CN105237725A - Medium-hardness high cold-resistance thermal-adhesion-resistance smooth mirror surface layer polyurethane resin and preparation method thereof - Google Patents
Medium-hardness high cold-resistance thermal-adhesion-resistance smooth mirror surface layer polyurethane resin and preparation method thereof Download PDFInfo
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- CN105237725A CN105237725A CN201510581307.XA CN201510581307A CN105237725A CN 105237725 A CN105237725 A CN 105237725A CN 201510581307 A CN201510581307 A CN 201510581307A CN 105237725 A CN105237725 A CN 105237725A
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- surface layer
- cold
- urethane resin
- adhesion
- heat resistanceheat
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- 239000002344 surface layer Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920005749 polyurethane resin Polymers 0.000 title abstract 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 229920005862 polyol Polymers 0.000 claims abstract description 18
- 229920002545 silicone oil Polymers 0.000 claims abstract description 17
- 239000004970 Chain extender Substances 0.000 claims abstract description 15
- -1 polyol compound Chemical class 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 50
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 26
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 14
- 125000003827 glycol group Chemical group 0.000 claims description 14
- 229920000570 polyether Polymers 0.000 claims description 14
- 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 12
- 150000002148 esters Chemical class 0.000 claims description 12
- 229920005906 polyester polyol Polymers 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003112 inhibitor Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920000728 polyester Polymers 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000013589 supplement Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims 1
- 239000010985 leather Substances 0.000 abstract description 16
- 239000002649 leather substitute Substances 0.000 abstract description 6
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 229910052797 bismuth Inorganic materials 0.000 abstract 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 150000002009 diols Chemical group 0.000 abstract 1
- 239000012948 isocyanate Substances 0.000 abstract 1
- 150000002513 isocyanates Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000012795 verification Methods 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
- C08G18/70—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
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
-
- 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
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
-
- 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
- C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 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
-
- 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
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0016—Foam properties semi-rigid
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention discloses a medium-hardness high cold-resistance thermal-adhesion-resistance smooth mirror surface layer polyurethane resin and a preparation method thereof, wherein the polyurethane resin is mainly prepared from the following components by weight: 9-11 parts of isocyanate, 0.5-5 parts of organic silicone oil, 13-20 parts of a polyol compound, 1-4 parts of a diol chain extender, 0-0.3 part of an antioxidant, and 0-0.05 part of a reaction terminating agent, wherein the addition amount of the organic tin or organic bismuth catalyst is 0.001-0.05% of the weight of the polyol compound. According to the present invention, the cold resistance and the thermal-adhesion-resistance of the medium-hardness mirror surface layer polyurethane resin are substantially improved, and the manufactured synthetic leather shoe leather is durable and has market competitiveness.
Description
Technical field
The present invention relates to synthetic leather manufacture field, specifically cold-resistant heat resistanceheat resistant adhesion agreeable type minute surface surface layer urethane resin of hard height and preparation method thereof in one.
Background technology
Due to the continuous expansion in Synthetic Leather footwear leather market, the requirement of people to footwear leather physical property is more and more higher, especially the environment for use of sports play shoes, make the warping strength performance improving urethane particularly crucial, both required soft comfortable, warping strength performance is good, and feel is smooth again, prevent adhesion, preventing dust is scribbled.But existing urethane resin is difficult to take into account snappiness, winter hardiness, prevent the smooth degree of adhesion and leather surface.
Summary of the invention
The technical problem to be solved in the present invention is to provide cold-resistant heat resistanceheat resistant adhesion agreeable type minute surface surface layer urethane resin of hard height and preparation method thereof in one, solve existing urethane resin to be difficult to take into account snappiness, winter hardiness, prevents the problem of adhesion and the smooth degree of leather surface.
Technical scheme of the present invention is:
The cold-resistant heat resistanceheat resistant adhesion agreeable type minute surface surface layer urethane resin of hard height in one, is mainly prepared from by weight by following component:
Isocyanic ester 9-11 part;
Organic silicone oil 0.5-5 part;
Polyol compound 13-20 part;
Glycol chain extender 1-4 part;
Oxidation inhibitor 0-0.3 part;
Reaction terminating agent 0-0.05 part;
Organic tin or organo-bismuth class catalyzer, addition is the 0.001-0.05% of polyol compound weight.
Described isocyanic ester is 4,4 '-diphenylmethanediisocyanate.
The molecular weight of described organic silicone oil is 2000.
Described polyol compound includes polyester polyol and polyether glycol, and wherein, the mass ratio of polyester polyol and polyether glycol is 1:2-3; The molecular-weight average of described polyol compound is 1000-3000.
Described glycol chain extender is one or both the mixture in ethylene glycol, BDO, 1,6-hexylene glycol, be preferably ethylene glycol or BDO, when ethylene glycol and 1, when 4-butyleneglycol two kinds of alcohol are used in combination, the molar ratio of two kinds of alcohol is 0.1-10:1.
Described reaction terminating agent is methyl alcohol.
Described polyester polyol selects hexanodioic acid system polyester polyol; Described polyether glycol selects polytetrahydrofuran ethoxylated polyhydric alcohol.
The functionality of described organic silicone oil is 2; The functionality of described polyester polyol is 2; The functionality of described polyether glycol is 2.
A preparation method for the cold-resistant heat resistanceheat resistant adhesion agreeable type minute surface surface layer urethane resin of middle hard height, specifically includes following steps:
(1), polyol compound, oxidation inhibitor, organic silicone oil are added together, add organic tin or organo-bismuth class catalyzer after being uniformly mixed and account for the isocyanic ester of isocyanic ester gross weight about 40%, in 65-75 DEG C of reactions 60 minutes, generate the isocyanate-terminated performed polymer of polyester polyether polyol and organic silicone oil diol copolymer;
(2), in the performed polymer of step 1) synthesis, organic solvent is added, be diluted to admittedly containing the organic system of 40-50%, add glycol chain extender again, the isocyanic ester of surplus is progressively added after stirring, reaction 30-40 minutes are often walked at 65-75 DEG C, increase glutinous reaction 3-5h altogether, in the process of reaction, make final viscosity control at 80-120Pas/25 DEG C along with the increase of system viscosity constantly supplements organic solvent, solid content controls 29-31%, adds reaction terminating agent methyl alcohol after having reacted.
Described organic solvent selects N, N '-dimethyl formamide; The water ratio of described polyol compound, isocyanic ester, glycol chain extender, solvent is all less than 500ppm.
Advantage of the present invention:
Urethane resin prepared by the present invention solves existing urethane resin and is difficult to take into account snappiness, winter hardiness, prevents the problem of adhesion and the smooth degree of leather surface.The composition leather shoes leather using the cold-resistant heat resistanceheat resistant adhesion agreeable type minute surface surface layer urethane resin of middle hard height of the present invention to make has the features such as winter hardiness is high, heat resistanceheat resistant adhesive is good, the smooth degree of leather surface is good, and product is durable in use, and product specification is high, has the market competitiveness.
Embodiment
Provide embodiment below to be specifically described the present invention; what be necessary to herein means out is that following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, some nonessential improvement that the person skilled in the art in this field makes the present invention according to content of the present invention and adjustment still belong to protection scope of the present invention.
embodiment 1
The cold-resistant heat resistanceheat resistant adhesion agreeable type minute surface surface layer urethane resin of hard height in one, is mainly prepared from by weight by following component:
| Material name | Weight (unit K g) |
| 4,4-diphenylmethanediisocyanate (MDI) | 600 |
| Organic silicone oil | 30 |
| Polyester polyol (SP-1) | 280 |
| Polyether glycol (PTMG-2) | 640 |
| Glycol chain extender ethylene glycol (EG) | 120 |
| Oxidation inhibitor I-1010 | 10 |
| Terminator methyl alcohol | 1 |
| Organo-bismuth class catalyzer | 0.1 |
| DMF (DMF) | 3900 |
A preparation method for the cold-resistant heat resistanceheat resistant adhesion agreeable type minute surface surface layer urethane resin of middle hard height, specifically includes following steps:
(1), SP-1, PTMG-2, oxidation inhibitor I-1010, organic silicone oil are added together, organo-bismuth class catalyzer (BiCAT 8106 is added after being uniformly mixed, the leading chemical company of the U.S. is produced) and account for the MDI of MDI gross weight 39%, in 65-75 DEG C of reactions 60 minutes, generate the isocyanate-terminated performed polymer of polyester polyether polyol and organic silicone oil diol copolymer;
(2), in the performed polymer of step 1) synthesis, DMF solvent is added, be diluted to admittedly containing the organic system of 40-50%, add glycol chain extender again, the MDI of surplus is progressively added after stirring, at 65-75 DEG C, often walk reaction 30-40 minutes, increase glutinous reaction 3-5h altogether, in the process of reaction, make final viscosity control at 80-120Pas/25 DEG C along with the increase of system viscosity constantly supplements DMF solvent, solid content controls 29-31%, adds reaction terminating agent methyl alcohol after having reacted.
Wherein, the water ratio of above-mentioned SP-1, PTMG-2, MDI, glycol chain extender, DMF solvent is all less than 500ppm.
embodiment 2
The cold-resistant heat resistanceheat resistant adhesion agreeable type minute surface surface layer urethane resin of hard height in one, is mainly prepared from by weight by following component:
| Material name | Weight (unit K g) |
| 4,4-diphenylmethanediisocyanate (MDI) | 560 |
| Organic silicone oil | 40 |
| Polyester polyol (SP-1) | 280 |
| Polyether glycol (PTMG-2) | 640 |
| Glycol chain extender ethylene glycol (EG) | 110 |
| Oxidation inhibitor I-1010 | 10 |
| Terminator methyl alcohol | 1 |
| Organo-bismuth class catalyzer | 0.1 |
| DMF (DMF) | 3900 |
A preparation method for the cold-resistant heat resistanceheat resistant adhesion agreeable type minute surface surface layer urethane resin of middle hard height, specifically includes following steps:
(1), SP-1, PTMG-2, oxidation inhibitor I-1010, organic silicone oil are added together, organo-bismuth class catalyzer (BiCAT 8106 is added after being uniformly mixed, the leading chemical company of the U.S. is produced) and account for the MDI of MDI gross weight about 41%, in 65-75 DEG C of reactions 60 minutes, generate the isocyanate-terminated performed polymer of polyester polyether polyol and organic silicone oil diol copolymer;
(2), in the performed polymer of step 1) synthesis, DMF solvent is added, be diluted to admittedly containing the organic system of 40-50%, add glycol chain extender again, the MDI of surplus is progressively added after stirring, at 65-75 DEG C, often walk reaction 30-40 minutes, increase glutinous reaction 3-5h altogether, in the process of reaction, make final viscosity control at 80-120Pas/25 DEG C along with the increase of system viscosity constantly supplements DMF solvent, solid content controls 29-31%, adds reaction terminating agent methyl alcohol after having reacted.
Wherein, the water ratio of above-mentioned SP-1, PTMG-2, MDI, glycol chain extender, DMF solvent is all less than 500ppm.
verification the verifying results scheme:
In order to verify that the cold-resistant heat resistanceheat resistant adhesion agreeable type minute surface surface layer urethane resin of middle hard height of the present invention has higher winter hardiness, there is good heat resistanceheat resistant adhesive, the resin prepared by above-mentioned embodiment 1-2 and the contrast of common winter hardiness minute surface resin, make synthetic leather according to the following formulation, concrete process hides formula is as follows:
Surface layer: resin 90;
DMF (DMF) 70;
1A70 toner 1;
The colourless coating 150 of tack coat: SA-3635;
IA70 toner 1;
End base: black non-woven fabrics height is peeled off 16 hours hydrolysis and pasted mirror surface leather wet method crust leather;
Wherein, 1A70 toner is the product of Foshan Shunde Baosite Pigment Co., Ltd..
The colourless coating of SA-3635 is the product of Hefei Anli New Material Polyurethane Co., Ltd..
Production technique: two cutter thickness are all coated with 15, bake out temperature 130-135 DEG C
With the Synthetic Leather that above-mentioned formula is made, bend 80,000 times in-20 DEG C of cold-resistant machines, find that this product leather surface does not ftracture, minute surface surface layer cold tolerance is improved as can be seen here.Leather sample is cut into 10 × 10 ㎝ square two, leather surface is to after subsides, press the square iron block that 3 ㎏ are heavy in the above, at 100 DEG C of baking ovens, constant temperature is taken out after placing 1 hour, 30 minutes are placed in room temperature, torn by two pieces of leather with puller system, compared with the synthetic leather product of common winter hardiness minute surface production of resins, the present invention is firmly little again, illustrate that the heat resistanceheat resistant adhesive of this minute surface surface layer improves, leather surface is more smooth.
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.What describe in above-mentioned embodiment and specification sheets 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.Application claims protection domain is defined by appending claims and jljl thereof.
Claims (10)
1. the cold-resistant heat resistanceheat resistant adhesion agreeable type minute surface surface layer urethane resin of hard height in, is characterized in that: be mainly prepared from by weight by following component:
Isocyanic ester 9-11 part;
Organic silicone oil 0.5-5 part;
Polyol compound 13-20 part;
Glycol chain extender 1-4 part;
Oxidation inhibitor 0-0.3 part;
Reaction terminating agent 0-0.05 part;
Organic tin or organo-bismuth class catalyzer, addition is the 0.001-0.05% of polyol compound weight.
2. the cold-resistant heat resistanceheat resistant adhesion agreeable type minute surface surface layer urethane resin of hard height in one according to claim 1, is characterized in that: described isocyanic ester is 4,4 '-diphenylmethanediisocyanate.
3. the cold-resistant heat resistanceheat resistant adhesion agreeable type minute surface surface layer urethane resin of hard height in one according to claim 1, is characterized in that: the molecular weight of described organic silicone oil is 2000.
4. the cold-resistant heat resistanceheat resistant adhesion agreeable type minute surface surface layer urethane resin of hard height in one according to claim 1, it is characterized in that: described polyol compound includes polyester polyol and polyether glycol, wherein, the mass ratio of polyester polyol and polyether glycol is 1:2-3; The molecular-weight average of described polyol compound is 1000-3000.
5. the cold-resistant heat resistanceheat resistant adhesion agreeable type minute surface surface layer urethane resin of hard height in one according to claim 1, it is characterized in that: described glycol chain extender is ethylene glycol, 1,4-butyleneglycol, 1, one or both mixture in 6-hexylene glycol, be preferably ethylene glycol or BDO, when ethylene glycol and 1, when 4-butyleneglycol two kinds of alcohol are used in combination, the molar ratio of two kinds of alcohol is 0.1-10:1.
6. the cold-resistant heat resistanceheat resistant adhesion agreeable type minute surface surface layer urethane resin of hard height in one according to claim 1, is characterized in that: described reaction terminating agent is methyl alcohol.
7. the cold-resistant heat resistanceheat resistant adhesion agreeable type minute surface surface layer urethane resin of hard height in one according to claim 4, is characterized in that: described polyester polyol selects hexanodioic acid system polyester polyol; Described polyether glycol selects polytetrahydrofuran ethoxylated polyhydric alcohol.
8. the cold-resistant heat resistanceheat resistant adhesion agreeable type minute surface surface layer urethane resin of hard height in one according to claim 4, is characterized in that: the functionality of described organic silicone oil is 2; The functionality of described polyester polyol is 2; The functionality of described polyether glycol is 2.
9. the preparation method of the cold-resistant heat resistanceheat resistant adhesion agreeable type minute surface surface layer urethane resin of a kind of middle hard height according to claim 1, is characterized in that: specifically include following steps:
(1), polyol compound, oxidation inhibitor, organic silicone oil are added together, add organic tin or organo-bismuth class catalyzer after being uniformly mixed and account for the isocyanic ester of isocyanic ester gross weight about 40%, in 65-75 DEG C of reactions 60 minutes, generate the isocyanate-terminated performed polymer of polyester polyether polyol and organic silicone oil diol copolymer;
(2), in the performed polymer of step 1) synthesis, organic solvent is added, be diluted to admittedly containing the organic system of 40-50%, add glycol chain extender again, the isocyanic ester of surplus is progressively added after stirring, reaction 30-40 minutes are often walked at 65-75 DEG C, increase glutinous reaction 3-5h altogether, in the process of reaction, make final viscosity control at 80-120Pas/25 DEG C along with the increase of system viscosity constantly supplements organic solvent, solid content controls 29-31%, adds reaction terminating agent methyl alcohol after having reacted.
10. the preparation method of the cold-resistant heat resistanceheat resistant adhesion agreeable type minute surface surface layer urethane resin of a kind of middle hard height according to claim 1, is characterized in that: described organic solvent selects N, N '-dimethyl formamide; The water ratio of described polyol compound, isocyanic ester, glycol chain extender, solvent is all less than 500ppm.
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