CN115651156B - Solvent-free polyurethane resin and preparation method and application thereof - Google Patents
Solvent-free polyurethane resin and preparation method and application thereof Download PDFInfo
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- CN115651156B CN115651156B CN202211384274.6A CN202211384274A CN115651156B CN 115651156 B CN115651156 B CN 115651156B CN 202211384274 A CN202211384274 A CN 202211384274A CN 115651156 B CN115651156 B CN 115651156B
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 229920002635 polyurethane Polymers 0.000 claims abstract description 101
- 239000004814 polyurethane Substances 0.000 claims abstract description 101
- 229920005862 polyol Polymers 0.000 claims abstract description 85
- 150000003077 polyols Chemical class 0.000 claims abstract description 84
- 150000001718 carbodiimides Chemical class 0.000 claims abstract description 55
- 239000002649 leather substitute Substances 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 27
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 18
- 150000003384 small molecules Chemical group 0.000 claims abstract description 14
- 239000004970 Chain extender Substances 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000002344 surface layer Substances 0.000 claims description 41
- 150000002009 diols Chemical class 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- -1 1, 4-cyclohexanedimethanol hydroquinone bis (2-hydroxyethyl) ether Chemical compound 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- 230000014759 maintenance of location Effects 0.000 claims description 12
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims description 8
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000004417 polycarbonate Substances 0.000 claims description 7
- 229920000515 polycarbonate Polymers 0.000 claims description 7
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 6
- 230000003111 delayed effect Effects 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 4
- 229940035437 1,3-propanediol Drugs 0.000 claims description 4
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 claims description 3
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 claims description 3
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940031826 phenolate Drugs 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 32
- 239000010410 layer Substances 0.000 description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000005266 casting Methods 0.000 description 9
- 238000001514 detection method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229920001410 Microfiber Polymers 0.000 description 6
- 239000003658 microfiber Substances 0.000 description 6
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 6
- 101000974007 Homo sapiens Nucleosome assembly protein 1-like 3 Proteins 0.000 description 4
- 102100022398 Nucleosome assembly protein 1-like 3 Human genes 0.000 description 4
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 4
- 239000010985 leather Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
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- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000004872 foam stabilizing agent Substances 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- 150000004707 phenolate Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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Landscapes
- Polyurethanes Or Polyureas (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention discloses a solvent-free polyurethane resin and a preparation method and application thereof, wherein the solvent-free polyurethane resin comprises a component A and a component B, wherein the component A consists of 85-95 parts of carbodiimide modified polyol, 4-13 parts of small molecule chain extender, 0.1-0.5 part of small molecule cross-linking agent, 0.4-1 part of leveling agent, 0.4-1 part of catalyst and 0.1-0.5 part of antioxidant; the component B consists of 35-65 parts of carbodiimide modified polyol, 20-35 parts of diisocyanate, 15-30 parts of organosilicon polyol and 0.1-0.5 part of antioxidant. The solvent-free polyurethane resin contains carbodiimide modified polyol, and the interface binding force between the solvent-free polyurethane layer and the aqueous polyurethane layer can be improved by applying the solvent-free polyurethane resin to the aqueous/solvent-free polyurethane synthetic leather, so that high peel strength is obtained.
Description
Technical Field
The invention belongs to the technical field of polyurethane synthetic leather, and particularly relates to a solvent-free polyurethane resin, a preparation method of the solvent-free polyurethane resin, and application of the solvent-free polyurethane resin in water-based/solvent-free polyurethane synthetic leather.
Background
Along with the transformation development of the synthetic leather industry, the water-based synthetic leather, the solvent-free synthetic leather and the TPU synthetic leather rapidly develop, and bring new opportunities for the environmental protection and cleaning of the synthetic leather industry. Among them, the development of aqueous/solventless synthetic leather is most remarkable, and the aqueous/solventless synthetic leather product has a porous structure of solvent-free foaming and does not need to add a harmful solvent in the production process, so that the aqueous/solventless synthetic leather product has the advantages of various color and feel and excellent environmental protection performance, and is therefore paid attention to.
However, the existing water-based/solvent-free synthetic leather product is generally only applicable to synthetic leather such as clothing leather, sofa leather and the like with low requirements on peeling strength due to the problem of poor bonding strength of a water-based polyurethane surface layer and a solvent-free polyurethane foaming layer, and is difficult to apply to shoe leather with high requirements on peeling strength; the preparation method is mainly characterized in that in the water-based/solvent-free process, most of water-based polyurethane in the market is carboxylic acid, dimethylolpropionic acid (DMPA) is mainly used as a hydrophilic group, triethylamine (TEA) is used as a neutralizer, and the water-based polyurethane film contains more carboxyl after the triethylamine volatilizes along with the rise of temperature in the film forming process of the water-based polyurethane; the carboxyl is acidic and can inhibit the curing reaction of the solvent-free bi-component polyurethane at the interface, so that the interface is insufficient in curing and weak in strength, the stripping force between the solvent-free intermediate layer and the water-based surface layer is usually only under the actions of Van der Waals force and hydrogen bond, the effect of intertwining molecular chains is difficult to achieve, and obvious interfaces exist, so that the acting force between the interfaces is weak; the peel strength is only between 30 and 90N/3cm, and high peel level (more than or equal to 120N/3 cm) is difficult to achieve.
Disclosure of Invention
In view of the above, the present invention is to provide a solvent-free polyurethane resin, which is prepared by reacting a polyol having a carbodiimide structure with a solvent-free polyurethane main body by modifying the polyol with carbodiimide, and by reacting the carbodiimide with a large amount of carboxyl groups in the aqueous polyurethane, so that the solvent-free polyurethane layer and the aqueous polyurethane surface layer are bonded by chemical bonds, thereby improving the interfacial bonding force between the solvent-free polyurethane layer and the aqueous polyurethane layer, and realizing the preparation of the aqueous/solvent-free polyurethane synthetic leather with high peel strength.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention provides a solvent-free polyurethane resin, which comprises a component A and a component B, wherein the component A consists of 85-95 parts of carbodiimide modified polyol, 4-13 parts of small molecule chain extender, 0.1-0.5 part of small molecule cross-linking agent, 0.4-1 part of leveling agent, 0.4-1 part of catalyst and 0.1-0.5 part of antioxidant according to parts by weight;
The component B consists of 35-65 parts of carbodiimide modified polyol, 20-35 parts of diisocyanate, 15-30 parts of organosilicon polyol and 0.1-0.5 part of antioxidant.
Further, the mass ratio of the component A to the component B is 100:80-100:135.
Further, the carbodiimide modified polyol is obtained by reacting carbodiimide modified diisocyanate with oligomer dihydric alcohol under the action of a catalyst.
Further, the oligomer dihydric alcohol is one selected from polytetrahydrofuran dihydric alcohol, polypropylene oxide dihydric alcohol, polycarbonate dihydric alcohol, polycaprolactone dihydric alcohol and polymer dihydric alcohol, and the molecular weight of the oligomer dihydric alcohol is between 1000 and 3000.
Further, the small molecule chain extender is selected from one of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, diethylene glycol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, and 1, 4-cyclohexanedimethanol hydroquinone bis (2-hydroxyethyl) ether;
the small molecule cross-linking agent is selected from one of glycerol and trimethylolpropane;
The leveling agent is an organosilicon leveling agent, and the organosilicon leveling agent is selected from one of BYK-322, BYK-333, BYK-345 and BYK-361N;
The catalyst is selected from one of delayed type environment-friendly metal catalyst or phenolate, formate and hydrochloride thereof, and the delayed type environment-friendly catalyst is selected from one of BiCAT 8106, biCAT 8108, biCAT 8124, biCAT 3228, borchi Kat 22, borchi Kat 24, biCAT 4130, biCAT 4232 and MB 20;
The antioxidant is selected from one of antioxidant 245, antioxidant 1010, antioxidant 1035, antioxidant 1076, antioxidant 1098 or antioxidant 3114;
The diisocyanate is selected from one of 4,4' -diphenylmethane diisocyanate, a mixture of 2, 4-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate in a mass ratio of 1:1, isophorone diisocyanate, hexamethylene diisocyanate and 4,4' -dicyclohexylmethane diisocyanate;
the organosilicon polyol is selected from one of TECH-2120, TECH-2127, TECH-2420, TECH-2135 and SF-9201.
The invention further provides a preparation method of the solvent-free polyurethane resin, which comprises the following steps:
Preparation of carbodiimide-modified polyol: stirring carbodiimide modified diisocyanate and oligomer dihydric alcohol and a catalyst at 60-90 ℃ for reaction for 1-3h to prepare carbodiimide modified polyol;
Preparing a component A: mixing the carbodiimide modified polyol after vacuum dehydration with a micromolecular chain extender, a micromolecular crosslinking agent, a catalyst, an antioxidant and a leveling agent at 30-40 ℃, then heating to 60-80 ℃ and stirring for 1-3h to obtain a component A;
And (3) preparing a component B: stirring carbodiimide modified polyol, diisocyanate and an antioxidant for 10-20min, then adding organosilicon polyol, and stirring at 60-90 ℃ for 2-4h to prepare a component B;
preparing solvent-free polyurethane resin: and fully mixing the component A and the component B according to the mass ratio of 100:80-100:135 to obtain the solvent-free polyurethane resin.
The invention further provides a preparation method of the polyurethane synthetic leather, which comprises the following steps:
forming a water-based polyurethane surface layer;
pouring and coating the solvent-free polyurethane resin on the surface of the water-based polyurethane surface layer, pre-reacting for 30-90s at 100-140 ℃, attaching the base cloth, and then continuously reacting for 5-10min at 100-140 ℃ to crosslink, solidify and form the water-based polyurethane surface layer;
and (5) rolling and stripping after molding to obtain the water-based/solvent-free polyurethane synthetic leather.
Further, the aqueous polyurethane surface layer is obtained by coating anionic surface layer resin on release paper, and then drying and molding.
The invention also provides polyurethane synthetic leather which is prepared by adopting the preparation method, wherein the peel strength of the polyurethane synthetic leather can reach more than 120N/3cm, and the retention rate of the peel strength of the polyurethane synthetic leather after 10 weeks at the constant temperature and humidity of 95% RH at 70 ℃ is more than 75%.
Compared with the prior art, the invention has the following beneficial effects:
In the solvent-free polyurethane resin, the invention adopts carbodiimide modified polyol innovatively, the polyol containing carbodiimide structure is reacted on the solvent-free polyurethane main body, and the carbodiimide is reacted with a large amount of carboxyl in the aqueous polyurethane: on one hand, the solvent-free polyurethane layer and the water-based polyurethane surface layer can be combined through chemical bonds, so that the interfacial bonding force between the solvent-free polyurethane layer and the water-based polyurethane surface layer is obviously improved, and the adverse effect of carboxyl on the solvent-free polyurethane reaction is avoided; on the other hand, the hydrolysis resistance of the water-based polyurethane surface layer after carboxyl groups are reacted can be greatly improved.
The organic silicon is introduced into the solvent-free polyurethane resin, so that the solvent-free polyurethane resin has the characteristic of low surface energy, and can be easily coated on the surface of the water-based polyurethane surface layer under the condition that a leveling agent is not needed.
In addition, the solvent-free polyurethane resin disclosed by the invention does not contain any organic solvent, is environment-friendly, and can meet the high environment-friendly requirement of zero DMF.
Drawings
FIG. 1 is a schematic diagram of interfacial bonding of a solvent-free polyurethane layer and an aqueous polyurethane topcoat in accordance with the present invention.
Detailed Description
The following detailed description of embodiments of the invention is exemplary and is provided merely to illustrate the invention and is not to be construed as limiting the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The invention provides a solvent-free polyurethane resin, which comprises a component A and a component B, wherein the component A consists of 85-95 parts by mass of carbodiimide modified polyol, 4-13 parts by mass of small molecule chain extender, 0.1-0.5 part by mass of small molecule cross-linking agent, 0.4-1 part by mass of leveling agent, 0.4-1 part by mass of catalyst and 0.1-0.5 part by mass of antioxidant;
The component B consists of 35-65 parts of carbodiimide modified polyol, 20-35 parts of diisocyanate, 15-30 parts of organosilicon polyol and 0.1-0.5 part of antioxidant.
According to the invention, the carbodiimide modified polyol is introduced into the solvent-free polyurethane resin, the polyol containing the carbodiimide structure is reacted on the solvent-free polyurethane resin main body, and in the subsequent process of preparing the synthetic leather, the carbodiimide reacts with a large amount of carboxyl groups in the aqueous polyurethane, so that the solvent-free polyurethane layer and the aqueous polyurethane surface layer are combined through chemical bonds, and the interfacial bonding force between the solvent-free polyurethane layer and the aqueous polyurethane surface layer is obviously improved.
The mass ratio of the component a to the component B is not particularly limited, and may be adjusted according to the known and actual conditions in the art, and in some specific embodiments of the present invention, the mass ratio of the component a to the component B is 100: (80-135).
Specifically, the carbodiimide modified polyol in the component A is obtained by reacting carbodiimide modified diisocyanate with oligomer diol under the action of a catalyst. For example, taking the reaction of carbodiimide-modified diphenylmethane diisocyanate (MDI) with an oligomeric diol, the specific reaction is as follows:
It will be appreciated that the preparation of carbodiimide-modified diisocyanates is well known to those skilled in the art, i.e. the polycondensation of the diisocyanate itself takes place under heating with the presence of an organophosphine as catalyst to give compounds containing carbodiimide groups (-n=c=n-). It will be appreciated that it may be prepared by conventional methods, or may be obtained directly from commercial sources, and in some specific embodiments of the invention, the carbodiimide modified diphenylmethane diisocyanate (MDI) described above is prepared by the reaction:
it will be appreciated that the above carbodiimide-modified diphenylmethane diisocyanate (MDI) is merely exemplary of the invention and that other types of diisocyanates may be used in the present invention, the specific reaction mechanism or mechanisms of which are similar to those described above and will not be specifically described herein.
According to the embodiment of the invention, raw materials adopted for preparing the carbodiimide modified polyol are specifically as follows in parts by mass: 20-35 parts of diisocyanate, 0.4-1 part of triethyl phosphate, 65-80 parts of oligomer dihydric alcohol and 0.1-0.5 part of catalyst. The preparation method comprises the following specific steps: preparing carbodiimide modified diisocyanate by reacting diisocyanate at high temperature (stirring for 2-3h at 180-230 ℃) under the action of catalyst triethyl phosphate; and then reacting the carbodiimide modified diisocyanate with the oligomer dihydric alcohol under the action of a catalyst (reacting for 1-3h at 60-90 ℃) to prepare the carbodiimide modified polyol.
Wherein the diisocyanates described herein are distinguished by the number of-NCO groups, which are conventional choices in the art, specific examples that may be mentioned include, but are not limited to, 4' -diphenylmethane diisocyanate (MDI-100), a mixture of 2, 4-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate in a 1:1 mass ratio (MDI-50), isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), 4' -dicyclohexylmethane diisocyanate (HMDI).
The oligomeric polyols described herein are polyols having a molecular weight between 1000 and 3000, and in some embodiments of the present invention, the oligomeric polyols are selected from one of polytetrahydrofuran diol, polyoxypropylene diol, polycarbonate diol, polycaprolactone diol, and polymer diol.
The catalyst is an environment-friendly delayed metal catalyst and the like which are well known in the art and used for the reaction of diisocyanate and polyol, and are not specifically described herein.
Further, the small molecule chain extender in the component a is a small molecule diol, specifically an alcohol containing two hydroxyl groups in the molecule, and may be selected according to the routine in the art, and in some specific embodiments of the present invention, the small molecule chain extender is selected from one of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, diethylene glycol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol hydroquinone bis (2-hydroxyethyl) ether.
Further, the small molecule cross-linking agent in the component a is a small molecule polyol, that is, an alcohol containing three or more hydroxyl groups in the molecule, and may be selected according to the well known to those skilled in the art, and in some specific embodiments of the present invention, the small molecule cross-linking agent is one selected from glycerol and trimethylolpropane.
Further, the leveling agent described in the A-component is preferably an organosilicon-based leveling agent, which can be used as is well known to those skilled in the art, and specific examples include, but are not limited to, one of BYK-322, BYK-333, BYK-345, BYK-361N;
Further, both the catalyst and the antioxidant described in component a may be used as is well known to those skilled in the art, wherein in some embodiments of the present invention the catalyst is selected from a delayed type environmentally friendly metal catalyst selected from one of BiCAT 8106, biCAT 8108, biCAT 8124, biCAT3228, borchi Kat 22, borchi Kat 24, biCAT 4130, biCAT 4232, MB20, or one of its phenolates, formates, hydrochlorides; the antioxidant is selected from one of antioxidant 245, antioxidant 1010, antioxidant 1035, antioxidant 1076, antioxidant 1098 or antioxidant 3114;
Further, the part of the raw materials in the component B and the part of the raw materials in the component A have the same meaning, so that the details are not described. Among them, silicone polyols described in the B component are well known to those skilled in the art, and specific examples that may be mentioned include, but are not limited to, one of TECH-2120, TECH-2127, TECH-2420, TECH-2135, SF-9201. By introducing the organosilicon, the solvent-free polyurethane can be easily coated on the surface of the water-based polyurethane surface layer under the condition of no need of a leveling agent by utilizing the characteristic of low surface energy of the organosilicon.
According to a second aspect of the present invention, there is provided a method for preparing a solvent-free polyurethane resin according to the first aspect of the present invention, comprising the steps of:
Preparation of carbodiimide-modified polyol: stirring carbodiimide modified diisocyanate and oligomer dihydric alcohol and a catalyst at 60-90 ℃ for reaction for 1-3h to prepare carbodiimide modified polyol; wherein the carbodiimide-modified diisocyanate is obtained in a manner well known in the art, and in some embodiments of the invention is prepared by reacting a triethyl phosphate catalyst with stirring at 180-230 ℃ for 2-3 hours;
Preparing a component A: mixing the carbodiimide modified polyol after vacuum dehydration with a micromolecular chain extender, a micromolecular crosslinking agent, a catalyst, an antioxidant and a leveling agent at 30-40 ℃, then heating to 60-80 ℃ and stirring for 1-3h to obtain a component A;
And (3) preparing a component B: stirring carbodiimide modified polyol, diisocyanate and an antioxidant for 10-20min, then adding organosilicon polyol, and stirring at 60-90 ℃ for 2-4h to prepare a component B;
Preparing solvent-free polyurethane resin: and fully mixing the component A and the component B according to the mass ratio of 100:80-100:135 to obtain the solvent-free polyurethane resin, wherein a carbodiimide structure is contained on a solvent-free polyurethane main body of the solvent-free polyurethane resin.
The third aspect of the present invention provides a method for preparing polyurethane synthetic leather, which applies the solvent-free polyurethane resin to aqueous/solvent-free polyurethane synthetic leather, thereby remarkably improving interfacial binding force between a solvent-free polyurethane layer and an aqueous polyurethane layer, the preparation of the polyurethane synthetic leather comprising the steps of:
forming a water-based polyurethane surface layer;
Casting and coating the solvent-free polyurethane resin according to the third aspect of the invention on the surface of the water-based polyurethane surface layer, pre-reacting for 30-90s at 100-140 ℃, attaching the base cloth, and then continuously reacting for 5-10min at 100-140 ℃ to crosslink, solidify and form the water-based polyurethane surface layer;
and (5) rolling and stripping after molding to obtain the water-based/solvent-free polyurethane synthetic leather.
The preparation of the aqueous polyurethane surface layer is not particularly limited, and may be performed in a conventional manner in the art, and in some specific embodiments of the present invention, the aqueous polyurethane surface layer is obtained by coating an anionic surface layer resin on release paper and then drying and molding.
According to the invention, the polyurethane synthetic leather is prepared by adopting the preparation method according to the third aspect of the invention, and the carbodiimide structure is contained in the solvent-free polyurethane main body, so that after the carbodiimide structure is coated on the surface of the aqueous polyurethane surface layer, chemical bonds are formed by crosslinking and curing reaction of a large number of carboxyl groups in the aqueous polyurethane, and the interfacial bonding force between the aqueous polyurethane surface layer and the solvent-free polyurethane layer is remarkably improved, and the specific principle can be seen in fig. 1. According to the embodiment of the invention, the peel strength of the prepared aqueous/solvent-free polyurethane synthetic leather can reach more than 120N/3cm, and the retention rate of the peel strength after 10 weeks at 70 ℃ under 95% RH constant temperature and humidity is more than 75%.
The present invention will be described below by way of specific examples, which are given for illustration only and are not intended to limit the scope of the present invention in any way, and unless otherwise specified, the conditions or steps are not specifically described and the parts, etc. are all conventional.
The reagent or material information used in the examples and comparative examples are specifically as follows:
Polytetrahydrofuran diol, shanxi three-dimensional group Co., ltd; polycarbonate diol, japan chemical company; polycaprolactone diol, japanese cellophane Co; polyoxypropylene diols, bode Federal Co., ltd;
4,4' -diphenylmethane diisocyanate, a mixture of 2, 4-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate in a mass ratio of 1:1, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate, carbodiimide-modified diisocyanate, tabacco vandergar group limited;
TECH-2120, TECH-2127, TECH-2420, TECH-2135, tager polymers Inc.; SF-9201, zhejiang forward chemical Co., ltd;
catalysts BiCAT 8106, biCAT 8108, biCAT 8124, biCAT 3228, borchi Kat 22, borchi Kat 24, biCAT 4130, biCAT 4232, MB20, american leading chemicals company;
Ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, glycerol, trimethylolpropane, antioxidants, foam stabilizers, amine catalysts, leveling agents, blocked isocyanate curing agents are all commercially available.
Example 1
Preparation of carbodiimide-modified polyol
Adding 20 parts of MDI-50 and 1 part of triethyl phosphate catalyst into a three-neck flask filled with nitrogen protection, rapidly heating to 180 ℃ and stirring for 3 hours to prepare carbodiimide modified diisocyanate;
then 80 parts of polytetrahydrofuran dihydric alcohol with the molecular weight of 1000 and 0.5 part of BiCAT 8108 are added after the temperature is reduced to 90 ℃, and the carbodiimide modified polyol is prepared after stirring for 1 hour.
Preparation of component A
85 Parts of carbodiimide modified polyol is added into a reaction kettle, the temperature is raised to 100 ℃, and dehydration is carried out for 3 hours under the vacuum condition of minus 0.08MPa to minus 0.1 MPa; then 13 parts of 1, 3-propanediol, 0.5 part of glycerol, 1 part of BiCAT 8124, 0.5 part of antioxidant 1010 and 1 part of flatting agent BYK-361N are added in sequence after the temperature is reduced to 30 ℃, and the component A is prepared after the temperature is increased to 80 ℃ and stirring is carried out for 1 h.
Preparation of component B
35 Parts of carbodiimide modified polyol, 35 parts of 4,4' -diphenylmethane diisocyanate (MDI-100) and 0.1 part of antioxidant 1010 are added into a reaction kettle, stirred for 20min, then 30 parts of organosilicon polyol TECH-2120 is added, and stirred and reacted for 4h at 60 ℃ to prepare the component B.
Preparation of solvent-free polyurethane resin
And (3) placing the component A and the component B in a low-pressure casting machine according to the mass ratio of 100:80, and fully mixing to obtain the solvent-free polyurethane resin.
Application example 1
The aqueous/solvent-free polyurethane synthetic leather was prepared using the solvent-free polyurethane resin of example 1, and the specific steps were as follows:
And pouring and coating the solvent-free polyurethane resin fully mixed in a low-pressure pouring machine on a water-based polyurethane surface layer (the water-based polyurethane surface layer is formed by coating anionic surface layer resin KL-718 of new material Co., ltd. Of synthetic polyurethane on release paper, drying and forming at 130 ℃ and then forming a dry film of 0.08 mm), pre-reacting for 90s at 100 ℃ and then attaching a microfiber of 0.8mm, and then continuously reacting for 10min at 100 ℃ to crosslink and solidify and form the polyurethane surface layer, winding and stripping the release paper after forming to obtain the water-based/solvent-free polyurethane synthetic leather with high interfacial bonding force.
The water-based/solvent-free polyurethane synthetic leather has the following properties through detection: peel strength 133N/3cm (GB/T8949); the retention rate of the peeling strength at 70 ℃ and 95% RH constant temperature and humidity for 10 weeks is 82% (ASTM D3690); 15℃and 4 ten thousand times of deflection (QB/T2714-2005).
Example 2
Preparation of carbodiimide-modified polyol
Adding 30 parts of MDI-100 and 0.7 part of triethyl phosphate catalyst into a three-neck flask filled with nitrogen protection, rapidly heating to 200 ℃, and stirring for 2.5 hours to obtain carbodiimide modified diisocyanate;
Then 70 parts of polyoxypropylene dihydric alcohol with the molecular weight of 2000 and 0.3 part of BiCAT 4130 are added after the temperature is reduced to 75 ℃, and the carbodiimide modified polyol is prepared after stirring for 2 hours.
Preparation of component A
Adding 95 parts of carbodiimide modified polyol into a reaction kettle, heating to 110 ℃, and dehydrating for 2 hours under the vacuum condition of minus 0.08MPa to minus 0.1 MPa; then 4 parts of 1, 4-butanediol, 0.1 part of trimethylolpropane, 0.4 part of Borchi Kat 22, 0.1 part of antioxidant 1035 and 0.4 part of flatting agent BYK-345 are added in sequence after the temperature is reduced to 40 ℃, and the component A is prepared after the temperature is raised to 70 ℃ and stirred for 2 hours.
Preparation of component B
50 Parts of carbodiimide modified polyol, 30 parts of isophorone diisocyanate and 0.5 part of antioxidant 1035 are added into a reaction kettle, stirred for 10min, then 20 parts of organosilicon polyol TECH-2127 are added, and stirred at 90 ℃ for 2h to prepare the component B.
Preparation of solvent-free polyurethane resin
And (3) placing the component A and the component B in a low-pressure casting machine according to the mass ratio of 100:120, and fully mixing to obtain the solvent-free polyurethane resin.
Application example 2
The aqueous/solvent-free polyurethane synthetic leather was prepared using the solvent-free polyurethane resin of example 2, and the specific steps were as follows:
And (3) pouring and coating the solvent-free polyurethane resin fully mixed in a low-pressure pouring machine on a water-based polyurethane surface layer (the surface layer is the same as the application example 1) through a cutter head with a gap of 0.3mm, pre-reacting for 50s at 110 ℃, attaching the microfiber with a thickness of 0.8mm, then continuously reacting for 5min at 140 ℃ to crosslink and solidify the microfiber, forming, rolling and stripping release paper after forming, so as to prepare the water-based/solvent-free polyurethane synthetic leather with high interfacial bonding force.
The water-based/solvent-free polyurethane synthetic leather is tested (the test is the same as that of application example 1), and the performances are as follows: the peeling strength is 137N/3cm; the retention rate of the peeling strength at 70 ℃ and 95% RH constant temperature and humidity for 10 weeks is 80%; and the temperature is 15 ℃ below zero and the bending is qualified for 4 ten thousands of times.
Example 3
Preparation of carbodiimide-modified polyol
Adding 35 parts of MDI-100 and 0.4 part of triethyl phosphate catalyst into a three-neck flask filled with nitrogen protection, rapidly heating to 230 ℃ and stirring for 2 hours to prepare carbodiimide modified diisocyanate;
then 65 parts of polycarbonate diol with a molecular weight of 3000 and 0.1 part of MB20 are added after the temperature is reduced to 60 ℃, and the carbodiimide modified polyol is prepared after stirring for 3 hours.
Preparation of component A
90 Parts of carbodiimide modified polyol is added into a reaction kettle, the temperature is raised to 115 ℃, and dehydration is carried out for 2 hours under the vacuum condition of minus 0.08MPa to minus 0.1 MPa; then 8.5 parts of diethylene glycol, 0.2 part of trimethylolpropane, 0.5 part of MB20, 0.3 part of antioxidant 1076 and 0.5 part of flatting agent BYK-322 are added in sequence after the temperature is reduced to 40 ℃, and the component A is prepared after the temperature is increased to 90 ℃ and stirred for 2 hours.
Preparation of component B
65 Parts of carbodiimide modified polyol, 20 parts of 4,4' -dicyclohexylmethane diisocyanate and 0.3 part of antioxidant 1076 are added into a reaction kettle, after stirring for 20min, 15 parts of organosilicon polyol TECH-2135 are added, and stirring reaction is carried out for 3h at 60 ℃ to obtain the component B.
Preparation of solvent-free polyurethane resin
And (3) placing the component A and the component B in a low-pressure casting machine according to the mass ratio of 100:90, and fully mixing to obtain the solvent-free polyurethane resin.
Application example 3
The aqueous/solvent-free polyurethane synthetic leather was prepared using the solvent-free polyurethane resin of example 3, and the specific steps were as follows:
And (3) pouring and coating the solvent-free polyurethane resin fully mixed in a low-pressure pouring machine on a water-based polyurethane surface layer (the surface layer is the same as the application example 1) through a cutter head with a gap of 0.3mm, pre-reacting for 30s at 140 ℃, attaching the microfiber with a thickness of 0.8mm, then continuously reacting for 8min at 130 ℃, cross-linking, solidifying and forming the microfiber, rolling the molded microfiber, and stripping the release paper to obtain the water-based/solvent-free polyurethane synthetic leather with high interfacial bonding force.
The water-based/solvent-free polyurethane synthetic leather is tested (the test is the same as that of application example 1), and the performances are as follows: the peel strength is 130N/3cm; the retention rate of the peeling strength at 70 ℃ and 95% RH constant temperature and humidity for 10 weeks is 83%; and the temperature is 15 ℃ below zero and the bending is qualified for 4 ten thousands of times.
Comparative example 1
Preparation of component A
The same embodiment as in example 1 was used, except that: the polyol used in this comparative example was a polyol having no carbodiimide structure, specifically polytetrahydrofuran diol having a molecular weight of 1000.
Preparation of component B
The same embodiment as in example 1 was used, except that: the polyol used in this comparative example was a polyol having no carbodiimide structure, specifically a polytetrahydrofuran diol having a molecular weight of 1000.
Preparation of solvent-free polyurethane resin
And (3) placing the component A and the component B in a low-pressure casting machine according to the mass ratio of 100:80, and fully mixing to obtain the solvent-free polyurethane resin.
Comparative application example 1
The same embodiment as in application example 1 was used to produce an aqueous/solventless polyurethane synthetic leather, with the difference that: the A and B components were prepared as in comparative example 1.
The water-based/solvent-free polyurethane synthetic leather has the following properties through detection: the peeling strength is 87N/3cm; the retention rate of the peeling strength at 70 ℃ and 95% RH constant temperature and humidity for 10 weeks is 63%; and the flexure at 15 ℃ below zero for 4 ten thousand times is not qualified.
Comparative example 2
Preparation of component A
The same embodiment as in example 2 was used, except that: the polyol used in this comparative example was a polyol having no carbodiimide structure, specifically a polyoxypropylene diol having a molecular weight of 2000.
Preparation of component B
The same embodiment as in example 2 was used, except that: the polyol used in this comparative example was a polyol having no carbodiimide structure, specifically a polyoxypropylene diol having a molecular weight of 2000.
Preparation of solvent-free polyurethane resin
And (3) placing the component A and the component B in a low-pressure casting machine according to the mass ratio of 100:120, and fully mixing to obtain the solvent-free polyurethane resin.
Comparative application example 2
The same embodiment as in application example 2 was used to produce an aqueous/solvent-free polyurethane synthetic leather, with the difference that: the A and B components were prepared as in comparative example 2.
The water-based/solvent-free polyurethane synthetic leather has the following properties through detection: peel strength of 78N/3cm; the retention rate of the peeling strength at 70 ℃ and 95% RH constant temperature and humidity for 10 weeks is 60%; and the flexure at 15 ℃ below zero for 4 ten thousand times is not qualified.
Comparative example 3
Preparation of component A
The same embodiment as in example 3 was used, except that: the polyol used in this comparative example was a polyol having no carbodiimide structure, specifically a polycarbonate diol having a molecular weight of 3000.
Preparation of component B
The same embodiment as in example 3 was used, except that: the polyol used in this comparative example was a polyol having no carbodiimide structure, specifically a polycarbonate diol having a molecular weight of 3000.
Preparation of solvent-free polyurethane resin
And (3) placing the component A and the component B in a low-pressure casting machine according to the mass ratio of 100:90, and fully mixing to obtain the solvent-free polyurethane resin.
Comparative application example 3
The same embodiment as in application example 3 was used to produce an aqueous/solventless polyurethane synthetic leather, with the difference that: the A and B components were prepared as in comparative example 3.
The water-based/solvent-free polyurethane synthetic leather has the following properties through detection: the peeling strength is 69N/3cm; the retention rate of the peeling strength at 70 ℃ under 95% RH constant temperature and humidity for 10 weeks is 58%; and the flexure at 15 ℃ below zero for 4 ten thousand times is not qualified.
Comparative example 4
This comparative example maintains the A component of example 1 unchanged, i.e., the carbodiimide-modified polyol was used; and the component B does not contain carbodiimide-modified polyol, and is specifically prepared as follows:
Preparation of carbodiimide-modified polyol
As in example 1.
Preparation of component A
As in example 1.
Preparation of component B
The same embodiment as in example 1 was used, except that: the polyol used in this comparative example was a polyol having no carbodiimide structure, specifically a polytetrahydrofuran diol having a molecular weight of 1000.
Preparation of solvent-free polyurethane resin
And (3) placing the component A and the component B in a low-pressure casting machine according to the mass ratio of 100:80, and fully mixing to obtain the solvent-free polyurethane resin.
Comparative application example 4
The same embodiment as in application example 1 was used to produce an aqueous/solventless polyurethane synthetic leather, with the difference that: the A and B components were prepared as in comparative example 4.
The water-based/solvent-free polyurethane synthetic leather has the following properties through detection: the peeling strength is 89N/3cm; the retention rate of the peeling strength at 70 ℃ and 95% RH constant temperature and humidity for 10 weeks is 66%; and the flexure at 15 ℃ below zero for 4 ten thousand times is not qualified.
Comparative example 5
This comparative example maintains the component B of example 2 unchanged, i.e., the carbodiimide-modified polyol was used; while the A component does not contain carbodiimide-modified polyol, the specific preparation is as follows:
Preparation of carbodiimide-modified polyol
As in example 2.
Preparation of component A
The same embodiment as in example 2 was used, except that: the polyol used in this comparative example was a polyol having no carbodiimide structure, specifically a polyoxypropylene diol having a molecular weight of 2000.
Preparation of component B
As in example 2.
Preparation of solvent-free polyurethane resin
And (3) placing the component A and the component B in a low-pressure casting machine according to the mass ratio of 100:120, and fully mixing to obtain the solvent-free polyurethane resin.
Comparative application example 5
The same embodiment as in application example 2 was used to produce an aqueous/solvent-free polyurethane synthetic leather, with the difference that: the A and B components were prepared as in comparative example 5.
The water-based/solvent-free polyurethane synthetic leather has the following properties through detection: the peeling strength is 82N/3cm; the retention rate of the peeling strength at 70 ℃ and 95% RH constant temperature and humidity for 10 weeks is 62%; and the flexure at 15 ℃ below zero for 4 ten thousand times is not qualified.
Table 1 comparison of Water-based/solvent-free polyurethane synthetic leather Performance test
As can be seen from comparison of the test results in Table 1, the components A, B of examples 1-3 all use carbodiimide modified polyols, which produce solvent-free polyurethane resins with higher levels of carbodiimide groups that react with carboxyl groups in the aqueous face layer to form stronger chemical bonds, thus achieving good peel strength. In contrast, the solvent-free polyurethane prepared in comparative examples 1 to 3 does not contain carbodiimide groups, and in comparative examples 4 and 5, only the A-or B-component contains carbodiimide groups, and the total amount is small, so that the peel strength is improved as compared with comparative examples 1 to 3, but the peel strength is still not satisfactory, and therefore, it is difficult to obtain good peel strength without effective chemical crosslinking between the aqueous surface layer and the solvent-free layer in comparative examples, and the peel interface is between the aqueous surface layer/the solvent-free layer. And the carboxyl reaction of the surface layer with higher carbodiimide content in the examples 1-3 improves the bonding force of the interface, and greatly helps the flexibility, otherwise, similar to the comparative examples 1-5, the flexibility is disqualified due to the insufficient bonding force of the interface. Meanwhile, as carbodiimide reacts with carboxyl in the aqueous polyurethane surface layer, the hydrophilicity and acidity of the aqueous surface layer are reduced, and the hydrolysis resistance of the coating is improved, so that the retention rate of peel strength after constant temperature and humidity detection of examples 1-3 is obviously higher than that of comparative examples 1-5.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (7)
1. The solvent-free polyurethane resin comprises a component A and a component B, and is characterized in that the component A consists of 85-95 parts of carbodiimide modified polyol, 4-13 parts of small molecular chain extender, 0.1-0.5 part of small molecular cross-linking agent, 0.4-1 part of leveling agent, 0.4-1 part of catalyst and 0.1-0.5 part of antioxidant according to parts by weight;
the component B consists of 35-65 parts of carbodiimide modified polyol, 20-35 parts of diisocyanate, 15-30 parts of organosilicon polyol and 0.1-0.5 part of antioxidant;
wherein the mass ratio of the component A to the component B is 100:80-100:135;
the carbodiimide modified polyol is obtained by reacting carbodiimide modified diisocyanate with oligomer dihydric alcohol under the action of a catalyst.
2. The solventless polyurethane resin of claim 1 wherein the oligomeric diol is selected from one of polytetrahydrofuran diol, polypropylene oxide diol, polycarbonate diol, polycaprolactone diol, and polymer diol and has a molecular weight between 1000 and 3000.
3. The solvent-free polyurethane resin of claim 1, wherein the small molecule chain extender is selected from one of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, neopentyl glycol, diethylene glycol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol hydroquinone bis (2-hydroxyethyl) ether;
the small molecule cross-linking agent is selected from one of glycerol and trimethylolpropane;
The leveling agent is an organosilicon leveling agent, and the organosilicon leveling agent is selected from one of BYK-322, BYK-333, BYK-345 and BYK-361N;
The catalyst is selected from one of delayed type environment-friendly metal catalyst or phenolate, formate and hydrochloride thereof, and the delayed type environment-friendly catalyst is selected from one of BiCAT 8106, biCAT 8108, biCAT 8124, biCAT 3228, borchi Kat 22, borchi Kat 24, biCAT 4130, biCAT 4232 and MB 20;
The antioxidant is selected from one of antioxidant 245, antioxidant 1010, antioxidant 1035, antioxidant 1076, antioxidant 1098 or antioxidant 3114;
The diisocyanate is selected from one of 4,4' -diphenylmethane diisocyanate, a mixture of 2, 4-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate in a mass ratio of 1:1, isophorone diisocyanate, hexamethylene diisocyanate and 4,4' -dicyclohexylmethane diisocyanate;
the organosilicon polyol is selected from one of TECH-2120, TECH-2127, TECH-2420, TECH-2135 and SF-9201.
4. A process for the preparation of the solvent-free polyurethane resin as claimed in any one of claims 1 to 3, comprising the steps of:
Preparation of carbodiimide-modified polyol: stirring carbodiimide modified diisocyanate and oligomer dihydric alcohol and a catalyst at 60-90 ℃ for reaction for 1-3h to prepare carbodiimide modified polyol;
Preparing a component A: mixing the carbodiimide modified polyol after vacuum dehydration with a micromolecular chain extender, a micromolecular crosslinking agent, a catalyst, an antioxidant and a leveling agent at 30-40 ℃, then heating to 60-80 ℃ and stirring for 1-3h to obtain a component A;
And (3) preparing a component B: stirring carbodiimide modified polyol, diisocyanate and an antioxidant for 10-20min, then adding organosilicon polyol, and stirring at 60-90 ℃ for 2-4h to prepare a component B;
preparing solvent-free polyurethane resin: and fully mixing the component A and the component B according to the mass ratio of 100:80-100:135 to obtain the solvent-free polyurethane resin.
5. The preparation method of the polyurethane synthetic leather is characterized by comprising the following steps of:
forming a water-based polyurethane surface layer;
Pouring and coating the solvent-free polyurethane resin according to any one of claims 1-3 on the surface of the water-based polyurethane surface layer, pre-reacting for 30-90s at 100-140 ℃, attaching the base cloth, and then continuously reacting for 5-10min at 100-140 ℃ to crosslink, solidify and form the water-based polyurethane surface layer;
and (5) rolling and stripping after molding to obtain the water-based/solvent-free polyurethane synthetic leather.
6. The method according to claim 5, wherein the aqueous polyurethane surface layer is obtained by coating an anionic surface layer resin on release paper, and drying and molding.
7. The polyurethane synthetic leather is characterized in that the peel strength of the polyurethane synthetic leather can reach more than 120N/3cm, and the retention rate of the peel strength of the polyurethane synthetic leather after the polyurethane synthetic leather is subjected to constant temperature and humidity for 10 weeks at 70 ℃ and 95% RH is more than 75%.
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| CN106008891A (en) * | 2016-05-20 | 2016-10-12 | 合肥安利聚氨酯新材料有限公司 | Polyurethane resin for solvent-free crease-free microfiber mirror-surface synthetic leather and preparation method and application of polyurethane resin |
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| JP4318828B2 (en) * | 1999-04-30 | 2009-08-26 | 日本ペイント株式会社 | Method for producing hydrophilized modified polycarbodiimide compound, hydrophilized modified polycarbodiimide compound, and room temperature curable aqueous coating composition containing the same |
| KR102441738B1 (en) * | 2016-11-18 | 2022-09-08 | 닛신보 케미칼 가부시키가이샤 | polycarbodiimide copolymer |
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| CN110066373B (en) * | 2019-03-19 | 2021-09-21 | 合肥科天水性科技有限责任公司 | Solvent-free polyurethane resin for synthetic leather, preparation method thereof and application of solvent-free polyurethane resin in water-based/solvent-free polyurethane synthetic leather |
| CN112048278B (en) * | 2020-09-15 | 2022-12-09 | 山东一诺威聚氨酯股份有限公司 | Steaming-resistant bi-component solvent-free polyurethane laminating adhesive and preparation method thereof |
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| CN104334624A (en) * | 2012-06-05 | 2015-02-04 | 莱茵化学莱瑙有限公司 | Novel carbodiimide-containing compositions and method for the production and use thereof |
| CN106008891A (en) * | 2016-05-20 | 2016-10-12 | 合肥安利聚氨酯新材料有限公司 | Polyurethane resin for solvent-free crease-free microfiber mirror-surface synthetic leather and preparation method and application of polyurethane resin |
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