massfraction) is added to reactor A, middle reaction 3h, temperature is controlled at 75 ℃; After completion of the reaction by solvent dimethyl formamide, butanone (dimethyl formamide and butanone add according to mass ratio 70/30) 2090.18g to reactor, and remaining MDI is added to continuation reaction 4h in reactor A, temperature is controlled at 75 ℃, after having reacted, residual solvent 2786.90 is added in reactor A, after stirring, obtain performed polymer A.
(4) in reactor B, add PTMG (f=2 simultaneously with (2) step, molecular weight 1000), PPG (f=2, molecular weight 2000) two kinds of each 3000g of poly-dihydric alcohol and oxidation inhibitor 6g, catalyzer 3g, and add 1,4-butyleneglycol 75.12g, solvent dimethyl formamide, butanone (adding according to mass ratio 70/30) 4615.2g, temperature of reaction kettle is risen to 65 ℃, insulation 30min.
(5) HDI259.01g (50% massfraction) is added in reactor B, reaction 3h, temperature is controlled at 75 ℃; After completion of the reaction, solvent dimethyl formamide, butanone (according to mass ratio 70/30) 4615.2g are added in reactor, and remaining HDI is added in reactor B, continue reaction 4h, temperature is controlled at 75 ℃, after having reacted, residual solvent 6153.6g is added in reactor B, after stirring, obtain performed polymer B.
(6) the performed polymer 14506.38g in reactor B is added and in reactor A, carry out polyreaction (A, B performed polymer-NCO/-OH=1.01/1), temperature of reaction is controlled at 75 ℃, treats that final product viscosity reaches 4.3 * 10
4in the time of MPa.S/25 ℃, add the methyl alcohol 0.96g termination reaction that accounts for total isocyanate group mole number 1% in performed polymer A, the solid content of final product is 30%.
(7) cooling, obtain final product.
Embodiment 2
A component :-OH/-NCO=0.55/1
B component :-NCO/-OH=0.55/1
Ratio when performed polymer A and B polyreaction, according to isocyanate group and hydroxyl mol ratio 1.011:1, adds 12387.13g performed polymer B in the reactor of synthetic performed polymer A.
Operating process:
(1) poly-dihydric alcohol used is dewatered under the vacuum condition of 100 ℃, to reduce the generation of side reaction, dewatering time 5h.
(2) in reactor A, add PCG (f=2, molecular weight 1000), PCG (f=2, molecular weight 3000) two kinds of poly-dihydric alcohol 1000g, 1200g and oxidation inhibitor 2.2g, catalyzer 1.1g, and add deionized water 11g, 1,4-butanediamine 26.94g, add solvent dimethyl formamide, ethyl acetate (adding according to mass ratio 70/30) 2173.02g, temperature of reaction kettle is risen to 65 ℃, insulation 30min.
(3) MDI433.185g (50% massfraction) is added in reactor A and reacts 4h, temperature is controlled at 70 ℃; After completion of the reaction solvent dimethyl formamide, ethyl acetate (according to mass ratio 70/30) 2173.02g are added in reactor A, and remaining MDI is added to continuation reaction 5h in reactor A, temperature is controlled at 70 ℃, after having reacted, residual solvent 2897.36g is added in reactor A, after stirring, obtain performed polymer A.
(4) in reactor B, add PTMG (f=2 simultaneously with (2) step, molecular weight 1000), PTMG (f=2, molecular weight 2000) two kinds of each 3000g of poly-dihydric alcohol and oxidation inhibitor 6g, catalyzer 3g, and add glycol ether 88.43g, solvent dimethyl formamide, ethyl acetate (adding according to mass ratio 70/30) 4651.16g, temperature of reaction kettle is risen to 65 ℃, insulation 30min.
(5) HDI278.04g (50% massfraction) is added in reactor B and reacts 4h, temperature is controlled at 75 ℃; After completion of the reaction solvent dimethyl formamide, ethyl acetate (according to mass ratio 70/30) 4651.16g are added in reactor B, and remaining HDI is added to continuation reaction 5h in reactor B, temperature is controlled at 75 ℃, after having reacted, residual solvent 6201.54g is added in reactor B, after stirring, obtain performed polymer B.
(6) the performed polymer 12387.13g in reactor B is added in reactor A to reaction (A, B performed polymer-NCO/-OH=1.011/1), temperature of reaction is controlled at 75 ℃, treats that final product viscosity reaches 5.5 * 10
4in the time of MPa.S/25 ℃, add the methyl alcohol 0.81g termination reaction that accounts for total isocyanate group mole number 1.1% in performed polymer A, the solid content of final product is 30%.
(7) cooling, obtain final product.
Embodiment 3
A component :-OH/-NCO=0.60/1
| Material name | Rank | Quality |
| PCDL PCG | Technical grade molecular weight 1000 | 1000g |
| PCDL PCG | Technical grade molecular weight 4000 | 1200g |
| Deionized water | Analytical pure | 11g |
| Oxidation inhibitor-2,6 di tert butyl 4 methyl phenol | Technical grade | 2.2g |
| Catalyzer-Xin certain herbaceous plants with big flowers acid bismuth | Technical grade | 1.1g |
| Ursol D | Technical grade | 33.05g |
| TDI (tolylene diisocyanate) | Technical grade | 537g |
| Solvent: dimethyl formamide, toluene (mass ratio 70/30) | Technical grade | 6489.12g |
B component :-NCO/-OH=0.60/1
| Material name | Rank | Quality |
| Polyether Glycols PPG | Technical grade molecular weight 1000 | 3000g |
| Polyether Glycols PPG | Technical grade molecular weight 2000 | 3000g |
| 1,6-hexylene glycol | Technical grade | 98.44g |
| Oxidation inhibitor-2,6 di tert butyl 4 methyl phenol | Technical grade | 6g |
| Catalyzer-Xin certain herbaceous plants with big flowers acid bismuth | Technical grade | 3g |
| IPDI (isophorone diisocyanate) | Technical grade | 785.35g |
| Solvent: dimethyl formamide, toluene (mass ratio 70/30) | Technical grade | 16062.18g |
Ratio when performed polymer A and B polyreaction, according to isocyanate group and hydroxyl mol ratio 1.012:1, adds 10921.26g performed polymer B in the reactor of synthetic performed polymer A.
Operating process:
(1) poly-dihydric alcohol used is dewatered under the vacuum condition of 100 ℃, to reduce the generation of side reaction, dewatering time 5h.
(2) in reactor A, add PCG (f=2, molecular weight 1000), PCG (f=2, molecular weight 4000) two kinds of poly-dihydric alcohol 1000g, 1200g and oxidation inhibitor 2.2g, catalyzer 1.1g, and add deionized water 11g, Ursol D 33.05g, add solvent dimethyl formamide, toluene (adding according to mass ratio 70/30) 1946.74g, temperature of reaction kettle is risen to 65 ℃, insulation 30min.
(3) TDI268.5g (50% massfraction) is added in reactor A and reacts 3.5h, temperature is controlled at 75 ℃; After completion of the reaction solvent dimethyl formamide, toluene (according to mass ratio 70/30) 1946.74g are added in reactor, and remaining TDI is added to continuation reaction 4.5h in reactor A, temperature is controlled at 75 ℃, after having reacted, residual solvent 2595.65g is added in reactor A, after stirring, obtain performed polymer A.
(4) in reactor B, add PPG (f=2 simultaneously with (2) step, molecular weight 1000), PPG (f=2, molecular weight 2000) two kinds of each 3000g of poly-dihydric alcohol and oxidation inhibitor 6g, catalyzer 3g, and add 1,6-hexylene glycol 98.44g, solvent dimethyl formamide, toluene (adding according to mass ratio 70/30) 4818.65g, temperature of reaction kettle is risen to 65 ℃, insulation 30min.
(5) IPDI392.67g (50% massfraction) is added in reactor B and reacts 3.5h, temperature is controlled at 80 ℃; After completion of the reaction solvent dimethyl formamide, toluene are added in reactor by (according to mass ratio 70/30) 4818.65g, and remaining IPDI is added to continuation reaction 4.5h in reactor B, temperature is controlled at 80 ℃, after having reacted, residual solvent 6424.87g is added in reactor B, after stirring, obtain performed polymer B.
(6) the performed polymer 10921.26g in reactor B is added in reactor A to reaction (A, B performed polymer-NCO/-OH=1.012/1), temperature of reaction is controlled at 80 ℃, treats that final product viscosity reaches 6.0 * 10
4in the time of MPa.S/25 ℃, add the methyl alcohol 0.66g termination reaction that accounts for total isocyanate group mole number 1.2% in performed polymer A, the solid content of final product is 30%.
(7) cooling, obtain final product.
Embodiment 4
A component :-OH/-NCO=0.65/1
B component :-NCO/-OH=0.65/1
Ratio when performed polymer A and B polyreaction, according to isocyanate group and hydroxyl mol ratio 1.013:1, adds 20647.87g performed polymer B in the reactor of synthetic performed polymer A.
Operating process:
(1) poly-dihydric alcohol used is dewatered under the vacuum condition of 100 ℃, to reduce the generation of side reaction, dewatering time 5h.
(2) in reactor A, add PCG (f=2, molecular weight 1000), PCG (f=2, molecular weight 5000) two kinds of poly-dihydric alcohol 1000g, 1200g and oxidation inhibitor 2.2g, catalyzer 1.1g, and add deionized water 11g, quadrol 9.18g, 1,4-butanediamine 13.47g, add solvent dimethyl formamide, butanone, toluene (adding according to mass ratio 70/20/10) 1907.88g, temperature of reaction kettle is risen to 65 ℃, insulation 30min.
(3) TDI245.95g (50% massfraction) is added in reactor A and reacts 3h, temperature is controlled at 75 ℃; After completion of the reaction solvent dimethyl formamide, butanone, toluene (according to mass ratio 70/20/10) 1907.88g are added in reactor, and remaining TDI is added to continuation reaction 5h in reactor A, temperature is controlled at 75 ℃, after having reacted, residual solvent 2543.84g is added in reactor A, after stirring, obtain performed polymer A.
(4) in reactor B, add PPG (f=2 simultaneously with (2) step, molecular weight 3000), PTMG (f=2, molecular weight 3000) two kinds of each 3000g of poly-dihydric alcohol and oxidation inhibitor 6g, catalyzer 3g, and add 1,4-butyleneglycol 37.53g, glycol ether 44.19g, solvent dimethyl formamide, butanone, toluene (adding according to mass ratio 70/20/10) 4589.11g, temperature of reaction kettle is risen to 65 ℃, insulation 30min.
(5) IPDI237.08g (50% massfraction) is added in reactor B and reacts 3h, temperature is controlled at 78 ℃; After completion of the reaction solvent dimethyl formamide, butanone, toluene (according to mass ratio 70/20/10) 4589.11g are added in reactor, and remaining IPDI is added to continuation reaction 5h in reactor B, temperature is controlled at 78 ℃, after having reacted, residual solvent 6118.81g is added in reactor B, after stirring, obtain performed polymer B.
(6) the performed polymer 20647.87g in reactor B is added in reactor A to reaction (A, B performed polymer-NCO/-OH=1.013/1), temperature of reaction is controlled at 80 ℃, treats that final product viscosity reaches 4.0 * 10
4in the time of MPa.S/25 ℃, add the methyl alcohol 0.56g termination reaction that accounts for total isocyanate group mole number 1.3% in performed polymer A, the solid content of final product is 30%.
(7) cooling, obtain final product.
Embodiment 5
A component :-OH/-NCO=0.50/1
B component :-NCO/-OH=0.50/1
Ratio when performed polymer A and B polyreaction, according to isocyanate group and hydroxyl mol ratio 1.014:1, adds 12903.04g performed polymer B in the reactor of synthetic performed polymer A.
Operating process:
(1) poly-dihydric alcohol used is dewatered under the vacuum condition of 100 ℃, to reduce the generation of side reaction, dewatering time 5h.
(2) in reactor A, add PCG (f=2, molecular weight 2000), PCG (f=2, molecular weight 3000) two kinds of poly-dihydric alcohol 1000g, 1200g and oxidation inhibitor 2.2g, catalyzer 1.1g, and add deionized water 11g, quadrol 9.18g, Ursol D 16.52g, add solvent dimethyl formamide, ethyl acetate, toluene (adding according to mass ratio 70/20/10) 1969.23g, temperature of reaction kettle is risen to 65 ℃, insulation 30min.
(3) TDI 118.29g, MDI 169.96g (50% massfraction) are added in reactor A and react 4h, temperature is controlled at 73 ℃; After completion of the reaction solvent dimethyl formamide, ethyl acetate, toluene (according to mass ratio 70/20/10) 1969.23g are added in reactor, and remaining TDI, MDI are added to continuation reaction 5h in reactor A, temperature is controlled at 76 ℃, after having reacted, residual solvent 2625.64g is added in reactor A, after stirring, obtain performed polymer A.
(4) in reactor B, add PTMG (f=2 simultaneously with (2) step, molecular weight 2000), PPG (f=2, molecular weight 2000) two kinds of each 3000g of poly-dihydric alcohol and oxidation inhibitor 6g, catalyzer 3g, and add 1,4-butyleneglycol 37.53g, 1,6-hexylene glycol 49.22g, solvent dimethyl formamide, ethyl acetate, toluene (adding according to mass ratio 70/20/10) 4579.41g, rise to 65 ℃ by temperature of reaction kettle, insulation 30min.
(5) IPDI 129.65g, HDI97.99g (50% massfraction) are added in reactor B and react 3h, temperature is controlled at 75 ℃; After completion of the reaction solvent dimethyl formamide, ethyl acetate, toluene (according to mass ratio 70/20/10) 4579.41g are added in reactor, and remaining IPDI, HDI are added to continuation reaction 4h in reactor B, temperature is controlled at 75 ℃, after having reacted, residual solvent 6105.88g is added in reactor B, after stirring, obtain performed polymer B.
(6) the performed polymer 12903.04g in reactor B is added in reactor A (A, B performed polymer-NCO/-OH=1.014/1), temperature of reaction is controlled at 75 ℃, treats that final product viscosity reaches 4.9 * 10
4in the time of MPa.S/25 ℃, add the methyl alcohol 0.81g termination reaction that accounts for total isocyanate group mole number 1.4% in performed polymer A, the solid content of final product is 30%.
(7) cooling, obtain final product.
Embodiment 6
A component :-OH/-NCO=0.65/1
B component :-NCO/-OH=0.65/1
Ratio when performed polymer A and B polyreaction adds 17372.08g performed polymer B in the reactor of synthetic performed polymer A according to isocyanate group and hydroxyl mol ratio 1.015:1.
Operating process:
(1) poly-dihydric alcohol used is dewatered under the vacuum condition of 100 ℃, to reduce the generation of side reaction, dewatering time 5h.
(2) in reactor A, add PCG (f=2, molecular weight 2000), PCG (f=2, molecular weight 4000) two kinds of poly-dihydric alcohol 1000g, 1200g and oxidation inhibitor 2.2g, catalyzer 1.1g, and add deionized water 11g, butanediamine 13.47g, Ursol D 16.52g, add solvent dimethyl formamide, ethyl acetate, butanone, toluene (adding according to mass ratio 70/10/10/10) 1887.68g, temperature of reaction kettle is risen to 65 ℃, insulation 30min.
(3) TDI93.50g, MDI 134.35g (50% massfraction) are added in reactor A and react 3.5h, temperature is controlled at 74 ℃; After completion of the reaction solvent dimethyl formamide, ethyl acetate, butanone, toluene (according to mass ratio 70/10/10/10) 1887.68g are added in reactor, and remaining TDI, MDI are added to continuation reaction 4.5h in reactor A, temperature is controlled at 77 ℃, after having reacted, residual solvent 2516.90g is added in reactor A, after stirring, obtain performed polymer A.
(4) in reactor B, add PTMG (f=2 simultaneously with (2) step, molecular weight 4000), PPG (f=2, molecular weight 4000) two kinds of each 3000g of poly-dihydric alcohol and oxidation inhibitor 6g, catalyzer 3g, and add glycol ether 44.19g, 1,6-hexylene glycol 49.22g, add solvent dimethyl formamide, ethyl acetate, butanone, toluene (adding according to mass ratio 70/10/10/10) 4512.36g, temperature of reaction kettle is risen to 65 ℃, insulation 30min.
(5) IPDI 100.48g, HDI 75.94g (50% massfraction) are added in reactor B and react 3h, temperature is controlled at 74 ℃; After completion of the reaction solvent dimethyl formamide, ethyl acetate, butanone, toluene (according to mass ratio 70/10/10/10) 4512.36g are added in reactor, and remaining IPDI, HDI are added to continuation reaction 4h in reactor B, temperature is controlled at 76 ℃, after having reacted, residual solvent 6016.48g is added in reactor B, after stirring, obtain performed polymer B.
(6) the performed polymer 17372.08g in reactor B is added in reactor A (A, B performed polymer-NCO/-OH=1.015/1), temperature of reaction is controlled at 76 ℃, treats that final product viscosity reaches 5.7 * 10
4in the time of MPa.S/25 ℃, add the methyl alcohol 0.41g termination reaction that accounts for total isocyanate group mole number 1.5% in performed polymer A, the solid content of final product is 30%.
(7) cooling, obtain final product.
The various embodiments described above synthesized urethane folding quality test result is as following table:
| Embodiment numbering | Probe temperature (25 ℃) | Probe temperature (5 ℃) | Probe temperature (10 ℃) |
| 1 | 40000 times | 21000 times | 9000 times |
| 2 | 44000 times | 25000 times | 11000 times |
| 3 | 47000 times | 27000 times | 12000 times |
| 4 | 51000 times | 32000 times | 14500 times |
| 5 | 46000 times | 28000 times | 12300 times |
| 6 | 59000 times | 39000 times | 24500 times |
| Conventional resin | 30000 times | 12000 times | 5000 times |
As can be known from the above table, the folding test result under 25,5 ,-5 ℃ of conditions of conventional polyurethanes is 5000-30000 time, compares with conventional products, and the folding quality of the sample of 6 embodiment gained under relevant temperature all obviously improves.
Folding test requires to carry out according to GB/T8949-1995, in urethane dry method leatheroid GB, requires folding 2.5 ten thousand times, flawless.Conventional resin model HX-6053 in folding test is the dry method urethane resin of Jiaxing Hexin Chemical Industrial Co., Ltd's production.
Claims (5)
1. a preparation method for the high folding urethane resin of use for synthetic leather, is characterized in that comprising the following steps:
(I) adds hot preparation performed polymer A by PCDL, vulcabond, water, binary amine chainextender, oxidation inhibitor, catalyzer in solvent, and wherein vulcabond is excessive;
(II) adds hot preparation performed polymer B by polyether Glycols, vulcabond, di-alcohols chainextender, oxidation inhibitor, catalyzer in solvent, and wherein polyether Glycols is excessive;
In the performed polymer A that the performed polymer B that (III) obtains II step adds I step to obtain, carry out polyreaction, the ratio of performed polymer A and B is: in A in isocyanate groups total mole number and B hydroxyl total mole number than being (1.01-1.015): 1; After reaction certain hour, it is predetermined while finally requiring that reactant viscosity reaches, and adds appropriate small molecules monohydroxy-alcohol termination reaction, obtains final product.
2. the preparation method of the high folding urethane resin of use for synthetic leather as claimed in claim 1, the amount of the vulcabond adding while it is characterized in that the synthetic performed polymer A of I step is comprised of two portions: the mole number of the mole number+chainextender of the mole number=water of first part's vulcabond, in second section vulcabond, in the mole number of isocyanate group and PCDL, the ratio of the mole number of hydroxyl is 1:(0.50～0.65), the add-on of water is 0.5% of PCDL total mass, the mole number of the addition of chainextender be water add-on mole number 50%, temperature of reaction is controlled at 70～75 ℃, the amount of the vulcabond adding while synthesizing performed polymer B in II step is comprised of two portions: the mole number of first part's vulcabond equates with the mole number of chainextender, in the mole number of the isocyanate group in second section vulcabond and polyether Glycols, the ratio of hydroxyl mole number is (0.50～0.65): 1, the chainextender total mole number that the addition of chainextender adds during with synthetic performed polymer A is identical, and temperature of reaction is controlled at 75～80 ℃, in III step, the mixed temperature of reaction of performed polymer A, B is controlled at 75～80 ℃, and final product viscosity controller is 4.0 * 10
4～6.0 * 10
4mPa.S/25 ℃, in mole number=performed polymer A of described small molecules monohydroxy-alcohol add-on 1%～1.5% of total isocyanate group mole number.
3. the preparation method of the high folding urethane resin of use for synthetic leather as claimed in claim 1 or 2, is characterized in that the PCDL described in I step is that molecular weight is one or more of 1000～5000 PCDL; Described water is deionized water; Described vulcabond is one or more in aromatics vulcabond; Described binary amine chainextender is one or more in straight chain small molecules diamine; Polyether Glycols described in II step is one or more in PTMG or PPG class polyether Glycols, and molecular weight is 1000～4000; Described vulcabond is one or more in non-aromatic class vulcabond; Described di-alcohols chainextender is one or more in conventional small molecules di-alcohols chainextender.
4. the preparation method of the high folding urethane resin of use for synthetic leather as claimed in claim 3, is characterized in that the vulcabond described in I step is a kind of of 4,4'-diphenylmethanediisocyanate or tolylene diisocyanate or two kinds; Described binary amine chainextender is one or more in quadrol, Putriscine or Ursol D; Vulcabond described in II step is a kind of in hexamethylene-diisocyanate or isophorone diisocyanate or two kinds; Described di-alcohols chainextender is one or more in BDO, glycol ether or 1,6-hexylene glycol.
5. the preparation method of the high folding urethane resin of use for synthetic leather as claimed in claim 4, it is characterized in that the oxidation inhibitor described in I, II step is 2,6-di-tert-butyl-4-methy phenol, described catalyzer is one or more in isocaprylic acid bismuth, two lauric acid bismuths, neodecanoic acid bismuth, and described solvent is a kind of several in dimethyl formamide, toluene, butanone or ethyl acetate.
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| CN106478919A (en) * | 2016-09-28 | 2017-03-08 | 合肥科天水性科技有限责任公司 | A kind of aqueous polyurethane for clothing leather facing material and preparation method thereof |
| CN106866927A (en) * | 2017-02-24 | 2017-06-20 | 耿佃勇 | Enhanced water resistance clear prepolymer and preparation method thereof |
| CN107141434A (en) * | 2017-06-08 | 2017-09-08 | 合肥科天水性科技有限责任公司 | It is a kind of for waterborne polyurethane resin of synthetic leather fabric and preparation method thereof |
| CN110041746A (en) * | 2019-04-17 | 2019-07-23 | 扬州市立达树脂有限公司 | A kind of silane coupling agent of water paint and preparation method thereof |
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| CN110041746A (en) * | 2019-04-17 | 2019-07-23 | 扬州市立达树脂有限公司 | A kind of silane coupling agent of water paint and preparation method thereof |
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Address after: 314003 Dongfang Road, Jiaxing economic and Technological Development Zone, Jiaxing, Zhejiang Province, 1 Building 3 Patentee after: Zhejiang Hexin Technology Co., Ltd. Address before: 314003 wo he Xin Industrial Park, No. 1568 Dongfang Road, Zhejiang, Jiaxing Patentee before: Jiaxing Hexin Chemical Industry Co.,Ltd. |