CN115651156A - 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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- CN115651156A CN115651156A CN202211384274.6A CN202211384274A CN115651156A CN 115651156 A CN115651156 A CN 115651156A CN 202211384274 A CN202211384274 A CN 202211384274A CN 115651156 A CN115651156 A CN 115651156A
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- 229920002635 polyurethane Polymers 0.000 claims abstract description 95
- 239000004814 polyurethane Substances 0.000 claims abstract description 95
- 229920005862 polyol Polymers 0.000 claims abstract description 83
- 150000003077 polyols Chemical class 0.000 claims abstract description 74
- 150000001718 carbodiimides Chemical class 0.000 claims abstract description 57
- 239000002649 leather substitute Substances 0.000 claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 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
- -1 silicon polyol Chemical class 0.000 claims abstract description 19
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 239000010703 silicon Substances 0.000 claims abstract description 16
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- 239000002344 surface layer Substances 0.000 claims description 37
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 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
- 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 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
- 238000010438 heat treatment Methods 0.000 claims description 12
- 230000014759 maintenance of location Effects 0.000 claims description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 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
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000005096 rolling process 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
- 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
- 238000000465 moulding Methods 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
- 150000003384 small molecules Chemical group 0.000 claims description 5
- 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
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- 239000002184 metal Substances 0.000 claims description 4
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- 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
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
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- 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
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 11
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- 230000009471 action Effects 0.000 description 6
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 6
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 4
- 101000974007 Homo sapiens Nucleosome assembly protein 1-like 3 Proteins 0.000 description 3
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- 102100022398 Nucleosome assembly protein 1-like 3 Human genes 0.000 description 3
- 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 3
- 238000001816 cooling Methods 0.000 description 3
- 239000010985 leather Substances 0.000 description 3
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- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
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- 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 comprises 85-95 parts of carbodiimide modified polyol, 4-13 parts of micromolecule chain extender, 0.1-0.5 part of micromolecule cross-linking agent, 0.4-1 part of flatting agent, 0.4-1 part of catalyst and 0.1-0.5 part of antioxidant; the component B comprises 35-65 parts of carbodiimide modified polyol, 20-35 parts of diisocyanate, 15-30 parts of organic silicon polyol and 0.1-0.5 part of antioxidant. The solvent-free polyurethane resin contains carbodiimide modified polyol, and when the solvent-free polyurethane resin is applied to aqueous/solvent-free polyurethane synthetic leather, the interface bonding force between a solvent-free polyurethane layer and an aqueous polyurethane layer can be improved, and 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 waterborne/solvent-free polyurethane synthetic leather.
Background
With the transformation development of the synthetic leather industry, the water-based synthetic leather, the solvent-free synthetic leather and the TPU synthetic leather develop rapidly, and new opportunities are brought to the environment-friendly and clean way of the synthetic leather industry. Among them, the development of the aqueous/solvent-free synthetic leather is the most outstanding, and the aqueous/solvent-free synthetic leather product has a solvent-free foamed porous structure and does not need to add harmful solvents in the production process, so that the aqueous/solvent-free synthetic leather has the advantages of various design and color handfeel and excellent environmental protection performance, and is widely concerned.
However, the current aqueous/solvent-free synthetic leather product has the problem of poor bonding strength between the aqueous polyurethane surface layer and the solvent-free polyurethane foaming layer, so that the product can only be used for synthetic leather with low requirement on peel strength, such as clothing leather, sofa leather and the like, but is difficult to be applied to shoe leather with high requirement on peel strength; the main reason is that in the waterborne/solvent-free process, most of waterborne polyurethane on the market is carboxylic acid type, the preparation method mainly uses dimethylolpropionic acid (DMPA) as a hydrophilic group and Triethylamine (TEA) as a neutralizer, and the waterborne polyurethane film contains more carboxyl groups after the triethylamine volatilizes along with the rise of temperature in the film forming process of the waterborne polyurethane; the carboxyl is acidic, so that the curing reaction of the solvent-free bi-component polyurethane on an interface can be inhibited, the curing of the interface is insufficient, the strength is weak, the peeling force between the solvent-free middle layer and the water-based surface layer is usually only dependent on the van der Waals force and the action of a hydrogen bond, the effect of mutual winding of molecular chains is difficult to achieve, and an obvious interface exists, so that the acting force between the interfaces is weak; generally, the peeling strength is only between 30 and 90N/3cm, and the high peeling level (more than or equal to 120N/3 cm) is difficult to achieve.
Disclosure of Invention
In view of the above, the present invention needs to provide a solvent-free polyurethane resin, in which a carbodiimide modified polyol is used to react a polyol containing a carbodiimide structure onto a solvent-free polyurethane main body, and a carbodiimide reacts with a large amount of carboxyl groups in aqueous polyurethane to bond a solvent-free polyurethane layer and an aqueous polyurethane surface layer through chemical bonds, so as to improve the interfacial bonding force between the solvent-free polyurethane layer and the aqueous polyurethane layer, and to implement the preparation of aqueous/solvent-free polyurethane synthetic leather with high peel strength.
In order to achieve the purpose, the 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 comprises 85-95 parts of carbodiimide modified polyol, 4-13 parts of micromolecular chain extender, 0.1-0.5 part of micromolecular cross-linking agent, 0.4-1 part of flatting agent, 0.4-1 part of catalyst and 0.1-0.5 part of antioxidant in parts by mass;
the component B comprises 35-65 parts of carbodiimide modified polyol, 20-35 parts of diisocyanate, 15-30 parts of organic silicon polyol and 0.1-0.5 part of antioxidant.
In a further scheme, the mass ratio of the component A to the component B is 100:80-100:135.
in a further scheme, the carbodiimide modified polyol is obtained by reacting carbodiimide modified diisocyanate and oligomer diol under the action of a catalyst.
Further, the oligomer diol is one selected from polytetrahydrofuran diol, polypropylene oxide diol, polycarbonate diol, polycaprolactone diol and polymer diol, and has a molecular weight of 1000-3000.
Further, the small molecular 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, 1,4-cyclohexanedimethanol hydroquinone bis (2-hydroxyethyl) ether;
the micromolecule cross-linking agent is selected from one of glycerol and trimethylolpropane;
the leveling agent is an organic silicon leveling agent, and the organic silicon 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 catalysts or phenate, formate and hydrochloride thereof, and the delayed-type environment-friendly catalyst is selected from one of BiCAT 8106, biCAT 8108, biCAT 8124, biCAT3228, 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 the mass ratio of 1:1, isophorone diisocyanate, hexamethylene diisocyanate, 4,4' -dicyclohexylmethane diisocyanate;
the organic silicon 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:
preparing carbodiimide modified polyol: stirring carbodiimide modified diisocyanate, oligomer dihydric alcohol and a catalyst at 60-90 ℃ to react for 1-3h to prepare carbodiimide modified polyol;
preparing a component A: mixing the carbodiimide modified polyol subjected to vacuum dehydration with a micromolecular chain extender, a micromolecular cross-linking agent, a catalyst, an antioxidant and a flatting agent at 30-40 ℃, and then heating to 60-80 ℃ and stirring for 1-3h to prepare a component A;
preparing a component B: stirring carbodiimide modified polyol, diisocyanate and antioxidant for 10-20min, adding organic silicon polyol, and stirring at 60-90 deg.C for 2-4h to obtain component B;
preparation of solvent-free polyurethane resin: and (2) fully mixing the component A with the component B according to the mass ratio of 100 to 100.
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 waterborne polyurethane surface layer, pre-reacting at 100-140 ℃ for 30-90s, then attaching to a base fabric, and continuing to react at 100-140 ℃ for 5-10min to crosslink, cure and form the polyurethane resin;
and rolling and stripping after molding to prepare the waterborne/solvent-free polyurethane synthetic leather.
In a further scheme, the waterborne polyurethane surface layer is obtained by coating anionic surface layer resin on release paper and then drying and forming.
The invention also provides polyurethane synthetic leather prepared by the preparation method, the peel strength of the polyurethane synthetic leather can reach more than 120N/3cm, and the peel strength retention rate is more than 75% after the polyurethane synthetic leather is subjected to constant temperature and humidity (RH) of 70 ℃ and 95% for 10 weeks.
Compared with the prior art, the invention has the following beneficial effects:
in the solvent-free polyurethane resin, carbodiimide modified polyol is innovatively adopted, polyol containing a carbodiimide structure is reacted on a solvent-free polyurethane main body, and carbodiimide reacts with a large amount of carboxyl in waterborne polyurethane: on one hand, the solvent-free polyurethane layer and the waterborne polyurethane surface layer can be combined through chemical bonds, so that the interface bonding force between the solvent-free polyurethane layer and the waterborne polyurethane surface layer is remarkably improved, and the adverse effect of carboxyl on the solvent-free polyurethane reaction is avoided; on the other hand, the hydrolysis resistance of the waterborne polyurethane surface layer can be greatly improved after the carboxyl is reacted.
According to the invention, the organic silicon is introduced into the solvent-free polyurethane resin, and the solvent-free polyurethane resin has the characteristic of low surface energy, so that the solvent-free polyurethane can be easily coated on the surface of the aqueous polyurethane surface layer without a leveling agent.
In addition, the solvent-free polyurethane resin does not contain any organic solvent, is green and environment-friendly, and can meet the high environmental protection requirement of zero DMF.
Drawings
FIG. 1 is a schematic diagram of the interfacial bonding between a solvent-free polyurethane layer and an aqueous polyurethane top layer in the present invention.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, 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 first aspect of the invention provides a solvent-free polyurethane resin, which comprises a component A and a component B, wherein the component A comprises, by mass, 85-95 parts of carbodiimide modified polyol, 4-13 parts of a small molecular chain extender, 0.1-0.5 part of a small molecular cross-linking agent, 0.4-1 part of a leveling agent, 0.4-1 part of a catalyst and 0.1-0.5 part of an antioxidant;
the component B comprises 35-65 parts of carbodiimide modified polyol, 20-35 parts of diisocyanate, 15-30 parts of organic silicon polyol and 0.1-0.5 part of antioxidant.
According to the invention, carbodiimide modified polyol is innovatively introduced into the solvent-free polyurethane resin, polyol containing a carbodiimide structure is reacted onto a solvent-free polyurethane resin main body, and in the subsequent synthetic leather preparation process, the carbodiimide reacts with a large number of carboxyl groups in the waterborne polyurethane, so that the solvent-free polyurethane layer and the waterborne polyurethane surface layer are combined through chemical bonds, and thus the interface bonding force between the solvent-free polyurethane layer and the waterborne polyurethane surface layer is remarkably improved.
The mass ratio of the component a and the component B is not particularly limited, and can be adjusted according to the conditions well known in the art and the practical situation, 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 dihydric alcohol under the action of a catalyst. For example, the reaction of carbodiimide-modified diphenylmethane diisocyanate (MDI) with oligomeric diol is exemplified by the following reaction:
it will be appreciated that the preparation of carbodiimide modified diisocyanates is well known to those skilled in the art, i.e. the reaction of the diisocyanate itself undergoes polycondensation under the action of heat in the presence of an organic phosphine as catalyst to form a compound containing a carbodiimide group (-N = C = N-). It will be appreciated that it may be prepared by conventional means, or may be obtained directly from commercial sources, and in some particular embodiments of the invention, the carbodiimide-modified diphenylmethane diisocyanate (MDI) described above is prepared by the reaction of:
it is to be understood that the above carbodiimide-modified diphenylmethane diisocyanate (MDI) is merely an example of the present invention, and that other types of diisocyanates can be used in the present invention, and the specific reaction mechanism or mechanism thereof is similar to that described above and will not be described in detail herein.
According to the embodiment of the invention, the preparation of the carbodiimide-modified polyol herein adopts the following raw materials 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: carrying out high-temperature reaction (stirring at 180-230 ℃ for 2-3 h) on diisocyanate under the action of catalyst triethyl phosphate to prepare carbodiimide modified diisocyanate; then the carbodiimide modified diisocyanate and oligomer dihydric alcohol react under the action of a catalyst (at the temperature of 60-90 ℃ for 1-3 h) to prepare the carbodiimide modified polyol.
Wherein the diisocyanates described herein are distinguished by the number of-NCO groups, which is a routine choice in the art, and specifically examples that may be mentioned include, but are not limited to, one of 4,4' -diphenylmethane diisocyanate (MDI-100), a mixture of 2,4-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate in a mass ratio of 1:1 (MDI-50), isophorone diisocyanate (IPDI), hexamethylene Diisocyanate (HDI), 4,4' -dicyclohexylmethane diisocyanate (HMDI).
The oligomer polyol described herein is a polyol having a molecular weight of between 1000 and 3000, and in some embodiments of the invention, the oligomer polyol is 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 used in the reaction of diisocyanate and polyol, which are well known in the art and will not be specifically described herein.
Further, the small molecule chain extender in the A component is a small molecule diol, specifically an alcohol containing two hydroxyl groups in the molecule, and can be selected according to the routine in the field, and in some specific embodiments of the invention, 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, 1,4-cyclohexanedimethanol hydroquinone bis (2-hydroxyethyl) ether.
Further, the small molecule cross-linking agent in the component a is a small molecule polyol, i.e. an alcohol containing three or more hydroxyl groups in the molecule, which can be selected according to the knowledge of those skilled in the art, and in some specific embodiments of the present invention, the small molecule cross-linking agent is selected from one of glycerol and trimethylolpropane.
Further, the leveling agent described in the a component is preferably an organic silicon-based leveling agent, which may be well known to those skilled in the art, and specifically, there may be mentioned, but not limited to, one of BYK-322, BYK-333, BYK-345, BYK-361N;
further, the catalyst and the antioxidant in the component a can be well known to those skilled in the art, wherein, in some specific embodiments of the present invention, the catalyst is selected from one of delayed-type environment-friendly metal catalysts or phenolate, formate and hydrochloride thereof, and the delayed-type environment-friendly catalyst is selected from one of BiCAT 8106, biCAT 8108, biCAT 8124, biCAT3228, 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;
in the further scheme, part of raw materials in the component B and the component A have the same meaning, so that the detailed description is omitted. Wherein, the organosilicon polyalcohol in the component B is well known to those skilled in the art, and specific examples include but are not limited to one of TECH-2120, TECH-2127, TECH-2420, TECH-2135 and SF-9201. By introducing the organic silicon and utilizing the characteristic of low surface energy, the solvent-free polyurethane can be easily coated on the surface of the aqueous polyurethane surface layer under the condition of not needing a leveling agent.
In a second aspect of the present invention, there is provided a method for preparing the solvent-free polyurethane resin according to the first aspect of the present invention, comprising the steps of:
preparing carbodiimide modified polyol: stirring carbodiimide modified diisocyanate, oligomer dihydric alcohol and a catalyst at 60-90 ℃ to react for 1-3h to prepare carbodiimide modified polyol; wherein the carbodiimide modified diisocyanate is obtained by a method well known in the art, and in some specific embodiments of the invention, is prepared by a triethyl phosphate catalyst at 180-230 ℃ for stirring reaction for 2-3 h;
preparing a component A: mixing the carbodiimide modified polyol subjected to vacuum dehydration with a micromolecular chain extender, a micromolecular cross-linking agent, a catalyst, an antioxidant and a flatting agent at 30-40 ℃, and then heating to 60-80 ℃ and stirring for 1-3h to prepare a component A;
preparing a component B: stirring carbodiimide modified polyol, diisocyanate and antioxidant for 10-20min, adding organic silicon polyol, and stirring at 60-90 deg.C for 2-4h to obtain component B;
preparation of solvent-free polyurethane resin: the solvent-free polyurethane resin is prepared by fully mixing the component A and the component B according to the mass ratio of 100 to 80-100.
The third aspect of the present invention provides a method for preparing polyurethane synthetic leather, wherein the solvent-free polyurethane resin is applied to aqueous/solvent-free polyurethane synthetic leather, so as to significantly improve the interface bonding force between the solvent-free polyurethane layer and the aqueous polyurethane layer, and the preparation method of the polyurethane synthetic leather comprises the following steps:
forming a water-based polyurethane surface layer;
pouring and coating the solvent-free polyurethane resin of the third aspect of the invention on the surface of the waterborne polyurethane surface layer, pre-reacting at 100-140 ℃ for 30-90s, then attaching to a base fabric, and continuing to react at 100-140 ℃ for 5-10min to enable the polyurethane resin to be crosslinked, cured and molded;
and rolling and stripping after molding to prepare the waterborne/solvent-free polyurethane synthetic leather.
The preparation of the aqueous polyurethane surface layer is not particularly limited, and can 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 fourth aspect of the invention, the polyurethane synthetic leather is prepared by the preparation method according to the third aspect of the invention, because the main body of the solvent-free polyurethane contains the carbodiimide structure, after the carbodiimide structure is coated on the surface of the aqueous polyurethane surface layer, the carbodiimide and a large amount of carboxyl groups in the aqueous polyurethane are subjected to crosslinking curing reaction to form chemical bonds, so that the interface bonding force between the aqueous polyurethane surface layer and the solvent-free polyurethane layer is obviously improved, and the specific principle can be seen in fig. 1. According to the embodiment of the invention, the peel strength of the prepared water-based/solvent-free polyurethane synthetic leather can reach more than 120N/3cm, and the peel strength retention rate after the constant temperature and humidity of 70 ℃ and 95% RH for 10 weeks is more than 75%.
The present invention is described below by way of specific examples, which are provided for illustrative purposes only and do not limit the scope of the present invention in any way, and unless otherwise specified, conditions or steps are not described in detail and the methods are conventional, and the parts, etc. are parts by mass.
The reagent or material information used in the examples and comparative examples are specifically as follows:
polytetrahydrofuran diol, shanxi three-dimensional group ltd; polycarbonate diol, japan asahi chemical company; polycaprolactone diol, japan xylonite corporation; polyoxypropylene glycol, zibode letter Federal Ltd;
4,4' -diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate and 4,4' -diphenylmethane diisocyanate in a mass ratio of 1:1, isophorone diisocyanate, 4,4' -dicyclohexylmethane diisocyanate, carbodiimide-modified diisocyanate, nicotiana Wanhua group GmbH;
TECH-2120, TECH-2127, TECH-2420, TECH-2135, TAGE POLYMER GmbH; SF-9201, zhejiang Shunfa chemical Co., ltd;
catalysts BiCAT 8106, biCAT 8108, biCAT 8124, biCAT3228, borchi Kat 22, borchi Kat 24, biCAT 4130, biCAT 4232, MB20, leading Chemicals USA;
ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, glycerol, trimethylolpropane, antioxidants, foam stabilizers, amine catalysts, leveling agents, blocked isocyanate curing agents are 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, quickly heating to 180 ℃, and stirring for 3 hours to prepare carbodiimide modified diisocyanate;
then, after the temperature is reduced to 90 ℃, 80 parts of polytetrahydrofuran dihydric alcohol with the molecular weight of 1000 and 0.5 part of BiCAT 8108 are added and stirred for 1 hour, and the carbodiimide modified polyol is prepared.
Preparation of component A
Adding 85 parts of carbodiimide modified polyol into a reaction kettle, heating to 100 ℃, and dehydrating for 3 hours under the vacuum condition of-0.08 MPa to-0.1 MPa; then cooling to 30 ℃, sequentially adding 13 parts of 1,3-propylene glycol, 0.5 part of glycerol, 1 part of BiCAT 8124, 0.5 part of antioxidant 1010 and 1 part of flatting agent BYK-361N, heating to 80 ℃, and stirring for 1h to obtain the component A.
Preparation of component B
Adding 35 parts of carbodiimide modified polyol, 35 parts of 4,4' -diphenylmethane diisocyanate (MDI-100) and 0.1 part of antioxidant 1010 into a reaction kettle, stirring for 20min, adding 30 parts of organosilicon polyol TECH-2120, and stirring and reacting at 60 ℃ for 4h to obtain the component B.
Preparation of solvent-free polyurethane resin
And (3) fully mixing the component A and the component B in a low-pressure casting machine according to the mass ratio of 100.
Application example 1
The solvent-free polyurethane resin in example 1 is used to prepare the aqueous/solvent-free polyurethane synthetic leather, and the specific steps are as follows:
the solvent-free polyurethane resin fully mixed in a low-pressure casting machine is cast and coated on a water-based polyurethane surface layer (the water-based polyurethane surface layer is formed by coating anion surface layer resin KL-718 of FeiAnli polyurethane new material company Limited on release paper and drying and forming at 130 ℃ to form a dry film of 0.08 mm), pre-reacting at 100 ℃ for 90s, attaching 0.8mm microfiber, continuously reacting at 100 ℃ for 10min to crosslink, solidify and form the release paper, rolling and peeling the release paper after forming to prepare the water-based/solvent-free polyurethane synthetic leather with high interface bonding force.
The water-based/solvent-free polyurethane synthetic leather has the following properties by detection: the peel strength was 133N/3cm (GB/T8949); a peel strength retention of 82% (ASTM D3690) at 70 ℃ and 95% RH constant temperature and humidity for 10 weeks; qualified for 4 ten thousand flexions at-15 ℃ (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, quickly heating to 200 ℃, and stirring for 2.5 hours to prepare carbodiimide modified diisocyanate;
then, after the temperature is reduced to 75 ℃,70 parts of polyoxypropylene diol with the molecular weight of 2000 and 0.3 part of BiCAT 4130 are added, and the mixture is stirred for 2 hours to prepare the carbodiimide modified polyol.
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-0.08 MPa to-0.1 MPa; then cooling to 40 ℃, sequentially adding 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, heating to 70 ℃, and stirring for 2 hours to obtain the component A.
Preparation of the B component
50 parts of carbodiimide modified polyol, 30 parts of isophorone diisocyanate and 0.5 part of antioxidant 1035 are put into a reaction kettle, stirred for 10min, then 20 parts of organosilicon polyol TECH-2127 is added, and stirred and reacted for 2h at 90 ℃ to obtain a component B.
Preparation of solvent-free polyurethane resin
And (3) fully mixing the component A and the component B in a low-pressure casting machine according to the mass ratio of 100.
Application example 2
The solvent-free polyurethane resin in example 2 is used to prepare the aqueous/solvent-free polyurethane synthetic leather, and the specific steps are as follows:
and (3) pouring and coating the fully mixed solvent-free polyurethane resin 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 at 110 ℃ for 50s, attaching 0.8mm microfiber, continuously reacting at 140 ℃ for 5min to enable the polyurethane resin to be cross-linked, cured and formed, rolling and peeling off release paper after forming, and thus obtaining the water-based/solvent-free polyurethane synthetic leather with high interface bonding force.
The water-based/solvent-free polyurethane synthetic leather is detected (the test is the same as the application example 1), and the performance is as follows: the peel strength is 137N/3cm; the peel strength retention rate at 70 ℃ and 95% RH constant temperature and humidity for 10 weeks is 80%; the temperature is 15 ℃ below zero, and 4 ten thousand times of deflection is qualified.
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, quickly heating to 230 ℃, and stirring for 2 hours to prepare carbodiimide modified diisocyanate;
then, after the temperature is reduced to 60 ℃, 65 parts of polycarbonate diol with the molecular weight of 3000 and 0.1 part of MB20 are added, and after stirring is carried out for 3 hours, the carbodiimide modified polyol is prepared.
Preparation of component A
Adding 90 parts of carbodiimide modified polyol into a reaction kettle, heating to 115 ℃, and dehydrating for 2 hours under the vacuum condition of-0.08 MPa to-0.1 MPa; then cooling to 40 ℃, sequentially adding 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, heating to 90 ℃, and stirring for 2 hours to obtain the component A.
Preparation of component B
Adding 65 parts of carbodiimide modified polyol, 20 parts of 4,4' -dicyclohexylmethane diisocyanate and 0.3 part of antioxidant 1076 into a reaction kettle, stirring for 20min, adding 15 parts of organosilicon polyol TECH-2135, and stirring for reaction for 3h at 60 ℃ to obtain the component B.
Preparation of solvent-free polyurethane resin
And (3) fully mixing the component A and the component B in a low-pressure casting machine according to the mass ratio of 100.
Application example 3
The solvent-free polyurethane resin in example 3 is used to prepare the aqueous/solvent-free polyurethane synthetic leather, and the specific steps are as follows:
and (3) pouring and coating the fully mixed solvent-free polyurethane resin 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 at 140 ℃ for 30s, attaching 0.8mm microfiber, continuously reacting at 130 ℃ for 8min to enable the polyurethane resin to be cross-linked, cured and formed, rolling and peeling off release paper after forming, and thus obtaining the water-based/solvent-free polyurethane synthetic leather with high interface bonding force.
The water-based/solvent-free polyurethane synthetic leather is detected (the test is the same as the application example 1), and the performance is as follows: the peel strength is 130N/3cm; the peel strength retention at 70 ℃ and 95% RH constant temperature and humidity for 10 weeks was 83%; qualified after 4 ten thousand times of deflection at the temperature of minus 15 ℃.
Comparative example 1
Preparation of component A
The same embodiment as in example 1 is used, with the difference 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 is used, with the difference that: the polyol used in this comparative example was a polyol not containing a carbodiimide structure, specifically polytetrahydrofuran diol having a molecular weight of 1000.
Preparation of solvent-free polyurethane resin
And (3) fully mixing the component A and the component B in a low-pressure casting machine according to the mass ratio of 100.
Comparative application example 1
Using the same embodiment as in application example 1, an aqueous/solvent-free polyurethane synthetic leather was produced, except that: the components A and B were prepared as in comparative example 1.
The water-based/solvent-free polyurethane synthetic leather has the following properties by detection: the peel strength was 87N/3cm; a peel strength retention of 63% at 70 ℃ in 95% RH constant temperature and humidity for 10 weeks; the film is unqualified at the temperature of 15 ℃ below zero and 4 ten thousand times of deflection.
Comparative example 2
Preparation of component A
The same embodiment as in example 2 was used, with the difference 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, with the difference 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) fully mixing the component A and the component B in a low-pressure casting machine according to the mass ratio of 100.
Comparative application example 2
The same embodiment as in application example 2 was used to prepare aqueous/solvent-free polyurethane synthetic leather, except that: the components A and B were prepared as in comparative example 2.
The water-based/solvent-free polyurethane synthetic leather has the following properties by detection: the peel strength is 78N/3cm; the peel strength retention rate at 70 ℃ and 95% RH constant temperature and humidity for 10 weeks is 60%; the film is unqualified at the temperature of 15 ℃ below zero and 4 ten thousand times of deflection.
Comparative example 3
Preparation of component A
The same embodiment as in example 3 was used, with the difference 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, with the difference that: the polyol used in this comparative example was a polyol containing no carbodiimide structure, specifically a polycarbonate diol having a molecular weight of 3000.
Preparation of solvent-free polyurethane resin
And (3) fully mixing the component A and the component B in a low-pressure casting machine according to the mass ratio of 100.
Comparative application example 3
Using the same embodiment as in application example 3, an aqueous/solvent-free polyurethane synthetic leather was produced, except that: the components A and B were prepared as in comparative example 3.
The water-based/solvent-free polyurethane synthetic leather has the following properties by detection: the peel strength is 69N/3cm; 95% at 70 ℃ and a peel strength retention of 58% at 10 weeks RH constant temperature and humidity; the film is unqualified at the temperature of 15 ℃ below zero and 4 ten thousand times of deflection.
Comparative example 4
This comparative example maintained the composition a of example 1 unchanged, i.e. a carbodiimide-modified polyol was used; the component B does not contain carbodiimide modified polyol, and is prepared specifically as follows:
preparation of carbodiimide-modified polyol
The same as in example 1.
Preparation of component A
The same as in example 1.
Preparation of component B
The same embodiment as in example 1 is used, with the difference that: the polyol used in this comparative example was a polyol not containing a carbodiimide structure, specifically polytetrahydrofuran diol having a molecular weight of 1000.
Preparation of solvent-free polyurethane resin
And (3) fully mixing the component A and the component B in a low-pressure casting machine according to the mass ratio of 100.
Comparative application example 4
Using the same embodiment as in application example 1, an aqueous/solvent-free polyurethane synthetic leather was produced, except that: the components A and B were prepared as in comparative example 4.
The water-based/solvent-free polyurethane synthetic leather has the following properties by detection: the peel strength is 89N/3cm; the peel strength retention rate at 70 ℃ and 95% RH constant temperature and humidity for 10 weeks is 66%; the film is unqualified at the temperature of 15 ℃ below zero and 4 ten thousand times of deflection.
Comparative example 5
This comparative example maintained the composition B of example 2 unchanged, i.e. a carbodiimide-modified polyol; the component A does not contain carbodiimide modified polyol, and is prepared specifically as follows:
preparation of carbodiimide-modified polyol
The same as in example 2.
Preparation of component A
The same embodiment as in example 2 was used, with the difference 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 as in example 2.
Preparation of solvent-free polyurethane resin
And (2) fully mixing the component A and the component B in a mass ratio of 100.
Comparative application example 5
Using the same embodiment as in application example 2, an aqueous/solvent-free polyurethane synthetic leather was produced, except that: the components A and B were prepared as in comparative example 5.
The water-based/solvent-free polyurethane synthetic leather has the following properties by detection: the peel strength was 82N/3cm; a peel strength retention of 62% at 70 ℃ in 95% RH constant temperature and humidity for 10 weeks; the film is unqualified at the temperature of 15 ℃ below zero and 4 ten thousand times of deflection.
TABLE 1 comparison of Performance tests on waterborne/solventless polyurethane synthetic leather
As can be seen from the comparison of the test results in Table 1, the carbodiimide-modified polyol was used in the A, B components of examples 1-3, and the solvent-free polyurethane resin prepared therefrom contained a relatively high content of carbodiimide groups, which reacted with carboxyl groups in the aqueous topcoat to form relatively strong chemical bonds, thereby achieving good peel strength. While the solvent-free polyurethanes prepared in comparative examples 1-3 do not contain carbodiimide groups, and only the A component or the B component in comparative examples 4 and 5 contain carbodiimide groups, the total amount is small, the peel strength is improved compared with that of comparative examples 1-3, but the requirements are still not met, so that the better peel strength is difficult to obtain without effective chemical crosslinking between the aqueous surface layer and the solvent-free layer in the comparative examples, and the peeling interface is between the aqueous surface layer and the solvent-free layer. And the carboxyl reaction of the surface layer containing higher content of carbodiimide in examples 1-3 improves the bonding force of the interface and greatly helps the deflection performance, otherwise, similar to comparative examples 1-5, the deflection is unqualified due to insufficient bonding force of the interface. Meanwhile, the carbodiimide reacts with the carboxyl in the waterborne polyurethane surface layer, so that the hydrophilicity and the acidity of the waterborne surface layer are reduced, and the hydrolysis resistance of the coating is improved, so that the peel strength retention rate after constant temperature and humidity detection of the examples 1-3 is obviously higher than that of the comparative examples 1-5.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. A solvent-free polyurethane resin comprises a component A and a component B, and is characterized in that the component A comprises 85-95 parts of carbodiimide modified polyol, 4-13 parts of micromolecular chain extender, 0.1-0.5 part of micromolecular cross-linking agent, 0.4-1 part of flatting agent, 0.4-1 part of catalyst and 0.1-0.5 part of antioxidant in parts by mass;
the component B comprises 35-65 parts of carbodiimide modified polyol, 20-35 parts of diisocyanate, 15-30 parts of organic silicon polyol and 0.1-0.5 part of antioxidant.
2. The solvent-free polyurethane resin according to claim 1, wherein the mass ratio of the A component to the B component is 100:80-100:135.
3. the solventless polyurethane resin of claim 1 wherein the carbodiimide-modified polyol is obtained by reacting a carbodiimide-modified diisocyanate with an oligomeric diol in the presence of a catalyst.
4. The solventless polyurethane resin of claim 3 wherein the oligomeric diol is selected from the group consisting of polytetrahydrofuran diol, polyoxypropylene diol, polycarbonate diol, polycaprolactone diol, and polymeric diol, and has a molecular weight of between 1000 and 3000.
5. The solventless 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 micromolecule cross-linking agent is selected from one of glycerol and trimethylolpropane;
the leveling agent is an organic silicon leveling agent, and the organic silicon 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 catalysts or phenate, formate and hydrochloride thereof, and the delayed-type environment-friendly catalyst is selected from one of BiCAT 8106, biCAT 8108, biCAT 8124, biCAT3228, 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 the mass ratio of 1:1, isophorone diisocyanate, hexamethylene diisocyanate, 4,4' -dicyclohexylmethane diisocyanate;
the organic silicon polyhydric alcohol is selected from one of TECH-2120, TECH-2127, TECH-2420, TECH-2135 and SF-9201.
6. A method for preparing the solvent-free polyurethane resin according to any one of claims 1 to 5, comprising the steps of:
preparing carbodiimide modified polyol: stirring carbodiimide modified diisocyanate, oligomer dihydric alcohol and a catalyst at 60-90 ℃ to react for 1-3h to prepare carbodiimide modified polyol;
preparing a component A: mixing the carbodiimide modified polyol subjected to vacuum dehydration with a micromolecular chain extender, a micromolecular cross-linking agent, a catalyst, an antioxidant and a flatting agent at 30-40 ℃, and then heating to 60-80 ℃ and stirring for 1-3h to prepare a component A;
preparing a component B: stirring carbodiimide modified polyol, diisocyanate and antioxidant for 10-20min, adding organic silicon polyol, and stirring at 60-90 deg.C for 2-4h to obtain component B;
preparation of solvent-free polyurethane resin: and (2) fully mixing the component A with the component B according to the mass ratio of 100 to 100.
7. A preparation method of polyurethane synthetic leather is characterized by comprising the following steps:
forming a water-based polyurethane surface layer;
pouring and coating the solvent-free polyurethane resin of any one of claims 1 to 5 on the surface of the waterborne polyurethane surface layer, pre-reacting at 100-140 ℃ for 30-90s, then attaching a base fabric, and continuously reacting at 100-140 ℃ for 5-10min to crosslink, cure and form the polyurethane resin;
and rolling and stripping after molding to prepare the waterborne/solvent-free polyurethane synthetic leather.
8. The preparation method of claim 7, wherein the aqueous polyurethane surface layer is obtained by coating an anionic surface layer resin on release paper, and drying and molding.
9. Polyurethane synthetic leather produced by the production method according to claim 7 or 8, wherein the peel strength of the polyurethane synthetic leather is 120N/3cm or more, and the retention rate of the peel strength after 10 weeks at 70 ℃ and 95% RH is more than 75%.
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