CN104387548A - Non-yellowing polyurethane resin for mirror synthetic leather and preparation method of polyurethane resin - Google Patents
Non-yellowing polyurethane resin for mirror synthetic leather and preparation method of polyurethane resin Download PDFInfo
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- CN104387548A CN104387548A CN201410663565.8A CN201410663565A CN104387548A CN 104387548 A CN104387548 A CN 104387548A CN 201410663565 A CN201410663565 A CN 201410663565A CN 104387548 A CN104387548 A CN 104387548A
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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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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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
- C08G18/4236—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
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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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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/70—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
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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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
- C08G18/70—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
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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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
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2203/00—Macromolecular materials of the coating layers
- D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06N2203/068—Polyurethanes
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- 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 invention discloses non-yellowing polyurethane resin for mirror synthetic leather and a preparation method of polyurethane resin. The non-yellowing polyurethane resin is prepared from following raw materials: polyol, a chain extender, diisocyanate, a solvent and an antioxidant, wherein polyol is a mixture of polytetramethylene ether glycol having a number average molecular weight of 2000, polytetramethylene ether glycol having a number average molecular weight of 3000, polydiol adipate having a number average molecular weight of 1000-3000; the chain extender is a mixture of C2-C6 aliphatic diol, piperazine and alicyclic diprimary amine; diisocyanate is aliphatic diisocyanate; the solvent comprises a solvent A, a solvent B and a solvent C, the solvent A is at least one selected from dimethylformamide and dimethylacetamide, the solvent B is at least one selected from toluene, butanone and ethyl acetate and the solvent C is at least one selected from isopropanol or isobutanol. By virtue of the non-yellowing polyurethane resin, the risk of generation of insoluble particulates and topical gel in the system is reduced and meanwhile, the non-yellowing polyurethane resin for synthetic leather has the characteristics of excellent low-temperature folding resistance and good anti-sticking performance.
Description
Technical field
The present invention relates to a kind of urethane resin and preparation method thereof, particularly a kind of mirror face synthetic leather non-yellow stain polyurethane resin and preparation method thereof.
Background technology
Along with the market competition that use for synthetic leather urethane resin deepens constantly, differentiation, novel, stable urethane resin becomes the object that everybody falls over each other to develop gradually.The mirror face synthetic leather non-yellow stain polyurethane resin of high added value is all the more so.
Chinese patent CN101381447B, CN102276783B, CN101857721A, CN102718942A disclose the method preparing non-yellow stain polyurethane resin respectively, all take first pre-polymerization again by the method for aliphatics or alicyclic diamine chain extension, but the diamine used is all binary primary amine.When preparing mirror face synthetic leather non-yellow stain polyurethane resin, a small amount of insoluble particulates or topical gel can be produced, reducing production stability and the quality of product.
In addition, the Intermolecular Forces of non-yellow stain polyurethane resin is more weak, mirror face synthetic leather non-stick property prepared therefrom is poor, and mirror face synthetic leather urethane resin causes its low temperature folding quality to be deteriorated because 100% modular ratio is higher, these problems all limit the development of mirror face synthetic leather urethane resin.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of mirror face synthetic leather non-yellow stain polyurethane resin and preparation method thereof is provided.
The present inventor finds, when preparing mirror face synthetic leather non-yellow stain polyurethane resin, pre-polymerization terminates rear isocyanic ester, and particularly free-diisocyanate content is higher, now add binary primary amine, because binary primary amine contains four reactive hydrogens, reactive behavior is very high, reacts fast and wayward, therefore can produce a small amount of insoluble particulates or topical gel.
According to above discovery, the invention provides a kind of mirror face synthetic leather non-yellow stain polyurethane resin, raw material comprises polyvalent alcohol, chainextender, vulcabond, solvent and oxidation inhibitor, preferably, also comprises functional agent, wherein:
(1) polyvalent alcohol described in is the mixture of the PTMG of number-average molecular weight 2000, the PTMG of number-average molecular weight 3000, the polyester adipate glycol of number-average molecular weight 1000 ~ 3000.
Preferably, described polyester adipate glycol is poly-hexanodioic acid C2 ~ C6 esterdiol, such as polyneopentyl glycol adipate glycol, polybutylene glyool adipate, polyhexamethylene adipate glycol.
Preferably, the number-average molecular weight of described polyester adipate glycol is 2000.
Preferably, the mol ratio of the polyester adipate glycol of the PTMG of described number-average molecular weight 2000, the PTMG of number-average molecular weight 3000, number-average molecular weight 1000 ~ 3000 is (3 ~ 4): (3 ~ 4): 1.
(2) chainextender described in is the mixture of C2 ~ C6 aliphatic diol, piperazine and alicyclic di-primary amine;
Preferably, described C2 ~ C6 aliphatic diol is ethylene glycol or butyleneglycol;
Described alicyclic binary primary amine is 4,4 '-diamino-dicyclohexyl methane;
Preferably, the molar weight sum of piperazine and alicyclic binary primary amine and the ratio of C2 ~ C6 aliphatic diol molar weight are 3 ~ 4:1, and the ratio of the molar weight of piperazine and alicyclic binary primary amine is 0.25 ~ 3:1;
(3) vulcabond described in is aliphatic diisocyanate, such as, be hexamethylene diisocyanate, 4,4'-dicyclohexyl methane diisocyanates, isophorone diisocyanate.
Preferably, described vulcabond is isophorone diisocyanate.
(4) solvent described in comprises solvent orange 2 A, solvent B and solvent C, wherein solvent orange 2 A is selected from least one in dimethyl formamide, N,N-DIMETHYLACETAMIDE, and solvent B is selected from least one in toluene, butanone, vinyl acetic monomer, and solvent C is selected from least one in Virahol, isopropylcarbinol.
Preferably, the ratio that described solvent orange 2 A accounts for weight of solvent is not less than 55%.Preferably, described solvent orange 2 A is dimethyl formamide, and solvent B is toluene, and solvent C is Virahol.
(5) oxidation inhibitor described in is Hinered phenols antioxidant, as antioxidant BHT, antioxidant 1010.
(6) functional agent described in is at least one in flow agent, UV light absorber or viscosity stabilizer;
Described flow agent is polysiloxane, modified polyorganosiloxane or acrylic ester polymer, as the BYK-L9565 of BYK company, the LA-221 of this company of hamming.
Described UV light absorber is benzotriazole compound, as the Tinuvin326 of BASF AG, the Chisorb320 of double bond chemical industry.
Described viscosity stabilizer is phthalic anhydride or oxysuccinic acid.Preferably, the weight percent of above-mentioned raw materials is:
The per-cent sum of each component is 100%
More preferably, the weight percent of above-mentioned raw materials is:
The per-cent sum of each component is 100%;
The preparation method of described mirror face synthetic leather non-yellow stain polyurethane resin, comprises the steps:
1) by partial solvent A, oxidation inhibitor, polyvalent alcohol and C2 ~ C6 aliphatic diol 50 ~ 60 DEG C of mixing;
Described partial solvent A refers to add that weight is solvent orange 2 A gross weight 20 ~ 30% of solvent orange 2 A;
2) then add vulcabond, after being warming up to 95 ~ 105 DEG C, pre-polymerization 3 ~ 4 hours, is then cooled to less than 40 DEG C;
3) add solvent B, remaining solvent orange 2 A and piperazine again, 30 ~ 40 DEG C are reacted 25 ~ 30 minutes;
4) add alicyclic binary primary amine, 40 ~ 50 DEG C are reacted 2 ~ 3 hours, and add solvent C, final viscosity controls, at 80 ~ 120PaS/25 DEG C, optionally to add functional agent, and stir to obtain described mirror face synthetic leather non-yellow stain polyurethane resin.
Compared with prior art, the invention has the beneficial effects as follows: when preparing mirror face synthetic leather non-yellow stain polyurethane resin, first add piperazine after pre-polymerization terminates to react, the content of effective reduction vulcabond particularly free vulcabond, and then carry out chain extending reaction with alicyclic binary primary amine, reduce the risk that system produces insoluble particulates and topical gel.Use for synthetic leather non-yellow stain polyurethane resin prepared by the present invention simultaneously has the advantages that low temperature folding quality is excellent and non-stick property is good.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be appreciated that, these embodiments only for illustration of the present invention, and are not intended to limit the scope of the invention.The improvement made according to the present invention of technician and adjustment, still belong to protection scope of the present invention in actual applications.Following examples are raw materials used be commercially available.
Embodiment 1
Raw materials used and the weight of the present embodiment is as following table 1.
Table 1
| Material name | Weight (gram) | Per-cent (%) |
| Antioxidant BHT | 0.51 | 0.02 |
| PTMG (number-average molecular weight 2000) | 144 | 5.65 |
| PTMG (number-average molecular weight 3000) | 216 | 8.47 |
| Polyneopentyl glycol adipate glycol (number-average molecular weight 2000) | 48 | 1.88 |
| Ethylene glycol | 6.4 | 0.25 |
| Piperazine | 5.31 | 0.21 |
| 4,4 '-diamino-dicyclohexyl methane | 52 | 2.04 |
| Isophorone diisocyanate | 129 | 5.06 |
| Dimethyl formamide | 1109.25 | 43.50 |
| Toluene | 369.75 | 14.50 |
| Virahol | 469.8 | 18.42 |
| Gross weight | 2550.02 | 100％ |
The preparation process of the mirror face synthetic leather non-yellow stain polyurethane resin of the present embodiment is as follows:
1), the polyneopentyl glycol adipate glycol of the PTMG of the PTMG of 221.85g dimethyl formamide, 0.51g antioxidant BHT, 144g molecular weight 2000,216g molecular weight 3000,48g molecular weight 2000,6.4g ethylene glycol are mixed at 50 ~ 60 DEG C;
2), then add 129g isophorone diisocyanate, after being warming up to 95 ~ 105 DEG C, pre-polymerization 3 ~ 4 hours, is then cooled to less than 40 DEG C;
3) add 369.75g toluene, 887.4g dimethyl formamide and 5.31g piperazine, again, 30 ~ 40 DEG C are reacted 25 ~ 30 minutes;
4), add 52g4,4 '-diamino-dicyclohexyl methane, 40 ~ 50 DEG C are reacted 2 ~ 3 hours, and add 469.8g Virahol, final viscosity controls at 80 ~ 120PaS/25 DEG C, and stir to obtain described mirror face synthetic leather non-yellow stain polyurethane resin.
Embodiment 2
Raw materials used and the weight of the present embodiment is as following table 2.
Table 2
| Material name | Weight (gram) | Per-cent (%) |
| Antioxidant BHT | 2.4 | 0.10 |
| PTMG (number-average molecular weight 2000) | 192 | 8.00 |
| PTMG (number-average molecular weight 3000) | 288 | 12.00 |
| Polybutylene glyool adipate (number-average molecular weight 2000) | 48 | 2.00 |
| Ethylene glycol | 11.23 | 0.47 |
| Piperazine | 46.73 | 1.95 |
| 4,4 '-diamino-dicyclohexyl methane | 38.04 | 1.58 |
| Isophorone diisocyanate | 248.75 | 10.36 |
| Dimethyl formamide | 1240 | 51.67 |
| Toluene | 175.4 | 7.30 |
| Virahol | 100 | 4.17 |
| Flow agent | 9.6 | 0.40 |
| Gross weight | 2400.15 | 100 |
Wherein, the chemical name of described flow agent is polyether-modified dimethyl polysiloxane, adopts the BYK-L9565 of BYK company.
The preparation process of the mirror face synthetic leather non-yellow stain polyurethane resin of the present embodiment is as follows:
1), the polybutylene glyool adipate of the PTMG of the PTMG of 372g dimethyl formamide, 2.4g antioxidant BHT, 192g molecular weight 2000,288g molecular weight 3000,48g molecular weight 2000,11.23g ethylene glycol are mixed at 50 ~ 60 DEG C;
2), then add 248.75g isophorone diisocyanate, after being warming up to 95 ~ 105 DEG C, pre-polymerization 3 ~ 4 hours, is then cooled to less than 40 DEG C;
3) add 175.4g toluene, 868g dimethyl formamide and 46.73g piperazine, again, 30 ~ 40 DEG C are reacted 25 ~ 30 minutes;
4), add 38.04g4,4 '-diamino-dicyclohexyl methane, 40 ~ 50 DEG C are reacted 2 ~ 3 hours, add 100g Virahol, final viscosity controls at 80 ~ 120PaS/25 DEG C, adds 9.6g flow agent, and stir to obtain described mirror face synthetic leather non-yellow stain polyurethane resin.
Embodiment 3
Raw materials used and the weight of the present embodiment is as following table 3.
Table 3
| Material name | Weight (gram) | Per-cent (%) |
| Antioxidant BHT | 0.41 | 0.02 |
| PTMG (number-average molecular weight 2000) | 144 | 7.06 |
| PTMG (number-average molecular weight 3000) | 216 | 10.59 |
| Polyneopentyl glycol adipate glycol (number-average molecular weight 2000) | 48 | 2.35 |
| Ethylene glycol | 7.82 | 0.38 |
| Piperazine | 6.51 | 0.32 |
| 4,4 '-diamino-dicyclohexyl methane | 63.62 | 3.12 |
| Isophorone diisocyanate | 146.39 | 7.18 |
| Dimethyl formamide | 914.85 | 44.84 |
| Toluene | 281.49 | 13.80 |
| Virahol | 211.12 | 10.34 |
| Gross weight | 2040.21 | 100 |
The preparation process of the mirror face synthetic leather non-yellow stain polyurethane resin of the present embodiment is as follows:
1), the polyneopentyl glycol adipate glycol of the PTMG of the PTMG of 182.97g dimethyl formamide, 0.41g antioxidant BHT, 144g molecular weight 2000,216g molecular weight 3000,48g molecular weight 2000,7.82g ethylene glycol are mixed at 50 ~ 60 DEG C;
2), then add 146.39g isophorone diisocyanate, be warming up to 95 ~ 105 DEG C, pre-polymerization 3 ~ 4 hours, is then cooled to less than 40 DEG C;
3) add 281.49g toluene, 731.88g dimethyl formamide, 6.51g piperazine, again, 30 ~ 40 DEG C are reacted 25 ~ 30 minutes;
4), 63.62g4 is added, 4 '-diamino-dicyclohexyl methane, 40 ~ 50 DEG C are reacted 2 ~ 3 hours, add 211.12g Virahol, final viscosity controls at 80 ~ 120PaS/25 DEG C, and stir to obtain described mirror face synthetic leather non-yellow stain polyurethane resin.
Embodiment 4
Raw materials used and the weight of the present embodiment is as following table 4.
Table 4
| Material name | Weight (gram) | Per-cent (%) |
| Antioxidant BHT | 0.71 | 0.02 |
| PTMG (number-average molecular weight 2000) | 192 | 6.67 |
| PTMG (number-average molecular weight 3000) | 288 | 10.01 |
| Polyneopentyl glycol adipate glycol (number-average molecular weight 2000) | 48 | 1.67 |
| Ethylene glycol | 9.39 | 0.33 |
| Piperazine | 39.07 | 1.36 |
| 4,4 '-diamino-dicyclohexyl methane | 31.81 | 1.11 |
| Isophorone diisocyanate | 220.39 | 7.66 |
| Dimethyl formamide | 1389.08 | 48.28 |
| Toluene | 347.27 | 12.07 |
| Isopropylcarbinol | 306.41 | 10.65 |
| UV light absorber | 5 | 0.17 |
| Gross weight | 2877.13 | 100 |
Wherein, the chemical name of described UV light absorber is 2-(2 '-hydroxyl-3 '-the tertiary butyl-5 '-aminomethyl phenyl)-5-chlorinated benzotriazole, adopts the Tinuvin326 of BASF AG.
The preparation process of the mirror face synthetic leather non-yellow stain polyurethane resin of the present embodiment is as follows:
1), the polyneopentyl glycol adipate glycol of the PTMG of the PTMG of 347.27g dimethyl formamide, 0.71g antioxidant BHT, 192g molecular weight 2000,288g molecular weight 3000,48g molecular weight 2000,9.39g ethylene glycol are mixed at 50 ~ 60 DEG C;
2), then add 220.39g isophorone diisocyanate, be warming up to 95 ~ 105 DEG C, pre-polymerization 3 ~ 4 hours, is then cooled to less than 40 DEG C;
3) add 347.27g toluene, 1041.81g dimethyl formamide and 39.07g piperazine, again, 30 ~ 40 DEG C are reacted 25 ~ 30 minutes;
4), add 31.81g4,4 '-diamino-dicyclohexyl methane, 40 ~ 50 DEG C are reacted 2 ~ 3 hours, add 306.41g isopropylcarbinol, final viscosity controls at 80 ~ 120PaS/25 DEG C, adds 5g UV light absorber, and stir to obtain described mirror face synthetic leather non-yellow stain polyurethane resin.
Embodiment 5
Raw materials used and the weight of the present embodiment is as following table 5.
Table 5
| Material name | Weight (gram) | Per-cent (%) |
| Antioxidant 1010 | 0.75 | 0.04 |
| PTMG (number-average molecular weight 2000) | 133.6 | 6.36 |
| PTMG (number-average molecular weight 3000) | 210 | 10.00 |
| Polyneopentyl glycol adipate glycol (number-average molecular weight 2000) | 43.2 | 2.06 |
| Butyleneglycol | 9.72 | 0.46 |
| Piperazine | 12.28 | 0.58 |
| 4,4 '-diamino-dicyclohexyl methane | 53.99 | 2.57 |
| 4,4'-dicyclohexyl methane diisocyanate | 174.73 | 8.32 |
| Dimethyl formamide | 949.88 | 45.25 |
| Toluene | 292.27 | 13.92 |
| Virahol | 219.2 | 10.44 |
| Gross weight | 2099.62 | 100 |
The preparation process of the mirror face synthetic leather non-yellow stain polyurethane resin of the present embodiment is as follows:
1), the polyneopentyl glycol adipate glycol of the PTMG of the PTMG of 269g dimethyl formamide, 0.75g antioxidant 1010,133.6g molecular weight 2000,210g molecular weight 3000,43.2g molecular weight 2000,9.72g butyleneglycol are mixed at 50 ~ 60 DEG C;
2), then add 174.73g4,4'-dicyclohexyl methane diisocyanate, be warming up to 95 ~ 105 DEG C, pre-polymerization 3 ~ 4 hours, is then cooled to less than 40 DEG C;
3) add 292.27g toluene, 680.88g dimethyl formamide and 12.28g piperazine, again, 30 ~ 40 DEG C are reacted 25 ~ 30 minutes;
4), add 53.99g4,4 '-diamino-dicyclohexyl methane, 40 ~ 50 DEG C are reacted 2 ~ 3 hours, and add 219.2g Virahol, final viscosity controls at 80 ~ 120PaS/25 DEG C, and stir to obtain described mirror face synthetic leather non-yellow stain polyurethane resin.
The applicating example of embodiment illustrates:
10 parts of color chips, 100 parts of above-mentioned urethane resins, 40 parts of dimethyl formamides, 35 parts of butanone are mixed and deaeration, be coated on mirror surface release paper with scraper with the thickness of 0.2mm, through 120 DEG C of oven for drying, apply the cold resisting type tie layer resins that 0.15mm is thick again, then to fit the superfine fiber synthetic leather base cloth of 1.2mm, dry and also peel off to obtain mirror face synthetic leather finished product from separate-type paper.The physical property of embodiment 1 to 5, commercially available mirror face synthetic leather non-yellow stain polyurethane resin sample detects in table 6.
The physical property detected result of table 6 embodiment and commercially available sample
As known from Table 6, the non-yellow stain polyurethane resin that prepared by the present invention has excellent low temperature folding quality and non-stick property.
Claims (13)
1. mirror face synthetic leather non-yellow stain polyurethane resin, is characterized in that, raw material comprises polyvalent alcohol, chainextender, vulcabond, solvent and oxidation inhibitor, wherein:
(1) polyvalent alcohol described in is the mixture of the PTMG of number-average molecular weight 2000, the PTMG of number-average molecular weight 3000, the polyester adipate glycol of number-average molecular weight 1000 ~ 3000;
(2) chainextender described in is the mixture of C2 ~ C6 aliphatic diol, piperazine and alicyclic di-primary amine;
(3) vulcabond described in is aliphatic diisocyanate;
(4) solvent described in comprises solvent orange 2 A, solvent B and solvent C, wherein solvent orange 2 A is selected from least one in dimethyl formamide, N,N-DIMETHYLACETAMIDE, and solvent B is selected from least one in toluene, butanone, vinyl acetic monomer, and solvent C is selected from least one in Virahol or isopropylcarbinol.
2. mirror face synthetic leather non-yellow stain polyurethane resin according to claim 1, is characterized in that, described polyester adipate glycol is poly-hexanodioic acid C2 ~ C6 esterdiol.
3. mirror face synthetic leather non-yellow stain polyurethane resin according to claim 2, is characterized in that, the number-average molecular weight of described polyester adipate glycol is 2000.
4. the mirror face synthetic leather non-yellow stain polyurethane resin according to any one of claims 1 to 3, it is characterized in that, the mol ratio of the polyester adipate glycol of the PTMG of described number-average molecular weight 2000, the PTMG of number-average molecular weight 3000, number-average molecular weight 1000 ~ 3000 is 3 ~ 4:3 ~ 4:1.
5. mirror face synthetic leather non-yellow stain polyurethane resin according to claim 1, is characterized in that, described C2 ~ C6 aliphatic diol is ethylene glycol or butyleneglycol; Described alicyclic binary primary amine is 4,4 '-diamino-dicyclohexyl methane.
6. mirror face synthetic leather non-yellow stain polyurethane resin according to claim 1 or 5, it is characterized in that, the molar weight sum of piperazine and alicyclic binary primary amine and the ratio of C2 ~ C6 aliphatic diol molar weight are 3 ~ 4:1, and the ratio of the molar weight of piperazine and alicyclic binary primary amine is 0.25 ~ 3:1.
7. mirror face synthetic leather non-yellow stain polyurethane resin according to claim 1, is characterized in that, described vulcabond is hexamethylene diisocyanate, 4,4'-dicyclohexyl methane diisocyanates or isophorone diisocyanate.
8. mirror face synthetic leather non-yellow stain polyurethane resin according to claim 1, is characterized in that, the ratio that described solvent orange 2 A accounts for weight of solvent is not less than 55%, and described solvent orange 2 A is dimethyl formamide, and solvent B is toluene, and solvent C is Virahol.
9. mirror face synthetic leather non-yellow stain polyurethane resin according to claim 1, it is characterized in that, raw material also comprises functional agent, and described functional agent is at least one in flow agent, UV light absorber or viscosity stabilizer.
10. mirror face synthetic leather non-yellow stain polyurethane resin according to claim 1, is characterized in that, the weight percent of raw material is:
11. mirror face synthetic leather non-yellow stain polyurethane resins according to claim 1, is characterized in that, the weight percent of raw material is:
The method of the mirror face synthetic leather non-yellow stain polyurethane resin described in 12. any one of preparation claim 1 ~ 8, is characterized in that, comprise the steps:
1) by partial solvent A, oxidation inhibitor, polyvalent alcohol and C2 ~ C6 aliphatic diol 50 ~ 60 DEG C of mixing;
Described partial solvent A refers to add that weight is solvent orange 2 A gross weight 20 ~ 30% of solvent orange 2 A;
2) then add vulcabond, after being warming up to 95 ~ 105 DEG C, pre-polymerization 3 ~ 4 hours, is then cooled to less than 40 DEG C;
3) add solvent B, remaining solvent orange 2 A and piperazine again, 30 ~ 40 DEG C are reacted 25 ~ 30 minutes;
4) add alicyclic binary primary amine, 40 ~ 50 DEG C are reacted 2 ~ 3 hours, and add solvent C, final viscosity controls at 80 ~ 120Pa.S/25 DEG C, and stir to obtain described mirror face synthetic leather non-yellow stain polyurethane resin.
The method of the mirror face synthetic leather non-yellow stain polyurethane resin described in 13. preparation any one of claim 9 ~ 11, is characterized in that, comprise the steps: 1) by partial solvent A, oxidation inhibitor, polyvalent alcohol and C2 ~ C6 aliphatic diol 50 ~ 60 DEG C of mixing;
Described partial solvent A refers to add that weight is solvent orange 2 A gross weight 20 ~ 30% of solvent orange 2 A;
2) then add vulcabond, after being warming up to 95 ~ 105 DEG C, pre-polymerization 3 ~ 4 hours, is then cooled to less than 40 DEG C;
3) add solvent B, remaining solvent orange 2 A and piperazine again, 30 ~ 40 DEG C are reacted 25 ~ 30 minutes;
4) add alicyclic binary primary amine, 40 ~ 50 DEG C are reacted 2 ~ 3 hours, and add solvent C, final viscosity controls, at 80 ~ 120Pa.S/25 DEG C, to add functional agent, and stir to obtain described mirror face synthetic leather non-yellow stain polyurethane resin.
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