CN104140520A - Super-soft high-elasticity hydrolysis resistance high-stripping wet polyurethane resin and preparation method thereof - Google Patents
Super-soft high-elasticity hydrolysis resistance high-stripping wet polyurethane resin and preparation method thereof Download PDFInfo
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- CN104140520A CN104140520A CN201410383713.0A CN201410383713A CN104140520A CN 104140520 A CN104140520 A CN 104140520A CN 201410383713 A CN201410383713 A CN 201410383713A CN 104140520 A CN104140520 A CN 104140520A
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- Prior art keywords
- polyol compound
- polyol
- isocyanic ester
- polyurethane resin
- polyhydric alcohol
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- 230000007062 hydrolysis Effects 0.000 title claims abstract description 16
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 16
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 229920005862 polyol Polymers 0.000 claims abstract description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004970 Chain extender Substances 0.000 claims abstract description 18
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 8
- 150000004291 polyenes Chemical class 0.000 claims abstract description 8
- 229920000570 polyether Polymers 0.000 claims abstract description 8
- 150000003077 polyols Chemical class 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- -1 Polyol compound Chemical class 0.000 claims description 30
- 150000002148 esters Chemical class 0.000 claims description 20
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 7
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 239000013589 supplement Substances 0.000 claims description 4
- IJMWOMHMDSDKGK-UHFFFAOYSA-N Isopropyl propionate Chemical compound CCC(=O)OC(C)C IJMWOMHMDSDKGK-UHFFFAOYSA-N 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 150000005846 sugar alcohols Polymers 0.000 abstract 8
- 150000001875 compounds Chemical class 0.000 abstract 6
- 239000012948 isocyanate Substances 0.000 abstract 2
- 150000002513 isocyanates Chemical class 0.000 abstract 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000002649 leather substitute Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 239000010985 leather Substances 0.000 description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- CAPNUXMLPONECZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-2-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=C(O)C(C(C)(C)C)=C1 CAPNUXMLPONECZ-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007719 peel strength test Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/2815—Monohydroxy compounds
- C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
-
- 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
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/6576—Compounds of group C08G18/69
- C08G18/6582—Compounds of group C08G18/69 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6588—Compounds of group C08G18/69 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
-
- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/698—Mixtures with compounds of group C08G18/40
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses super-soft high-elasticity hydrolysis resistance high-stripping wet polyurethane resin and a preparation method of the super-soft high-elasticity hydrolysis resistance high-stripping wet polyurethane resin. The super-soft high-elasticity hydrolysis resistance high-stripping wet polyurethane resin is composed of isocyanate, a polyhydric alcohol compound, a chain extender, antioxygen, reaction terminating agent methyl alcohol and catalyst by weight. The additive amount is 0.001%-0.05% of the mass of the polyhydric alcohol compound. The number-average molecular weight of the polyhydric alcohol compound is 1000-3000. The polyhydric alcohol compound is composed of polyester polyol, polyether polyol and polyene polyhydric alcohol, wherein the mass ratio of the polyester polyol, the polyether polyol and the polyene polyhydric alcohol is 1:0.8-1.2:0.1-0.3. The total molar ratio of NCO in the isocyanate to the hydroxyl in the polyhydric alcohol compound and the chain extender is 0.9-1:1. The molar ratio of the polyhydric alcohol compound and the chain extender is 1:1.3-1.7. The super-soft high-elasticity hydrolysis resistance high-stripping wet polyurethane resin greatly solves the problem that soft resin can not achieve high elasticity and high stripping strength at the same time, is durable in use and has market competitiveness.
Description
Technical field
The present invention relates to a kind of urethane resin, be specifically related to high Wet-type polyurethane resin of peeling off of a kind of ultra-soft matter snappiness hydrolysis and preparation method thereof.
Background technology
Due to corium resource-constrained, price is high, cannot meet the growing market requirement.And Synthetic Leather products material wide material sources, low price, good processability, has has met or exceeded the characteristic of natural leather, meets people's life seek completely.And Synthetic Leather products material wide material sources, low price, good processability, can meet people's life seek.The application of urethane resin aspect synthetic leather is mainly reflected in multiple fields such as clothes, case and bag, footwear, furniture, automobile, and leather is more and more faster with the tempo of urethane resin in recent years, in the face of the increasing gradually of the market requirement, it also proposed to higher requirement,
At present, men and women's leather shoes, sports shoes market are progressively to the future development of snugness of fit, and quality softness, good springiness, the excellent product of durability are subject to human consumer's welcome most.But existing urethane resin is difficult to take into account that modulus is low, good springiness, high these three features of intensity.
Summary of the invention
The present invention aims to provide high Wet-type polyurethane resin of peeling off of a kind of ultra-soft matter snappiness hydrolysis and preparation method thereof, improves elasticity, intensity and the anti-hydrolytic performance of mild polyurethane resin.
Technical solution problem of the present invention adopts following technical scheme:
The high Wet-type polyurethane resin of peeling off of ultra-soft matter snappiness hydrolysis, is prepared from by following raw materials in parts by weight:
Isocyanic ester
Polyol compound
Chainextender
Oxidation inhibitor
Reaction terminating agent methyl alcohol
Organic tin or organo-bismuth class catalyzer, addition is the 0.001-0.05% of polyol compound quality;
The number-average molecular weight of described polyol compound is 1000-3000;
Described polyol compound by polyester polyol, polyether glycol and polyene polyvalent alcohol in mass ratio for 1:0.8-1.2:0.1-0.3 forms;
The molecular weight of described polyester polyol is 2000, and it is by hexanodioic acid 4000kg, ethylene glycol or BDO 2500kg, and catalyst Ti isopropyl propionate 0.4 kg is prepared from;
The total mol ratio of hydroxyl in described isocyanic ester in isocyano and polyol compound and chainextender is 0.9-1:1;
The mol ratio of described polyol compound and chainextender is 1:1.3-1.7.
Further, described isocyanic ester is 4,4 '-diphenylmethanediisocyanate.
Described polyester polyol is that functionality is that 2 hexanodioic acid is polyester polyol;
Described polyether glycol is that functionality is 2 polytetrahydrofuran polyvalent alcohol or polyoxypropylene polyol;
Described polyene polyvalent alcohol is that functionality is 2 polybutadiene polyol.
Described chainextender is ethylene glycol, BDO, 1, one or both in 6-hexylene glycol, and wherein two kinds of mixing uses are to mix for 0.1:1 ~ 10:1 in molar ratio.
Described oxidation inhibitor is four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester (oxidation inhibitor 1-1010), 2,2'-methylene-bis (4-methyl-6-tert-butylphenol) (antioxidant 2246).
Another goal of the invention of the present invention is to provide a kind of preparation method of the above-mentioned high Wet-type polyurethane resin of peeling off of ultra-soft matter snappiness hydrolysis, and step is as follows:
1) first 60% and the oxidation inhibitor that account for polyol compound total mass are added in organic solvent to the solution that formation solid content is 20-30%; After stirring, add the 20%-25% that accounts for isocyanic ester total mass in 45-50 DEG C of reaction 1-2 hour; Then remaining polyol compound is added and continue reaction after 1-2 hour, then add the 15%-20% that accounts for isocyanic ester total mass, make in polyol compound the mol ratio 1:1.5 of isocyano in hydroxyl and vulcabond; Finally obtaining solid content in 55-65 DEG C of reaction is that 45-55%, viscosity are the prepolymer of 30-80 Pas/75 DEG C;
2) in prepolymer, add chainextender, surplus isocyanic ester and organic tin or organo-bismuth class catalyzer, after stirring, continue reaction 2-5h in 75-85 DEG C, in the process of reaction, make final viscosity be controlled at 80-120Pas/25 DEG C along with the increase of system viscosity constantly supplements organic solvent, after having reacted, add reaction terminating agent methyl alcohol to obtain urethane resin.
Further, the water ratio of described polyol compound, isocyanic ester, chainextender is all less than 500ppm.
The preferred N of described organic solvent, N '-dimethyl formamide (DMF).
The Wet-type polyurethane resin making by above-mentioned formula is applied to synthetic leather and produces, and the leather goods of making have good springiness, stripping strength is high, anti-hydrolytic performance is good feature.
Urethane resin of the present invention has been improved more greatly the physical property of elasticity, stripping strength and the hydrolysis aspect of soft resin, and product is durable in use, and product specification is high, has the market competitiveness.
Beneficial effect:
1, prepolymerization reaction temperature of the present invention is low, thereby has ensured molecule segment homogeneity;
2, in the first step prepolymerization reaction of the present invention, adopt and in batches MDI is added, make pre-polymerization have the crystallization of comparatively obvious two sections of different performances.
, amount 3, in the present invention polyol compound by polyester polyol, polyether glycol and polyene polyvalent alcohol in mass ratio for 1:0.8-1.2:0.1-0.3 forms; And polyester polyol is by hexanodioic acid 4000kg, ethylene glycol or 1,4-butyleneglycol 2500kg, catalyst Ti isopropyl propionate 0.4 kg is prepared from, and makes the rosin products of preparation in the aspect such as cost, performance comprehensive advantage, have that stripping strength is high, anti-hydrolytic performance good, and the feature such as good hand feeling.
Embodiment
For technique means, creation characteristic that the present invention is realized, reach object and effect is easy to understand, below in conjunction with embodiment, further set forth the present invention.
In embodiment, each component is as follows respectively below:
EG is ethylene glycol;
BG is BDO;
Described polyol compound by polyester polyol, polyether glycol and polyene polyvalent alcohol in mass ratio for 1:0.8-1.2:0.1-0.3 forms; Wherein SP-1 is that molecular weight is that 2000 hexanodioic acid is polyester polyol;
It is 1000,2000 Polyoxypropylene diol that PPG-1, PPG-2 are respectively molecular weight;
It is 1000,2000 polytetrahydrofuran dibasic alcohol that PTMG-1, PTMG-2 are respectively molecular weight;
It is 1000,2000 polyhutadiene dibasic alcohol that HTPB-1, HTPB-2 are respectively molecular weight;
Oxidation inhibitor I-1010 is commercially available oxidation inhibitor, entirely four [β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid] pentaerythritol ester by name;
MDI is 4,4 '-diphenylmethanediisocyanate;
Organo-bismuth is catalysts, and to be wherein better than organotin be to know altogether in industry to the feature of environmental protection of organo-bismuth;
DMF is solvent N, N '-dimethyl formamide, and methyl alcohol is reaction terminating agent.
Embodiment 1:
Raw material and proportioning:
1) first the HTPB-2 of the PTMG-2 of the SP-1 of 750kg, 370kg, 50kg and 3kg oxidation inhibitor I-1010 are added in organic solvent DMF to the solution that formation solid content is 30%; After stirring, add 130-140kg isocyanic ester in 45-50 DEG C of reaction 1-2 hour; Then the PTMG-1 of remaining 400kg is added and continue reaction after 2 hours, then add 100-120kg isocyanic ester, make in polyol compound the mol ratio 1:1.5 of isocyano in hydroxyl and vulcabond; Finally in the prepolymer that 65 DEG C of reactions obtain that solid content is 55%, viscosity is 80 Pas/75 DEG C;
2) in prepolymer, add 100 kg chainextender EG, isocyanic ester 360-390 kg and organo-bismuth class catalyzer (BiCAT 8106, the leading chemical company of the U.S. is produced) 0.2kg, after stirring, continue reaction 2-5h in 75-85 DEG C, in the process of reaction, make final viscosity be controlled at 120Pas/25 DEG C along with the increase of system viscosity constantly supplements organic solvent, after having reacted, add reaction terminating agent methyl alcohol 2kg to obtain urethane resin.
Embodiment 2:
1, raw material and proportioning:
1) first the PPG-1 of the PPG-2 of the SP-1 of 600kg, 400kg, 200 kg and 3kg oxidation inhibitor I-1010 are added in organic solvent DMF to the solution that formation solid content is 20%; After stirring, add 130-150kg isocyanic ester in 45 DEG C of reactions 1 hour; Then the HTPB-1 of remaining 30kg is added and continue reaction after 1 hour, then add 50-60 kg isocyanic ester, make in polyol compound the mol ratio 1:1.5 of isocyano in hydroxyl and vulcabond; Finally in the prepolymer that 55 DEG C of reactions obtain that solid content is 45%, viscosity is 30Pas/75 DEG C;
2) in prepolymer, add 100 kg chainextender EG, isocyanic ester 360-390 kg and organo-bismuth class catalyzer (BiCAT 8106, the leading chemical company of the U.S. is produced) 0.2kg, after stirring, continue reaction 2h in 75 DEG C, in the process of reaction, make final viscosity be controlled at 80Pas/25 DEG C along with the increase of system viscosity constantly supplements organic solvent, after having reacted, add reaction terminating agent methyl alcohol 0.5kg to obtain urethane resin.
Comparative example 1:
PTMG-2, polyester diol are dissolved in DMF, then add part MDI, make in polyol compound the mol ratio 1:1.5 of isocyano in hydroxyl and vulcabond carry out prepolymerization reaction, obtain prepolymer.Then in prepolymer, add MDI, catalyzer, the chainextender EG of surplus to continue reaction, make urethane resin.
In order to verify the performance of the high Wet-type polyurethane resin of peeling off of ultra-soft matter snappiness hydrolysis of the present invention, urethane resin prepared by embodiment 1-2 and comparative example 1 is made synthetic leather by existing wet processing, and concrete process hides formula is as follows:
Urethane resin 300 kg
DMF 100 kg
H
2O 2 kg
Permeate agent 4 kg
Foam stabilizer 2 kg
Wood powder 15 kg
Mill base is appropriate
Then draw a design according to synthetic leather industry ordinary method, carry out stripping strength, hydrolysis test, testing method refers to synthetic leather technology, Qu Jianbo etc. write, Chemical Industry Press (2010.3), P127-158 finished leather complete processing, P368 peel strength test method, P369 hydrolysis detection method, adopt quick alkaline-resisting survey to peel off, the slip-stick artist that wet production is please engaged in feel test for a long time judges, the results are shown in following table 1.
Table 1
| Physicals | Embodiment 1 | Embodiment 2 | Comparative example 1 |
| Resin state | Transparent liquid | Transparent liquid | Light yellow transparent liquid |
| Stripping strength N/3cm | 135 | 140 | 100 |
| Hydrolytic resistance N/3cm | 120 | 120 | 75 |
| Feel | Plentiful flexible | Plentiful flexible | Poor compared with plumpness |
As can be seen from Table 1, urethane resin of the present invention is all substantially exceeding ordinary resin aspect stripping strength, hydrolytic resistance and feel.
After testing, the Wet-type polyurethane synthetic leather made from the formula of above-mentioned enforcement, has good rebound resilience, stripping strength is high, durability is superior.
In claims of this specification sheets and the application, so-called system, refers to whole reaction system, is exactly the total amount of all substances.That in above-mentioned embodiment and specification sheets, describes just illustrates principle of the present invention, and the present invention also has various changes and modifications without departing from the spirit and scope of the present invention, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and jljl thereof.
Claims (6)
1. the high Wet-type polyurethane resin of peeling off of ultra-soft matter snappiness hydrolysis, is characterized in that: be prepared from by following raw materials in parts by weight:
Isocyanic ester
Polyol compound
Chainextender
Oxidation inhibitor
Reaction terminating agent methyl alcohol
Organic tin or organo-bismuth class catalyzer, addition is the 0.001-0.05% of polyol compound quality;
The number-average molecular weight of described polyol compound is 1000-3000;
Described polyol compound by polyester polyol, polyether glycol and polyene polyvalent alcohol in mass ratio for 1:0.8-1.2:0.1-0.3 forms;
The molecular weight of described polyester polyol is 2000, and it is by hexanodioic acid 4000kg, ethylene glycol or BDO 2500kg, and catalyst Ti isopropyl propionate 0.4 kg is prepared from;
The total mol ratio of hydroxyl in described isocyanic ester in isocyano and polyol compound and chainextender is 0.9-1:1;
The mol ratio of described polyol compound and chainextender is 1:1.3-1.7.
2. urethane resin according to claim 1, is characterized in that: described isocyanic ester is 4,4 '-diphenylmethanediisocyanate.
3. urethane resin according to claim 1, is characterized in that: described polyester polyol is that functionality is that 2 hexanodioic acid is polyester polyol;
Described polyether glycol is that functionality is 2 polytetrahydrofuran polyvalent alcohol or polyoxypropylene polyol;
Described polyene polyvalent alcohol is that functionality is 2 polybutadiene polyol.
4. urethane resin according to claim 1, is characterized in that: described chainextender is ethylene glycol, BDO, 1, one or both in 6-hexylene glycol, and wherein two kinds of mixing uses are to mix for 0.1:1 ~ 10:1 in molar ratio.
5. a preparation method for the high Wet-type polyurethane resin of peeling off of ultra-soft matter snappiness hydrolysis as claimed in claim 1, is characterized in that: step is as follows:
1) first 60% and the oxidation inhibitor that account for polyol compound total mass are added in organic solvent to the solution that formation solid content is 20-30%; After stirring, add the 20%-25% that accounts for isocyanic ester total mass in 45-50 DEG C of reaction 1-2 hour; Then remaining polyol compound is added and continue reaction after 1-2 hour, then add the 15%-20% that accounts for isocyanic ester total mass, make in polyol compound the mol ratio 1:1.5 of isocyano in hydroxyl and vulcabond; Finally obtaining solid content in 55-65 DEG C of reaction is that 45-55%, viscosity are the prepolymer of 30-80 Pas/75 DEG C;
2) in prepolymer, add chainextender, surplus isocyanic ester and organic tin or organo-bismuth class catalyzer, after stirring, continue reaction 2-5h in 75-85 DEG C, in the process of reaction, make final viscosity be controlled at 80-120Pas/25 DEG C along with the increase of system viscosity constantly supplements organic solvent, after having reacted, add reaction terminating agent methyl alcohol to obtain urethane resin.
6. preparation method according to claim 4, is characterized in that: the water ratio of described polyol compound, isocyanic ester, chainextender is all less than 500ppm; Described organic solvent is N, N '-dimethyl formamide.
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