Hydroxyl composition as well as antifouling polyurethane resin and application thereof

Abstract

The invention discloses a hydroxyl composition and antifouling polyurethane resin and application thereof, the hydroxyl composition comprises polymer polyol and a chain extender mixture, and the chain extender mixture comprises a combination of a fluorine-containing chain extender and a fluorine-free chain extender; the mass ratio of the fluorine-containing chain extender to the fluorine-free chain extender is (0.5: 1)-(6: 1); the polyurethane resin comprises the hydroxyl composition and an isocyanate composition, and the isocyanate composition comprises a polyurethane prepolymer; the polyurethane resin is applied to preparation of antifouling synthetic leather. And the resin is used as a middle layer or surface layer resin material of the synthetic leather. The invention also discloses an application in antifouling synthetic leather. The anti-fouling agent has excellent anti-fouling and weather-resistant properties, the anti-fouling treatment effect of leather can be remarkably improved when the anti-fouling agent is applied to the field of PU synthetic leather, the wear resistance and tear strength of the synthetic leather are also remarkably improved, and the weather-resistant property of the synthetic leather is also improved.

Description

Technical Field

[0001] The invention belongs to the technical field of polyurethane, in particular to a hydroxyl composition for preparing polyurethane resin and an antifouling polyurethane resin and application thereof. Background Art

[0002] With the recent development of new energy vehicles, interest in car interiors has increased. Car interiors not only serve as a decorative element but are also one of the components most frequently encountered by people. Consequently, stricter safety, environmental protection, and health requirements for interior materials are being placed on them. Leather is the primary material used for automotive interiors, including polyurethane (PU) synthetic leather, polyvinyl chloride (PVC) artificial leather, and genuine leather. PU synthetic leather, with its rich texture, odorlessness, and resistance to wear and scratching, has become the preferred alternative to genuine leather. Solvent-free polyurethane synthetic leather, which uses no solvents in its production process and consumes minimal energy, is gradually becoming the preferred material for automotive interiors.

[0003] Currently, solvent-free polyurethane resins generally consist of two components: a hydroxyl component and an isocyanate component. These components are mixed in a specific ratio and applied to a substrate. The hydroxyl component and isocyanate component react to form a solvent-free polyurethane resin, replacing the traditional solvent-based polyurethane production process and significantly reducing VOC emissions and energy consumption. However, as a two-component, instant-reaction product, solvent-free polyurethane resin typically only takes a few minutes to react and mature. Therefore, its structure is typically primarily a mesh structure, achieving rapid curing. However, this excessive mesh structure increases the cohesion of the solvent-free product, making it difficult for the treatment agent to adhere to the surface or easily fall off during subsequent anti-fouling treatments, posing a potential product risk. Increasing the proportion of linear structures further reduces the resin's weather resistance, making it difficult to meet the requirements of some automotive interior leather applications.

[0004] In response to the above problems, the present invention provides a hydroxyl composition, which reacts with an isocyanate composition to obtain a polyurethane resin with excellent anti-fouling and weather resistance. When applied in the field of PU synthetic leather, it can significantly improve the anti-fouling treatment effect of the leather, and the heat and weather resistance of the synthetic leather is also significantly improved, effectively promoting the application scope of PU synthetic leather in automotive interiors. Summary of the Invention

[0005] Technical Problem: The present invention aims to overcome the above-mentioned drawbacks by providing a hydroxyl composition, a polyurethane resin obtained from the hydroxyl composition, and its application in antifouling synthetic leather. The polyurethane resin exhibits excellent antifouling and weathering properties. Its application in the field of PU synthetic leather can significantly enhance the antifouling effect of leather, significantly improve the abrasion resistance and tear strength of synthetic leather, and improve its weathering resistance.

[0006] Technical solution: A hydroxy composition of the present invention includes a polymer polyol and a chain extender mixture, wherein the chain extender mixture includes a combination of a fluorine-containing chain extender and a fluorine-free chain extender; the mass ratio of the fluorine-containing chain extender to the fluorine-free chain extender is 0.5:1 to 6:1.

[0007] The fluorine-containing chain extender includes a reaction product of a dihydroxy alcohol amine and a fluorine-containing acrylate;

[0008] The hydroxyl group in the dihydroxy alcoholamine is a secondary hydroxyl group; preferably, the dihydroxy alcoholamine includes diisopropanolamine;

[0009] The fluorine-containing acrylate has more than 6 fluorine groups, including one or more of hexafluorobutyl (meth)acrylate, dodecafluoroheptyl (meth)acrylate, tridecafluorooctyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, and perfluorotetradecylethyl (meth)acrylate.

[0010] The fluorine-free chain extender includes C2 to C8 diols, including one or more of ethylene glycol, diethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, hexanediol, heptanediol, and decanediol.

[0011] The polymer polyol includes polyether polyol and / or polyester polyol, the polyether polyol includes one or more of polyethylene oxide polyol, polypropylene oxide polyol, polyethylene oxide-propylene oxide polyol, and polytetramethylene ether polyol; the polyester polyol includes a polyol obtained by reacting at least one small molecule diol and at least one small molecule dibasic acid, the small molecule diol includes one or more of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, and nonanediol, and the small molecule dibasic acid includes one or more of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid; the number average molecular weight of the polymer polyol is 500-6000 g / mol;

[0012] The OH value of the hydroxyl composition is 50-380 mg KOH / g.

[0013] The hydroxy composition comprises the following components in parts by weight:

[0014] 80-120 parts by weight of polymer polyol;

[0015] 1 to 30 parts by weight of chain extender

[0016] The hydroxy composition further comprises any one of a foaming agent and a foam leveling agent or a combination of both.

[0017] The polyurethane resin prepared from the hydroxyl composition of the present invention comprises the hydroxyl composition and an isocyanate composition, wherein the isocyanate composition comprises a polyurethane prepolymer; the molar ratio of NCO in the isocyanate composition to the groups reactive toward NCO in the hydroxyl composition is 0.98:1 to 1.1:1; the polyurethane prepolymer is obtained by reacting a polymer polyol with a polyisocyanate, and the NCO mass content of the polyurethane prepolymer is 6-20%; the polyisocyanate comprises one or more of toluene diisocyanate TDI, diphenylmethane diisocyanate MDI, and isomers and / or derivatives and / or modified polymers thereof.

[0018] The polyurethane resin prepared from the hydroxy composition of the present invention is used to prepare antifouling synthetic leather and serves as the resin material of the middle layer or surface layer of the synthetic leather.

[0019] Beneficial effects: The polyurethane resin obtained by reacting the hydroxyl composition provided by the present invention with the isocyanate composition has excellent anti-fouling and weather resistance. When applied in the field of PU synthetic leather, it can significantly improve the anti-fouling treatment effect of the leather, and the wear resistance and tear strength of the synthetic leather are also significantly improved. Its weather resistance is also improved, and it can be applied in the field of automotive interiors. DETAILED DESCRIPTION

[0020] The hydroxy composition comprises a polymer polyol and a chain extender mixture;

[0021] The chain extender mixture includes a combination of a fluorine-containing chain extender and a fluorine-free chain extender;

[0022] The mass ratio of the fluorine-containing chain extender to the fluorine-free chain extender is 0.5:1 to 6:1; the fluorine-containing chain extender comprises a reaction product of dihydroxy alcohol amine and fluorine-containing acrylate;

[0023] The hydroxyl groups in the dihydroxy alcohol amine are secondary hydroxyl groups;

[0024] As an example, the dihydroxy alcohol amine includes diisopropanolamine;

[0025] The fluorine-containing acrylate has more than 6 fluorine groups, for example, hexafluorobutyl (meth)acrylate, dodecafluoroheptyl (meth)acrylate, tridecafluorooctyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, and perfluorotetradecylethyl (meth)acrylate;

[0026] The fluorine-free chain extender includes C2 to C8 diols, including one or more of ethylene glycol, diethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, hexanediol, heptanediol, and decanediol;

[0027] The polymer polyol includes polyether polyol and / or polyester polyol, wherein the polyether polyol includes one or more of polyethylene oxide polyol, polypropylene oxide polyol, polyethylene oxide-propylene oxide polyol, and polytetramethylene ether polyol; the polyester polyol includes a polyol obtained by the reaction of at least one small molecule diol and at least one small molecule dibasic acid, wherein the small molecule diol includes one or more of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, and nonanediol, and the small molecule dibasic acid includes one or more of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid.

[0028] The number average molecular weight of the polymer polyol is 500-6000 g / mol.

[0029] As an example, the OH value of the hydroxyl composition is 50 to 380 mg KOH / g;

[0030] In some embodiments of the present invention, the hydroxyl composition comprises the following composition in parts by weight:

[0031] 80-120 parts by weight of polymer polyol;

[0032] 1 to 30 parts by weight of a chain extender;

[0033] Preferably, the mass ratio of the fluorine-containing chain extender to the fluorine-free chain extender is 0.5:1 to 6:1;

[0034] Preferably, the hydroxy composition further comprises any one or a combination of a foaming agent and a foam leveling agent;

[0035] Preferably, the foaming agent comprises water;

[0036] Preferably, the foam leveling agent comprises silicone oil;

[0037] As an example, the foam leveling agent includes one or more of PMX-0930, silok4082, cm-226, PMX-0156, OFX-8040 and JF-802A;

[0038] Preferably, the amount of any one or a combination of the above-mentioned foaming agent and foam leveling agent added to the hydroxyl composition is not more than 4 parts by weight.

[0039] In some embodiments of the present invention, the hydroxyl composition comprises the following composition in parts by weight:

[0040]

[0041] Furthermore, the preparation method of the hydroxyl composition comprises: mixing a polymer polyol, a chain extender, an optional foaming agent, and an optional foam leveling agent to obtain the hydroxyl composition;

[0042] In some embodiments of the present invention, a polymer polyol, a chain extender, an optional foaming agent, and an optional foaming agent are added to a reaction kettle and stirred and mixed uniformly for 1 to 3 hours to obtain;

[0043] Preferably, the hydroxy composition is sealed and stored before use.

[0044] The present invention also provides a polyurethane resin, wherein the raw materials for preparing the polyurethane resin include a hydroxyl composition and an isocyanate composition, wherein the hydroxyl composition includes the hydroxyl composition described above, and the isocyanate composition includes a polyurethane prepolymer;

[0045] The molar ratio of NCO in the isocyanate composition to the groups reactive toward NCO in the hydroxyl composition is 0.98:1 to 1.1:1;

[0046] Preferably, in some embodiments of the present invention, when the hydroxyl composition does not contain a foaming agent, the OH value is 50 to 280 mg KOH / g; preferably, in some embodiments of the present invention, when the hydroxyl composition contains a foaming agent, the OH value of the hydroxyl composition is 60 to 380 mg KOH / g;

[0047] The polyurethane prepolymer is obtained by reacting a polymer polyol and a polyisocyanate, and the NCO mass content of the polyurethane prepolymer is 6 to 20%;

[0048] The polyisocyanate includes one or more of toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and their isomers and / or derivatives and / or modified polymers;

[0049] In some embodiments of the present invention, the polyisocyanate comprises diphenylmethane diisocyanate (MDI) and / or carbodiimide-uretonimine modified MDI (liquefied MDI);

[0050] The polymer polyol includes polyether polyol and / or polyester polyol;

[0051] In some embodiments of the present invention, the isocyanate composition comprises the following composition in parts by weight:

[0052] 50-150 parts by weight of polymer polyol;

[0053] 80-500 parts by weight of polyisocyanate.

[0054] Furthermore, the isocyanate composition further comprises a polymerization inhibitor, and the amount of the polymerization inhibitor added to the isocyanate composition is not higher than 1 part by weight.

[0055] As an example, the polymerization inhibitor includes one or more of phosphoric acid and acetic acid;

[0056] In some embodiments of the present invention, the isocyanate composition comprises the following composition in parts by weight:

[0057] 50-150 parts by weight of polymer polyol;

[0058] 80-500 parts by weight of polyisocyanate;

[0059] 0.05-1 parts by weight of polymerization inhibitor.

[0060] Furthermore, the preparation method of the isocyanate composition comprises: mixing isocyanate, polyether polyol, and an optional polymerization inhibitor to obtain the isocyanate;

[0061] As an example, the preparation method of the isocyanate composition includes the following steps:

[0062] Isocyanate and optional side reaction inhibitor are added to a reactor, stirred evenly, and then the required polyether polyol is added. The reaction is carried out at 70-80°C for 2-3 hours, and the NCO content is measured. The material is discharged after the NCO content is qualified and stable.

[0063] Preferably, the NCO mass content is 5 to 20%;

[0064] Preferably, the isocyanate composition is sealed and stored before use.

[0065] Preferably, the raw materials for preparing the polyurethane further include a catalyst composition;

[0066] Preferably, the catalyst composition comprises a combination of an organic zinc, an organic base and a phenolic compound.

[0067] The present invention also provides an antifouling synthetic leather, the synthetic leather comprising the polyurethane resin;

[0068] Preferably, the polyurethane resin is used as the surface layer or middle layer of the synthetic leather;

[0069] In some embodiments of the invention, the polyurethane resin is used as a surface layer material of synthetic leather without adding a foaming agent, and the polyurethane resin is used as a middle layer material of synthetic leather with adding a foaming agent;

[0070] As an example, the method for preparing antifouling synthetic leather includes the following steps:

[0071] The hydroxyl composition and the isocyanate composition are mixed and coated on the release paper through a casting machine, and then passed through a pre-baking oven at a temperature of 70 to 100° C. and a pre-baking time of 1 to 2 minutes. After pre-baking, the base fabric is bonded to the pre-baking paper, and then the pre-baking paper enters a post-baking oven for aging at a temperature of 120 to 130° C. and a heating time of 3 to 5 minutes to obtain anti-fouling synthetic leather.

[0072] The content and operation steps of the present invention are further illustrated by specific examples. The specific material ratios, process conditions and results described in the examples are only illustrative and do not limit the material ratios and process conditions.

[0073] Fluorinated chain extender 1: reaction product of diisopropanolamine and hexafluorobutyl methacrylate;

[0074] Fluorinated chain extender 2: reaction product of diisopropanolamine and dodecafluoroheptyl methacrylate;

[0075] Fluorinated chain extender 3: reaction product of diisopropanolamine and trifluoroethyl methacrylate;

[0076] Fluorinated chain extender 4: reaction product of diethanolamine and hexafluorobutyl methacrylate;

[0077] Preparation of fluorinated chain extender:

[0078] Add dihydroxy alcohol amine and fluorinated acrylic acid in a molar ratio of 1-1.15:1 to ethanol solvent, heat with stirring at a heating temperature of 70-75°C, and react for 8-12 hours to obtain a crude fluorinated chain extender. Wash and purify with deionized water, distill under reduced pressure, and dry to obtain a fluorinated chain extender, which is then stored for later use.

[0079] Hydroxyl composition 1-1

[0080] 100 parts by weight of polymer polyol;

[0081] 22 parts by weight of chain extender;

[0082] Wherein, the polymer polyol is polybutylene adipate polyol with an average number average molecular weight of 2000, and the chain extender is a combination of 9 parts by weight of fluorine-containing chain extender 1 and 13 parts by weight of ethylene glycol;

[0083] Hydroxyl composition 1-2

[0084]

[0085] Wherein, the polymer polyol is polybutylene adipate polyol with an average number average molecular weight of 2000, and the chain extender is a combination of 9 parts by weight of fluorine-containing chain extender 1 and 13 parts by weight of ethylene glycol;

[0086] Hydroxyl composition 2-1

[0087] 120 parts by weight of polymer polyol;

[0088] 29 parts by weight of chain extender;

[0089] Wherein, the polymer polyol is polyethylene adipate glycol butanediol polyol having an average number average molecular weight of 2000, and the chain extender is a combination of 24 parts by weight of a fluorine-containing chain extender 2 and 5 parts by weight of butanediol;

[0090] Hydroxyl composition 2-2

[0091]

[0092] Wherein, the polymer polyol is polyethylene adipate glycol butanediol polyol having an average number average molecular weight of 2000, and the chain extender is a combination of 24 parts by weight of a fluorine-containing chain extender 2 and 5 parts by weight of butanediol;

[0093] Hydroxyl composition 3-1

[0094] 100 parts by weight of polymer polyol;

[0095] 23 parts by weight of chain extender;

[0096] Wherein, the polymer polyol is polyoxypropylene polyol having an average number average molecular weight of 3000, and the chain extender is a combination of 8 parts by weight of fluorine-containing chain extender 1 and 15 parts by weight of butanediol;

[0097] Hydroxyl composition 3-2

[0098]

[0099] Wherein, the polymer polyol is polyoxypropylene polyol having an average number average molecular weight of 3000, and the chain extender is a combination of 8 parts by weight of fluorine-containing chain extender 1 and 15 parts by weight of butanediol;

[0100] Hydroxyl composition 4-1

[0101] 120 parts by weight of polymer polyol;

[0102] 12 parts by weight of chain extender;

[0103] The polymer polyol is a polyethylene oxide polyol having an average number average molecular weight of 6000, and the chain extender is a combination of 9 parts by weight of a fluorinated chain extender 2 and 3 parts by weight of butanediol;

[0104] Hydroxyl composition 4-2

[0105]

[0106] The polymer polyol is a polyethylene oxide polyol having an average number average molecular weight of 6000, and the chain extender is a combination of 9 parts by weight of a fluorinated chain extender 2 and 3 parts by weight of butanediol;

[0107] Hydroxyl composition 5-1

[0108] 100 parts by weight of polymer polyol;

[0109] 14 parts by weight of chain extender;

[0110] Wherein, the polymer polyol is a polyethylene oxide polyol having an average number average molecular weight of 4000, and the chain extender is a combination of 8 parts by weight of a fluorinated chain extender 2 and 6 parts by weight of ethylene glycol;

[0111] Hydroxyl composition 5-2

[0112]

[0113] Wherein, the polymer polyol is a polyethylene oxide polyol having an average number average molecular weight of 4000, and the chain extender is a combination of 8 parts by weight of a fluorinated chain extender 2 and 6 parts by weight of ethylene glycol;

[0114] Hydroxyl composition 6-1

[0115] 80 parts by weight of polymer polyol;

[0116] 5 parts by weight of chain extender;

[0117] Wherein, the polymer polyol is polytetramethylene glycol with an average number average molecular weight of 2000, and the chain extender is a combination of 3 parts by weight of a fluorine-containing chain extender and 2 parts by weight of ethylene glycol;

[0118] Hydroxyl composition 6-2

[0119]

[0120] Wherein, the polymer polyol is polytetramethylene glycol with an average number average molecular weight of 2000, and the chain extender is a combination of 3 parts by weight of a fluorine-containing chain extender and 2 parts by weight of ethylene glycol;

[0121] Hydroxyl composition 7-1

[0122] 100 parts by weight of polymer polyol;

[0123] 23 parts by weight of chain extender;

[0124] Wherein, the polymer polyol is polyoxypropylene polyol having an average number average molecular weight of 3000, and the chain extender is a combination of 8 parts by weight of fluorine-containing chain extender 4 and 15 parts by weight of butanediol;

[0125] Hydroxyl composition 7-2

[0126]

[0127] Wherein, the polymer polyol is polyoxypropylene polyol having an average number average molecular weight of 3000, and the chain extender is a combination of 8 parts by weight of fluorine-containing chain extender 4 and 15 parts by weight of butanediol;

[0128] Hydroxyl composition 8-1

[0129] 100 parts by weight of polymer polyol;

[0130] 23 parts by weight of chain extender;

[0131] Wherein, the polymer polyol is polyoxypropylene polyol having an average number average molecular weight of 3000, and the chain extender is a combination of 8 parts by weight of fluorine-containing chain extender 3 and 15 parts by weight of butanediol;

[0132] Hydroxyl composition 8-2

[0133]

[0134] Wherein, the polymer polyol is polyoxypropylene polyol having an average number average molecular weight of 3000, and the chain extender is a combination of 8 parts by weight of fluorine-containing chain extender 3 and 15 parts by weight of butanediol;

[0135] Hydroxyl composition 9-1

[0136] 100 parts by weight of polymer polyol;

[0137] 22 parts by weight of chain extender;

[0138] Wherein, the polymer polyol is polybutylene adipate polyol having an average number average molecular weight of 2000, and the chain extender is a combination of 6.9 parts by weight of fluorinated chain extender 1 and 15.1 parts by weight of ethylene glycol;

[0139] Hydroxyl composition 9-2

[0140]

[0141]

[0142] Wherein, the polymer polyol is polybutylene adipate polyol having an average number average molecular weight of 2000, and the chain extender is a combination of 6.9 parts by weight of fluorinated chain extender 1 and 15.1 parts by weight of ethylene glycol;

[0143] Hydroxyl composition 10-1

[0144] 120 parts by weight of polymer polyol;

[0145] 29 parts by weight of chain extender;

[0146] Wherein, the polymer polyol is polyethylene adipate glycol butanediol polyol having an average number average molecular weight of 2000, and the chain extender is a combination of 25.2 parts by weight of fluorine-containing chain extender 2 and 3.8 parts by weight of butanediol;

[0147] Hydroxyl composition 10-2

[0148]

[0149] Wherein, the polymer polyol is polyethylene adipate glycol butanediol polyol having an average number average molecular weight of 2000, and the chain extender is a combination of 25.2 parts by weight of fluorine-containing chain extender 2 and 3.8 parts by weight of butanediol;

[0150] Comparative Hydroxyl Composition 1-1

[0151] 100 parts by weight of polymer polyol;

[0152] 22 parts by weight of chain extender;

[0153] Wherein, the polymer polyol is polybutylene adipate polyol with an average number average molecular weight of 2000, and the chain extender is ethylene glycol;

[0154] Comparative Hydroxyl Compositions 1-2

[0155]

[0156] Wherein, the polymer polyol is polybutylene adipate polyol with an average number average molecular weight of 2000, and the chain extender is ethylene glycol;

[0157] Comparative Hydroxyl Composition 2-1

[0158] 100 parts by weight of polymer polyol;

[0159] 22 parts by weight of chain extender;

[0160] Wherein, the polymer polyol is polybutylene adipate polyol with an average number average molecular weight of 2000, and the chain extender is fluorine-containing chain extender 1;

[0161] Comparative Hydroxyl Composition 2-2

[0162]

[0163] Wherein, the polymer polyol is polybutylene adipate polyol with an average number average molecular weight of 2000, and the chain extender is fluorine-containing chain extender 1;

[0164] Isocyanate composition 1

[0165] 100 parts by weight of polyisocyanate;

[0166] 80 parts by weight of polymer polyol;

[0167] 0.1 parts by weight of phosphoric acid

[0168] Wherein, the polyisocyanate is MDI, and the polymer polyol is polybutylene adipate polyol with an average number average molecular weight of 2000;

[0169] Isocyanate composition 2

[0170] 80 parts by weight of polyisocyanate;

[0171] 55 parts by weight of polymer polyol;

[0172] 0.2 parts by weight of phosphoric acid

[0173] Wherein, the polyisocyanate is MDI, and the polymer polyol is polybutylene adipate polyol with an average number average molecular weight of 2000;

[0174] Isocyanate composition 3

[0175] 120 parts by weight of polyisocyanate;

[0176] 100 parts by weight of polymer polyol;

[0177] 0.1 parts by weight of phosphoric acid

[0178] Wherein, the polyisocyanate is MDI, and the polymer polyol is polytetramethylene glycol with an average number average molecular weight of 1000;

[0179] Isocyanate composition 4

[0180] 100 parts by weight of polyisocyanate;

[0181] 60 parts by weight of polymer polyol;

[0182] 0.2 parts by weight of phosphoric acid

[0183] Wherein, the polyisocyanate is liquefied MDI, and the polymer polyol is polytetramethylene glycol with an average number average molecular weight of 2000;

[0184] Isocyanate composition 5

[0185] 164 parts by weight of polyisocyanate;

[0186] 150 parts by weight of polymer polyol;

[0187] 0.1 parts by weight of phosphoric acid

[0188] Wherein, the polyisocyanate is liquefied MDI, and the polymer polyol is polytetramethylene glycol with an average number average molecular weight of 2000;

[0189] Isocyanate composition 6

[0190] 100 parts by weight of polyisocyanate;

[0191] 60 parts by weight of polymer polyol;

[0192] 0.1 parts by weight of phosphoric acid

[0193] The polyisocyanate is liquefied MDI, and the polymer polyol is polytetramethylene glycol with an average number average molecular weight of 1000.

[0194] Preparation of synthetic leather:

[0195] In order to more directly characterize and compare the performance of each embodiment and comparative example, the polyurethane resin prepared from the hydroxyl composition without a foaming agent in the embodiment of the present invention and the comparative example was used as the middle layer material of the synthetic leather, and the polyurethane resin prepared from the hydroxyl composition with a foaming agent in the embodiment of the present invention and the comparative example was used as the surface layer material of the synthetic leather, and different types of synthetic leather were prepared respectively;

[0196] When the polyurethane resin of the present invention is used as the intermediate layer, the synthetic leather preparation method is as follows:

[0197] First, a surface resin (a product of Zhejiang Synthetic Resin Company with the brand name JF-S-8050) is coated on the release paper and dried at 120-130°C for 2-5 minutes. Then, the hydroxyl composition and the isocyanate composition of the embodiment and the comparative example are mixed according to a molar ratio of NCO in the isocyanate composition to the reactive group with NCO in the hydroxyl composition of 1-1.07; the mixture is coated on the surface resin by a casting machine, passed through an oven at a drying temperature of 70-100°C for 1-2 minutes, and then laminated to a base fabric (stretch fabric) after drying. The mixture enters a subsequent oven for aging at a temperature of 120-130°C for 3-5 minutes, and the release paper is peeled off to the synthetic leather.

[0198] When the polyurethane resin of the present invention is used as the surface layer, the synthetic leather preparation method is as follows:

[0199] The hydroxyl composition and the isocyanate composition of the embodiment and the comparative example are mixed so that the molar ratio of NCO in the isocyanate composition to the group reactive toward NCO in the hydroxyl composition is 1-1; the mixture is coated on a base fabric (stretch fabric) by a casting machine, and then cured in an oven at a temperature of 120-130° C. for 6-7 minutes. The release paper is peeled off and the synthetic leather is directly obtained by integral molding.

[0200] The composition of synthetic leather is as follows:

[0201]

[0202]

[0203]

[0204] The above synthetic leathers were subjected to the following performance tests, and the specific performances are shown in the table below:

[0205] (1) Taber wear resistance: The test was conducted using a high-speed rail Taber wear resistance tester. Samples were cut using a mold and tested using an H-18 grinding wheel with a load of 1000g. The number of revolutions when damage appeared on the sample surface was recorded as the test result. Each sample was tested 3 times and the average value was taken.

[0206] (2) Tear strength: Use a leather material tear strength tester to test. Place the sample in a laboratory environment for more than 8 hours, prepare 25*150mm samples in the warp and weft directions, clamp the two ends of the sample on the upper and lower clamps of the tensile testing machine, keep the sample vertical, set the tensile testing machine speed to 200mm / min, record the maximum value of the tensile testing machine as the result, test each sample at least 3 times, and take the average value.

[0207] (3) Stain resistance: Cut a 50*50cm sample from the sample to be tested. After removing 50mm of width from both ends of the sample, cut a square sample with a side length of 200mm. Apply any one of ketchup, instant coffee, and gasoline engine oil evenly on the surface of the sample to produce two square stains with a side length of 30mm. After drying the sample with the stain at room temperature for 24 hours, perform a cleaning test and record the results. The test is characterized by a scale of 1 to 5, where level 1 indicates the worst stain resistance and level 5 indicates the best.

[0208] (4) Weather resistance: Cut the test sample into a size of 200*100mm, hang the sample vertically in a high-temperature aging test chamber at 120℃ and circulating hot air conditions, take out the sample and observe it every 24 hours. If the surface becomes sticky or numb, stop the test and record the test hours as the result.

[0209]

[0210]

Claims

1. A hydroxy composition, characterized in that The invention comprises a polymer polyol and a chain extender mixture, wherein the chain extender mixture comprises a combination of a fluorine-containing chain extender and a fluorine-free chain extender; and the mass ratio of the fluorine-containing chain extender to the fluorine-free chain extender is 0.5:1 to 6:

1.

2. The hydroxy composition according to claim 1, characterized in that The fluorine-containing chain extender comprises a reaction product obtained from dihydroxy alcohol amine and fluorine-containing acrylate.

3. The hydroxy composition according to claim 2, characterized in that The hydroxyl group in the dihydroxy alcoholamine is a secondary hydroxyl group; preferably, the dihydroxy alcoholamine includes diisopropanolamine.

4. The hydroxy composition according to claim 2, characterized in that The fluorine-containing acrylate has more than 6 fluorine groups, including one or more of hexafluorobutyl (meth)acrylate, dodecafluoroheptyl (meth)acrylate, tridecafluorooctyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, and perfluorotetradecylethyl (meth)acrylate.

5. The hydroxy composition according to claim 1, characterized in that The fluorine-free chain extender includes C2 to C8 diols, including one or more of ethylene glycol, diethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, hexanediol, heptanediol, and decanediol.

6. The hydroxy composition according to claim 1, characterized in that The polymer polyol includes polyether polyol and / or polyester polyol, and the polyether polyol includes one or more of polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, and polytetramethylene ether polyol; the polyester polyol includes a polyol obtained by reacting at least one small molecule diol and at least one small molecule dibasic acid, and the small molecule diol includes one or more of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, and nonanediol; the small molecule dibasic acid includes one or more of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid; the number average molecular weight of the polymer polyol is 500-6000 g / mol; and the OH value of the hydroxy composition is 50-380 mg KOH / g.

7. The hydroxy composition according to claim 1, characterized in that The hydroxy composition comprises the following components in parts by weight: 80-120 parts by weight of polymer polyol; 1 to 30 parts by weight of chain extender 8. The hydroxy composition according to claim 7, characterized in that The hydroxy composition further comprises any one of a foaming agent and a foam leveling agent or a combination of both.

9. A polyurethane resin prepared using the hydroxy composition according to claim 1, characterized in that: The polyurethane resin comprises the hydroxyl composition and the isocyanate composition, wherein the isocyanate composition comprises a polyurethane prepolymer; the molar ratio of NCO in the isocyanate composition to the groups reactive toward NCO in the hydroxyl composition is 0.98:1 to 1.1:1; the polyurethane prepolymer is obtained by reacting a polymer polyol with a polyisocyanate, and the NCO mass content of the polyurethane prepolymer is 6-20%; the polyisocyanate comprises one or more of toluene diisocyanate TDI, diphenylmethane diisocyanate MDI, and isomers and / or derivatives and / or modified polymers thereof.

10. A polyurethane resin prepared using the hydroxy composition according to claim 9, characterized in that: The polyurethane resin is used to prepare antifouling synthetic leather and as a resin material for an intermediate layer or a surface layer of the synthetic leather.

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