Compositions for forming polyurethanes, uses thereof, and articles made therefrom

Abstract

The present invention relates to the field of new polyurethane materials. Specifically, the present invention relates to a composition for forming polyurethane, its use and products made therefrom. The composition for forming polyurethane of the present invention comprises: A. an isocyanate reactive component, which comprises, a) a difunctional polyol; b) a multifunctional polyol; and c) a crosslinking agent, and B. an isocyanate prepolymer component, which is prepared from at least one non-aromatic polyisocyanate and at least one compound containing two or more hydroxyl groups, and C. a catalyst. The products obtained from the composition have significantly improved mechanical properties and yellowing resistance.

Description

Technical Field

[0001] The present invention relates to the field of new polyurethane materials, and in particular to a composition for forming polyurethane, its use and products made therefrom. Background Art

[0002] Polyurethane (PU), especially solvent-free polyurethane, has a wide range of applications in modern society. For example, the use of polyurethane in the manufacture of synthetic leather is known. Synthetic leather made of solvent-free polyurethane is a laminated polymer material that has been widely used in many industries such as furniture, clothing, car seat covers and footwear. Generally speaking, solvent-free polyurethane for making polyurethane synthetic leather is based on aromatic isocyanate, which can bring good mechanical properties and processing capabilities to the synthetic leather. However, the synthetic leather obtained in this way will turn yellow over time due to the poor weather resistance of the aromatic ring inside the polyurethane.

[0003] Therefore, it is necessary to obtain a polyurethane (especially a solvent-free type) so that the products made therefrom, especially synthetic leather products, not only have good mechanical properties and processing capabilities, but also have good weather resistance and can meet strict yellowing resistance requirements. Summary of the invention

[0004] In order to solve the problems in the prior art, the present invention provides a composition for preparing polyurethane, so that the products obtained from such polyurethane composition can achieve the desired performance. The composition of the present invention has good processing ability, and the obtained products not only have good mechanical properties, but also have good weather resistance and can meet strict yellowing resistance requirements.

[0005] A main aspect of the present invention relates to a composition comprising,

[0006] A. an isocyanate-reactive component comprising,

[0007] a) a difunctional polyol having a weight average molecular weight of 800 to 4000 g / mol;

[0008] b) a multifunctional polyol having a weight average molecular weight of 2000 to 6000 g / mol, wherein the functionality of the multifunctional polyol is greater than or equal to 2.4; and

[0009] c) a crosslinker having a weight average molecular weight of 90 g / mol to 1000 g / mol, wherein the functionality of the crosslinker is greater than or equal to 2.5, wherein the content of the crosslinker is 2.2 wt % to 9 wt % based on the total weight of component A and component C, and

[0010] B. an isocyanate prepolymer component prepared from at least one non-aromatic polyisocyanate and at least one compound containing two or more hydroxyl groups, and

[0011] C. A catalyst, wherein the catalyst is a combination of a tertiary amine catalyst and a metal catalyst, or the catalyst is a tin catalyst.

[0012] The present invention also relates to the use of the composition for manufacturing synthetic leather, and polyurethane products obtained by using the composition, such as polyurethane synthetic leather.

[0013] The composition of the present invention is based on non-aromatic isocyanates. The polyurethane obtained from the composition of the present invention can be used to manufacture various products, and is particularly suitable for manufacturing synthetic leather. Compared with polyurethane products obtained based on aromatic isocyanates, the polyurethane products of the present invention not only achieve comparable or even improved mechanical properties and processing characteristics, but also improve yellowing resistance. The composition of the present invention expands the application range of solvent-free polyurethane synthetic leather, and the composition of the present invention has good processing properties, especially dry processability, and is suitable for applications requiring strict yellowing resistance. DETAILED DESCRIPTION

[0014] The present invention is further described in detail below through specific embodiments. These specific embodiments are given for illustrative purposes only and are not intended to limit the scope of protection of the present invention. The scope of protection required by the present invention is defined by the claims.

[0015] Compositions of the present invention

[0016] A first aspect of the present invention relates to a composition comprising:

[0017] A. an isocyanate-reactive component comprising,

[0018] a) a difunctional polyol having a weight average molecular weight of 800 to 4000 g / mol, preferably 800 to 3000 g / mol;

[0019] b) a polyfunctional polyol having a weight average molecular weight of 2000 to 6000 g / mol, preferably 2500 to 5000 g / mol, the functionality of the polyfunctional polyol being greater than or equal to 2.4, preferably in the range of greater than 2.4 and less than or equal to 5, preferably in the range of 2.5 to 3.2, more preferably in the range of 2.5 to 3; and

[0020] c) a crosslinker having a weight average molecular weight of 90 to 1000 g / mol, preferably 100 to 800 g / mol, the functionality of the crosslinker being greater than or equal to 2.5, preferably greater than or equal to 3, for example in the range of 2.5 to 3.5 or 2.8 to 5, wherein the content of the crosslinker is 2.2 to 9% by weight, preferably 2.5 to 8% by weight, based on the total weight of component A and component C, and

[0021] B. an isocyanate prepolymer component prepared from at least one non-aromatic polyisocyanate and at least one compound containing two or more hydroxyl groups, and

[0022] C. A catalyst, wherein the catalyst is a combination of a tertiary amine catalyst and a metal catalyst, or the catalyst is a tin catalyst.

[0023] The composition of the present invention is a solvent-free composition.

[0024] The composition of the present invention is also a two-component type composition.

[0025] Isocyanate Reactive Component A

[0026] Component A in the composition of the present invention is an isocyanate reactive component, which comprises a difunctional polyol, a multifunctional polyol, and a crosslinking agent. Component A of the present invention may further comprise a chain extender.

[0027] Polyols

[0028] Component A in the composition of the invention comprises a polyol. In the present invention, the term "polyol" includes difunctional polyols and more functional polyols. Polyols are in principle those with two or more OH groups in the molecule. These polyol components suitable for the present invention preferably include or are selected from polyether polyols and / or polyester polyols. These are generally known and described, for example, in "Kunststoffhandbuch Polyurethane", Günter Oertel, Carl-Hanser-Verlag, 2nd edition, 1983, chapter 3.1.1.

[0029] Polyester polyols can be obtained by condensing polyfunctional alcohols having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, with polyfunctional carboxylic acids having 2 to 12 carbon atoms. Examples of polyfunctional alcohols include ethylene glycol, neopentyl glycol, 1,2-propylene glycol, 2,2-dimethyl-1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol and 1,2-cyclohexanedimethanol, and polyols such as trimethylolethane, trimethylolpropane, trimethylolhexane, 1,2,4-butanetriol, pentaerythritol and dipentaerythritol. Examples of the polyfunctional carboxylic acids include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and maleic acid. It is also possible to use polyester polyols derived from lactones (eg, ε-caprolactone) or hydroxycarboxylic acids (eg, ω-hydroxycaproic acid).

[0030] The polyether polyols generally comprise repeating units derived from alkylene oxides selected from ethylene oxide (EO) and ethylene oxide (PO), butylene oxide and tetrahydrofuran.

[0031] Polyether polyols are generally obtainable by anionic polymerization of one or more alkylene oxides selected from ethylene oxide (EO) and propylene oxide (PO), butylene oxide and tetrahydrofuran, for example using alkali metal hydroxides as catalysts and concomitantly adding starter molecules containing multiple active hydrogen atoms.

[0032] The alkylene oxides can be used individually, in succession or in a mixture. The use of EO-PO mixtures will give polyether polyols with randomly distributed PO / EO units. It is possible to start with a PO-EO mixture and then continue to use either PO or EO alone before the polymerization is terminated, and the product is a polyether polyol with PO end-capping or EO end-capping, respectively.

[0033] The starter molecules used are generally NH- or OH-functional compounds, such as water, amines or alcohols. Preference is given to using dihydric to hexahydric alcohols, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerol, trimethylolpropane, pentaerythritol and / or sorbitol.

[0034] It is also preferred to use polyether polyols obtained by ring-opening polymerization of tetrahydrofuran. In the related art, polytetrahydrofuran (=PTHF) is known by the following names: tetramethylene glycol (=PTMG), polytetramethylene glycol ether (=PTMEG) or polytetramethylene oxide (=PTMO).

[0035] In the present invention, the term "difunctional polyol" refers to a polyol with a functionality of 2. The difunctional polyol suitable for use as component a) of the present invention is preferably a polyether diol or a polyester diol or any combination thereof, preferably selected from polyethylene oxide diol, polypropylene oxide diol, poly(ethylene oxide-propylene oxide) diol, polytetrahydrofuran diol and polycaprolactone diol, in particular polytetrahydrofuran diol.

[0036] The weight average molecular weight of the difunctional polyols suitable for use as component a) of the present invention is in the range of 800 to 4000 g / mol. For example, the weight average molecular weight of the difunctional polyols suitable for use as component a) of the present invention can be 800 g / mol, 900 g / mol, 1000 g / mol, 1200 g / mol, 1400 g / mol, 1600 g / mol, 1800 g / mol, 2000 g / mol, 2200 g / mol, 2400 g / mol, 2600 g / mol, 2800 g / mol, 3000 g / mol, 3200 g / mol, 3400 g / mol, 3600 g / mol, 3800 g / mol, 4000 g / mol, or the weight average molecular weight can be any value between these values. In a preferred embodiment, the difunctional polyol suitable for use as component a) of the present invention may have a weight average molecular weight of 800 to 3000 g / mol, such as 800 to 2500 g / mol, such as 900 to 2000 g / mol.

[0037] The polyfunctional polyol suitable for use as component b) of the present invention is preferably a polyether polyol, a polyester polyol or any combination thereof, preferably selected from polyethylene oxide polyol, polypropylene oxide polyol, poly(ethylene oxide-propylene oxide) polyol, polytetramethylene oxide polyol and polycaprolactone polyol.

[0038] The functionality of the polyfunctional polyols suitable for use as component b) of the present invention is greater than or equal to 2.4. For example, the functionality of the polyfunctional polyols suitable for use as component b) of the present invention can be 2.4, 2.5, 2.8, 3.2, 3.6, 4.0, 4.5, 5.0, or any value between these values. In a preferred embodiment, the functionality of the polyfunctional polyols suitable for use as component b) of the present invention is in the range of 2.4 to 5, preferably in the range of 2.5 to 3.2, and more preferably in the range of 2.5 to 3.

[0039] The weight average molecular weight of the polyfunctional polyol suitable for use as component b) of the present invention is in the range of 2000 to 6000 g / mol. For example, the weight average molecular weight of the polyfunctional polyol suitable for use as component b) of the present invention can be 2000 g / mol, 2200 g / mol, 2400 g / mol, 2600 g / mol, 2800 g / mol, 3000 g / mol, 3200 g / mol, 3400 g / mol, 3600 g / mol, 3800 g / mol, 4000 g / mol, 4200 g / mol, 4400 g / mol, 4600 g / mol, 4800 g / mol, 5000 g / mol, 5200 g / mol, 5400 g / mol, 5600 g / mol, 5800 g / mol, 6000 g / mol, or the weight average molecular weight can be any value between these values. In a preferred embodiment, the weight average molecular weight of the multifunctional polyol suitable for use as component b) of the present invention may be 2500 to 5000 g / mol, such as 3000 to 5000 g / mol.

[0040] In a preferred embodiment of the present invention, based on the weight of component A in the present composition, the total content of component a) of the present invention and component b) can be in the range of 80 to 99% by weight. For example, based on the weight of component A in the present composition, the total content of component a) of the present invention and component b) can be 80% by weight, 83% by weight, 85% by weight, 87% by weight, 90% by weight, 93% by weight, 95% by weight, 97% by weight, 99% by weight, or the amount between any of these values. Preferably, based on the weight of component A in the present composition, the total content of component a) of the present invention and component b) is in the range of 85 to 99% by weight, more preferably in the range of 90 to 99% by weight.

[0041] In a preferred embodiment of the present invention, component a) and component b) may be present in the composition of the present invention in a weight ratio ranging from 3:1 to 1:3. For example, component a) and component b) may be present in the composition of the present invention in a weight ratio of 3:1, 2.5:1, 2:1, 1.5:1, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, or in a weight ratio of any value between these values. Preferably, in the composition of the present invention, the weight ratio of component a) and component b) is in the range of 2:1 to 1:2, more preferably in the range of 1.2:1 to 1:1.2.

[0042] Crosslinking agent

[0043] Component A of the present invention further comprises a crosslinker as component c).

[0044] The crosslinking agent suitable for use as component c) of the present invention has a functionality greater than or equal to 2.5 (i.e., has greater than or equal to 2.5 hydrogen atoms reactive toward isocyanate). Preferably, the crosslinking agent suitable for use as component c) of the present invention may have a functionality of 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.5, 4.0, 4.5, 5, or any value between these functionality values. Preferably, the crosslinking agent suitable for use as component c) of the present invention may have a functionality greater than or equal to 3, or the crosslinking agent suitable for use as component c) of the present invention may have a functionality in the range of 2.5 to 5 or 2.8 to 5, for example in the range of 2.5 to 3.5, in the range of 2.8 to 3.2.

[0045] In the present context, functionality, especially when referring to a polymer or oligomer, generally refers to the average functionality.

[0046] Preferably, the crosslinking agent suitable for component c) of the present invention is selected from compounds having 3 to 10 carbon atoms and at least 3 hydroxyl groups and their alkoxylation products, preferably selected from glycerol, trimethylolpropane, butanetriol, pentaerythritol, and their alkoxylation products. As examples of crosslinking agents suitable for component c) of the present invention, there can be cited triols, such as 1,2,4-trihydroxycyclohexane, 1,3,5-trihydroxycyclohexane, glycerol, butanetriol, and trimethylolpropane; tetraols such as pentaerythritol; and hydroxyl-containing low molecular weight polyoxyalkylenes based on ethylene oxide and / or 1,2-propylene oxide and the above triols or tetraols as starter molecules.

[0047] In some preferred embodiments, the crosslinking agent suitable for use as component c) of the present invention may be glycerol, ethoxylated and / or propoxylated glycerol, trimethylolpropane, ethoxylated and / or propoxylated trimethylolpropane, butanetriol, ethoxylated and / or propoxylated butanetriol, pentaerythritol, ethoxylated and / or propoxylated pentaerythritol, or any combination thereof.

[0048] In a preferred embodiment, the crosslinking agent is ethoxylated and / or propoxylated glycerol, ethoxylated and / or propoxylated trimethylolpropane, ethoxylated and / or propoxylated butanetriol or any combination thereof. By using these ethoxylated and / or propoxylated agents, significantly improved mechanical properties, especially peeling properties, are obtained.

[0049] The weight average molecular weight of the crosslinking agent suitable for use as component c) of the present invention is in the range of 90 to 1000 g / mol, for example, the weight average molecular weight of the crosslinking agent suitable for use as component c) of the present invention can be 90 g / mol, 92 g / mol, 100 g / mol, 134 g / mol, 150 g / mol, 200 g / mol, 250 g / mol, 300 g / mol, 350 g / mol, 400 g / mol, 450 g / mol, 500 g / mol, 550 g / mol, 600 g / mol, 650 g / mol, 700 g / mol, 750 g / mol, 800 g / mol, 850 g / mol, 900 g / mol, 950 g / mol, 990 g / mol, 1000 g / mol, or the weight average molecular weight can be any value between these values. In a preferred embodiment, the weight average molecular weight of the crosslinking agent suitable for use as component c) of the present invention may be from 100 to 800 g / mol, or from 150 to 600 g / mol, or from 100 to 400 g / mol.

[0050] Crosslinking agents suitable for use as component c) of the present invention may have a hydroxyl value in the range of 168 to 2000 mg KOH / g. For example, crosslinking agents suitable for use as component c) of the present invention may have a hydroxyl value of 168 mg KOH / g, 200 mg KOH / g, 300 mg KOH / g, 400 mg KOH / g, 500 mg KOH / g, 600 mg KOH / g, 700 mg KOH / g, 800 mg KOH / g, 900 mg KOH / g, 1000 mg KOH / g, 1100 mg KOH / g, 1200 mg KOH / g, 1300 mg KOH / g, 1400 mg KOH / g, 1500 mg KOH / g, 1600 mg KOH / g, 1700 mg KOH / g, 1800 mg KOH / g, 1900 mg KOH / g, 2000 mg KOH / g. Preferably, crosslinking agents suitable for use as component c) of the present invention may have a hydroxyl number in the range of 500 to 2000 mg KOH / g.

[0051] Based on the total weight of component A and component C in the composition of the present invention, the amount of component c) of the present invention is in the range of 2.2 wt % to 9 wt %. For example, based on the total weight of component A and component C in the composition of the present invention, the amount of component c) of the present invention can be 2.2 wt %, 2.4 wt %, 2.6 wt %, 2.8 wt %, 3.0 wt %, 3.2 wt %, 3.4 wt %, 3.6 wt %, 3.8 wt %, 4.0 wt %, 4.2 wt %, 4.4 wt %, 4.6 wt %, 4.8 wt %, 5.0 wt %, 5.2 wt %, 5.4 wt %, 5.6 wt %, 5.8 wt %, 6.0 wt %, 6.2 wt %, 6.4 wt %, 6.6 wt %, 6.8 wt %, 7.0 wt %, 7.2 wt %, 7.4 wt %, 7.6 wt %, 7.8 wt %, 8.0 wt %, 8.2 wt %, 8.4 wt %, 8.6 wt %, 8.8 wt %, 9.0 wt %, or an amount between any of these values. Preferably, the amount of component c) of the present invention may be in the range of 2.5 to 9 wt %, more preferably in the range of 2.5 to 8 wt %, based on the total weight of component A and component C in the composition of the present invention.

[0052] Chain Extender

[0053] Preferably, component A of the present invention also comprises a chain extender as component d). In this context, the term "chain extender" is used for molecules having two hydrogen atoms reactive toward isocyanate. That is, in this context, a chain extender is a molecule having a functionality of 2 and having hydrogen atoms reactive toward isocyanate.

[0054] As chain extenders suitable as component d) according to the invention, it is preferred to use, for example, straight-chain and branched aliphatic and cycloaliphatic diols having 2 to 14, preferably 2 to 10, more preferably 2 to 6 carbon atoms, these include 1,2-ethanediol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 1,6-hexanediol, 1,6-hexanediol, 1,6-hexanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 1,6-hexanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 1,6-hexanediol. -Hexanediol, 2,5-hexanediol, 1,2-heptanediol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol, 1,2-nonanediol, 1,9-nonanediol, 1,2-decanediol, 1,10-decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, 2-methyl-2-butyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-dimethyl-1,4-butanediol, pinacol, 2-ethyl-2-butyl-1,3-propanediol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, cyclopentanediol, cyclohexanediol, etc.

[0055] The weight average molecular weight of the chain extender suitable for use as component d) of the present invention is less than or equal to 500 g / mol. For example, the weight average molecular weight of the chain extender suitable for use as component d) of the present invention may be 60 g / mol, 80 g / mol, 90 g / mol, 100 g / mol, 150 g / mol, 200 g / mol, 250 g / mol, 300 g / mol, 350 g / mol, 400 g / mol, 450 g / mol, 500 g / mol, or the weight average molecular weight may be any value between these values. In a preferred embodiment, the weight average molecular weight of the chain extender suitable for use as component d) of the present invention may be 60 to 400 g / mol, or 60 to 300 g / mol.

[0056] Preferably, the content of component d) of the present invention is in the range of 1 wt % to 8 wt %, based on the total weight of component A and component C in the composition of the present invention. For example, based on the total weight of component A and component C in the composition of the present invention, the content of component d) of the present invention can be 1.0 wt %, 1.2 wt %, 1.4 wt %, 1.6 wt %, 1.8 wt %, 2.0 wt %, 2.2 wt %, 2.4 wt %, 2.6 wt %, 2.8 wt %, 3.0 wt %, 3.2 wt %, 3.4 wt %, 3.6 wt %, 3.8 wt %, 4.0 wt %, 4.2 wt %, 4.4 wt %, 4.6 wt %, 4.8 wt %, 5.0 wt %, 5.2 wt %, 5.4 wt %, 5.6 wt %, 5.8 wt %, 6.0 wt %, 6.2 wt %, 6.4 wt %, 6.6 wt %, 6.8 wt %, 7.0 wt %, 7.2 wt %, 7.4 wt %, 7.6 wt %, 7.8 wt %, 8.0 wt %, or any amount between these values. Preferably, the amount of component d) of the present invention may be in the range of 2 to 7 wt %, more preferably in the range of 2 to 6 wt %, based on the total weight of component A and component C in the composition of the present invention.

[0057] Isocyanate prepolymer component B

[0058] Component B in the composition of the present invention is an isocyanate prepolymer component prepared from at least one non-aromatic polyisocyanate and at least one compound containing two or more hydroxyl groups.

[0059] Isocyanates are N-substituted organic derivatives (RN=C=O) of isocyanic acid (HNCO) that tautomerize with cyanic acid in the free state. Organic isocyanates are compounds in which an isocyanate group (-N=C=O) is bonded to an organic group. Herein, the term "polyisocyanate" is a compound having two or more (e.g., 3, 4, 5, etc.) isocyanate groups in the molecule.

[0060] The polyisocyanates suitable for use in the present invention are non-aromatic polyisocyanates, including alicyclic and aliphatic polyisocyanates, provided that they have at least two reactive isocyanate groups. Suitable polyisocyanates are selected from compounds having 2 to 5 isocyanate groups, isocyanate prepolymers having an average of 2 to 5 isocyanate groups, and mixtures thereof. These include, for example, aliphatic and alicyclic diisocyanates, triisocyanates and higher polyisocyanates. Preferably, the polyisocyanates used to prepare the isocyanate prepolymer component B of the present invention have an average of 2 to 4 NCO groups. Preferably, diisocyanates are used, i.e., esters of isocyanic acid of the general structure O=C=N-R'-N=C=O, wherein R' is an aliphatic or alicyclic group.

[0061] As examples of non-aromatic polyisocyanates suitable for preparing the isocyanate prepolymer component B of the present invention, there can be mentioned ethylene diisocyanate, tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane, HDI), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, 4-isocyanatomethyl-1,6-diisocyanatohexane, HDI, ... 8-octamethylene diisocyanate, 1,6-diisocyanato-2,2,4-trimethylhexane, 1,6-diisocyanato-2,4,4-trimethylhexane, 2,3,3-trimethylhexamethylene diisocyanate, tetramethylhexane diisocyanate, lysine diisocyanate, isophorone diisocyanate (=3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5 -trimethylcyclohexane, IPDI), 1,4-cyclohexylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,2-cyclohexylene diisocyanate, 4,4'-bis(isocyanatocyclohexyl)methane, 2,4'-bis(isocyanatocyclohexyl)methane, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, 1-methyl-2,4-diisocyanatocyclohexane, 1-methyl-2,6- Diisocyanatocyclohexane, dicyclohexylmethane diisocyanate (HMDI), di(isocyanatomethylene)cyclohexane, tetramethoxybutane-1,4-diisocyanate, phosphorus-containing diisocyanates, sulfur-containing diisocyanates, anion-modified polyisocyanates, polyethylene oxide-containing isocyanates, oligomers of the aforementioned polyisocyanates containing urethane, allophanate, isocyanurate, uretdione, carbodiimide or biuret groups, and mixtures thereof.

[0062] Preferably, the non-aromatic polyisocyanate suitable for preparing the isocyanate prepolymer component B of the present invention is selected from C 4 -C 12 Aliphatic or C 6 -C 15 Alicyclic polyisocyanate, preferably the non-aromatic polyisocyanate is selected from dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, di(isocyanatomethylene)cyclohexane. More preferably, the non-aromatic polyisocyanate suitable for preparing the isocyanate prepolymer component B of the present invention is dicyclohexylmethane diisocyanate.

[0063] The compound containing two or more hydroxyl groups for preparing the isocyanate prepolymer component B of the present invention can be the polyol introduced above, which includes difunctional polyols and multifunctional polyols. Polyols are in principle those with two or more OH groups in the molecule. These polyol components suitable for the present invention preferably include or are selected from polyether polyols and / or polyester polyols. These are generally known and described in, for example, "KunststoffhandbuchPolyurethane", Günter Oertel, Carl-Hanser-Verlag, 2nd edition, 1983, chapter 3.1.1.

[0064] Polyester polyols can be obtained by condensing polyfunctional alcohols having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, with polyfunctional carboxylic acids having 2 to 12 carbon atoms. Examples of polyfunctional alcohols include ethylene glycol, neopentyl glycol, 1,2-propylene glycol, 2,2-dimethyl-1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol and 1,2-cyclohexanedimethanol, and polyols such as trimethylolethane, trimethylolpropane, trimethylolhexane, 1,2,4-butanetriol, pentaerythritol and dipentaerythritol. Examples of the polyfunctional carboxylic acids include succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and maleic acid. It is also possible to use polyester polyols derived from lactones (eg, ε-caprolactone) or hydroxycarboxylic acids (eg, ω-hydroxycaproic acid).

[0065] The polyether polyols generally comprise repeating units derived from alkylene oxides selected from ethylene oxide (EO) and ethylene oxide (PO), butylene oxide and tetrahydrofuran.

[0066] Polyether polyols are generally obtainable by anionic polymerization of one or more alkylene oxides selected from ethylene oxide (EO) and propylene oxide (PO), butylene oxide and tetrahydrofuran, for example using alkali metal hydroxides as catalysts and concomitantly adding starter molecules containing multiple active hydrogen atoms.

[0067] The alkylene oxides can be used individually, in succession or in a mixture. The use of EO-PO mixtures will give polyether polyols with randomly distributed PO / EO units. It is possible to start with a PO-EO mixture and then continue to use either PO or EO alone before the polymerization is terminated, and the product is a polyether polyol with PO end-capping or EO end-capping, respectively.

[0068] The starter molecules used are generally NH- or OH-functional compounds, such as water, amines or alcohols. Preference is given to using dihydric to hexahydric alcohols, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerol, trimethylolpropane, pentaerythritol and / or sorbitol.

[0069] It is also preferred to use polyether polyols obtained by ring-opening polymerization of tetrahydrofuran. In the related art, polytetrahydrofuran (=PTHF) is known by the following names: tetramethylene glycol (=PTMG), polytetramethylene glycol ether (=PTMEG) or polytetramethylene oxide (=PTMO).

[0070] Preferably, the compound containing two or more hydroxyl groups suitable for preparing the isocyanate prepolymer component B of the present invention is one or more polyether polyols or polyester polyols, such as polyether diols, polyether polyols with a functionality greater than 2, such as in the range of 2.3 to 5, or any combination thereof.

[0071] In some embodiments, the isocyanate prepolymer component B of the present invention prepared from at least one non-aromatic polyisocyanate and at least one compound containing two or more hydroxyl groups may have an isocyanate group content (NCO content) in the range of 3 to 25 wt%. For example, the isocyanate prepolymer component B of the present invention may have an NCO content in the range of 3 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, or 25 wt%, or any NCO content between these values. Preferably, the isocyanate prepolymer component B of the present invention may have an NCO content in the range of 5 to 15 wt%.

[0072] The isocyanate index of the composition of the present invention may be in the range of 90 to 120, for example in the range of 100 to 120, preferably in the range of 101 to 110. Herein, the isocyanate index of the composition is obtained by the following formula:

[0073] Isocyanate index of the composition = (number of moles of isocyanate groups in the composition / number of moles of isocyanate-reactive groups in the composition) × 100.

[0074] Catalyst component C

[0075] Component C in the composition of the present invention is a catalyst. These include catalysts based on amines and catalysts based on organometallic compounds.

[0076] The amine-based catalyst is preferably a tertiary amine catalyst. Some of the most commonly used tertiary amine catalysts are bis(2-dimethylaminoethyl)ether, N,N,N,N-pentamethyldiethylenetriamine, N,N,N-triethylaminoethoxyethanol, dimethylcyclohexylamine, dimethylbenzylamine, triethylamine, triethylenediamine, pentamethyldipropylenetriamine, dimethylethanolamine, N-methylimidazole, N-ethylimidazole, tetramethylhexamethylenediamine, tris(dimethylaminopropyl)hexahydrotriazine, dimethylaminopropylamine, N-ethylmorpholine, diazabicycloundecene and diazabicyclononene. Available tertiary amine catalysts may also include ECOADD® SA-1 and ECOADD® SA-8 purchased from Ye Innovation Materials (Shanghai) Co., Ltd., and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) with the brand name DY-DBU purchased from Shanghai Deyin Chemical Co., Ltd.

[0077] The catalyst based on organometallic compound is preferably a tin-based organometallic catalyst, a zinc or bismuth-based catalyst. Examples of tin-based organometallic catalysts may include, for example, tin (II) salts of organic carboxylic acids such as tin acetate (II), tin octoate (II), tin ethylhexanoate (II) and tin laurate (II), and dialkyltin (IV) salts of organic carboxylic acids such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, dioctyltin diacetate, di-n-octyl-bis-(2-ethylhexyl thioacetate) tin, such as Formaz UL-32 purchased from Galata Chemicals, Germany.

[0078] Examples of zinc or bismuth-based catalysts can be bismuth salts, preferably in the 2- or 3-valent oxidation state, especially in the 3-valent oxidation state. Zinc and / or bismuth salts of carboxylic acids are preferred. The carboxylic acids used are preferably carboxylic acids having 6 to 14 carbon atoms, more preferably carboxylic acids having 8 to 12 carbon atoms. Examples of suitable zinc and / or bismuth salts are bismuth (III) neodecanoate, bismuth 2-ethylhexanoate and bismuth octoate, zinc 2-ethylhexanoate, zinc neodecanoate.

[0079] The catalyst suitable for use as component C of the present invention is a combination of a tertiary amine catalyst and a metal catalyst, or the catalyst is a tin catalyst.

[0080] In some preferred embodiments, the zinc or bismuth based catalyst used in the composition of the present invention may be BiCAT® 8118, BiCAT® 8, or a combination of both available from Leading Chemical Company of America.

[0081] Preferably, the catalyst applicable to the present invention is a combination of a tertiary amine catalyst and an organic metal catalyst, and more preferably, the catalyst applicable to the present invention is a combination of a tertiary amine catalyst and a zinc or bismuth-based catalyst.

[0082] In some preferred embodiments, the catalyst in the composition of the present invention is a combination of a tertiary amine catalyst and a zinc or bismuth-based catalyst, wherein the zinc or bismuth-based catalyst is selected from BiCAT® 8118 and BiCAT® 8, and the tertiary amine catalyst is diazabicycloundecene.

[0083] Preferably, when the combination of a tertiary amine catalyst and an organometallic catalyst or preferably a combination of a tertiary amine catalyst and a zinc or bismuth-based catalyst is used as the catalyst component in the composition of the present invention, the combined weight ratio of the tertiary amine catalyst and the organometallic catalyst or preferably the tertiary amine catalyst and the zinc or bismuth-based catalyst is preferably in the range of 2:1 to 1:2, for example, the combined weight ratio may be 2:1, 1.5:1, 1:1, 1:1.5, 1:2, or any value between these values. Preferably, the combined weight ratio of the tertiary amine catalyst and the organometallic catalyst or preferably the tertiary amine catalyst and the zinc or bismuth-based catalyst is in the range of 1.5:1 to 1:1.5, more preferably in the range of 1.2:1 to 1:1.2.

[0084] Based on the total weight of component A and component C in the present composition, the amount of component C of the present invention is in the range of 0.02 % by weight to 1 % by weight. For example, based on the total weight of component A and component C in the present composition, the amount of component C of the present invention can be 0.02 % by weight, 0.03 % by weight, 0.04 % by weight, 0.05 % by weight, 0.10 % by weight, 0.15 % by weight, 0.20 % by weight, 0.25 % by weight, 0.30 % by weight, 0.35 % by weight, 0.40 % by weight, 0.45 % by weight, 0.50 % by weight, 0.55 % by weight, 0.60 % by weight, 0.65 % by weight, 0.70 % by weight, 0.75 % by weight, 0.80 % by weight, 0.85 % by weight, 0.90 % by weight, 0.95 % by weight, 1 % by weight, or the amount between any of these values. Preferably, based on the total weight of component A and component C in the present composition, the amount of component C of the present invention can be in the range of 0.02 to 0.2 % by weight, more preferably in the range of 0.03 to 0.1 % by weight.

[0085] Other components D

[0086] The composition of the present invention may further comprise other components as component D. Preferably, the other component may be an antioxidant.

[0087] Preferably, the antioxidant is selected from hindered phenols and mixtures of hindered phenols and phosphites. Suitable hindered phenol antioxidants can be selected, for example, from alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, side chain Linear or branched nonylphenols such as 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1-methylundecane-1-yl)phenol, 2,4-dimethyl-6-(1-methylheptadecan-1-yl)phenol, 2,4-dimethyl-6-(1-methyltridecane-1-yl)phenol and mixtures thereof; alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.

[0088] Suitable phosphites may be, for example, triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, tri(octadecyl) phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, di(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, di(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxy pentaerythritol diphosphite, di(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, di(2,4,6-tri(tert-butylphenyl) pentaerythritol diphosphite), tristearyl sorbitan triphosphite, and the like.

[0089] When used, the other component D can be used by those skilled in the art in an amount conventionally used in the art according to specific application scenarios.

[0090] Compositions of the present invention

[0091] From the composition of the present invention, for example, solvent-free polyurethane can be obtained.

[0092] In some embodiments, the present invention relates to a composition comprising or consisting of:

[0093] A. an isocyanate-reactive component comprising,

[0094] a) a difunctional polyol having a weight average molecular weight of 800 to 4000 g / mol;

[0095] b) a polyfunctional polyol having a weight average molecular weight of 2000 to 6000 g / mol, the functionality of the polyfunctional polyol being greater than or equal to 2.4, preferably in the range of 2.4 to 5, preferably in the range of 2.5 to 3.2, more preferably in the range of 2.5 to 3; and

[0096] c) a crosslinker having a weight average molecular weight of 90 to 1000 g / mol, the functionality of the crosslinker being greater than or equal to 2.5, preferably greater than or equal to 3, for example in the range of 2.5 to 3.5 or 2.8 to 5, wherein the content of the crosslinker is 2.2% to 9% by weight, preferably 2.5% to 8% by weight, based on the total weight of component A and component C, and

[0097] B. an isocyanate prepolymer component prepared from at least one non-aromatic polyisocyanate and at least one compound containing two or more hydroxyl groups, and

[0098] C. Catalyst.

[0099] In some embodiments, the present invention relates to a composition comprising or consisting of:

[0100] A. an isocyanate-reactive component comprising,

[0101] a) a difunctional polyol having a weight average molecular weight of 800 to 1200 g / mol;

[0102] b) a polyfunctional polyol having a weight average molecular weight of 3500 to 4500 g / mol, the functionality of the polyfunctional polyol being greater than or equal to 2.4, preferably in the range of 2.4 to 5, preferably in the range of 2.5 to 3.2, more preferably in the range of 2.5 to 3; and

[0103] c) a crosslinker having a weight average molecular weight of 150 g / mol to 500 g / mol, the functionality of the crosslinker being greater than or equal to 2.5, preferably greater than or equal to 3, for example in the range of 2.5 to 3.5 or 2.8 to 5, wherein the content of the crosslinker is 2.2% to 9% by weight, preferably 2.5% to 8% by weight, based on the total weight of component A and component C, and

[0104] B. an isocyanate prepolymer component prepared from at least one non-aromatic polyisocyanate and at least one compound containing two or more hydroxyl groups, and

[0105] C. Catalyst.

[0106] In some embodiments, the present invention relates to a composition comprising or consisting of:

[0107] A. an isocyanate-reactive component comprising,

[0108] a) a difunctional polyol having a weight average molecular weight of 800 to 1200 g / mol;

[0109] b) a polyfunctional polyol having a weight average molecular weight of 3500 to 4500 g / mol, the functionality of the polyfunctional polyol being greater than or equal to 2.4, preferably in the range of 2.4 to 5, preferably in the range of 2.5 to 3.2, more preferably in the range of 2.5 to 3; and

[0110] c) a crosslinker having a weight average molecular weight of 150 g / mol to 500 g / mol, the functionality of the crosslinker being greater than or equal to 2.5, preferably greater than or equal to 3, for example in the range of 2.5 to 3.5 or 2.8 to 5, the crosslinker being a polyether polyol starting from ethoxylated and / or propoxylated trimethylolpropane, preferably trimethylolpropane, wherein the content of the crosslinker is 2.2% to 9% by weight, preferably 2.5% to 8% by weight, based on the total weight of component A and component C, and

[0111] B. an isocyanate prepolymer component prepared from at least one non-aromatic polyisocyanate and at least one compound containing two or more hydroxyl groups, and

[0112] C. Catalyst.

[0113] In some embodiments, the present invention relates to a composition comprising or consisting of:

[0114] A. an isocyanate-reactive component comprising,

[0115] a) a difunctional polyol having a weight average molecular weight of 800 to 1200 g / mol;

[0116] b) a polyfunctional polyol having a weight average molecular weight of 3500 to 4500 g / mol, the functionality of the polyfunctional polyol being greater than or equal to 2.4, preferably in the range of 2.4 to 5, preferably in the range of 2.5 to 3.2, more preferably in the range of 2.5 to 3; and

[0117] c) a crosslinker having a weight average molecular weight of 150 g / mol to 500 g / mol, the functionality of the crosslinker being greater than or equal to 2.5, preferably greater than or equal to 3, for example in the range of 2.5 to 3.5 or 2.8 to 5, the crosslinker being a polyether polyol starting from ethoxylated and / or propoxylated trimethylolpropane, preferably trimethylolpropane, wherein the content of the crosslinker is 2.2% to 9% by weight, preferably 2.5% to 8% by weight, based on the total weight of component A and component C, and

[0118] B. an isocyanate prepolymer component prepared from at least one non-aromatic polyisocyanate and at least one compound containing two or more hydroxyl groups, and

[0119] C. A catalyst, wherein the catalyst is a combination of an organic metal catalyst and a tertiary amine catalyst, and more preferably the catalyst is a combination of a zinc or bismuth-based catalyst and a tertiary amine catalyst.

[0120] In the composition of the present invention, the ratio of (weight of component A+weight of component C): (weight of component B) is defined as the feed ratio. In a preferred embodiment, the feed ratio of the composition of the present invention is in the range of 50:100 to 100:50, preferably in the range of 70:100 to 100:70, more preferably in the range of 80:100 to 100:80. More preferably, the feed ratio of the composition of the present invention is in the range of 100:75 to 100:90, for example, in the range of 100:80 to 100:88, for example, in the range of 100:83 to 100:85.

[0121] Preparation and use of the composition of the present invention

[0122] The composition of the present invention is, for example, a two-component composition in which the isocyanate-reactive component A and the isocyanate prepolymer component B are stored separately from each other and are mixed with each other only shortly before use. The catalyst component C of the present invention can be stored separately from the isocyanate-reactive component A and the isocyanate prepolymer component B and mixed with them only shortly before use, or the catalyst component C of the present invention can also be directly incorporated into the isocyanate-reactive component A for storage and mixed with the isocyanate prepolymer component B only shortly before use.

[0123] Considering the storage, transportation and use of the composition of the present invention, the form of the composition of the present invention covers the cases where components A, B and C are present in separate or mixed forms, or components A and B are present in separate forms and component C is present in component A.

[0124] The composition of the present invention can be used to prepare various polyurethane materials and products. The composition of the present invention can be particularly used to manufacture synthetic leather, which can be widely used in a variety of industries such as furniture, clothing, car seat covers and footwear. The products obtained from the composition of the present invention, especially synthetic leather products, not only have good mechanical properties and processing capabilities, but also have good weather resistance and meet strict yellowing resistance requirements.

[0125] The composition of the present invention belongs to a solvent-free system, thus avoiding the environmental problems caused by the use of solvents.

[0126] Compared with the polyurethane products obtained from the two-component system based on aromatic isocyanate, the polyurethane products of the present invention not only achieve comparable or even improved mechanical properties and processing characteristics, but also improve the yellowing resistance.

[0127] The synthetic leather obtained from the composition of the present invention can have a strength of 40-120 N / cm 3 For example, the synthetic leather obtained from the composition of the present invention can have a peel strength of 40N / cm 3 , 50N / cm 3 , 60N / cm 3 , 70N / cm 3 , 80N / cm 3 , 90N / cm 3 , 100N / cm 3 , 110N / cm 3 , 120N / cm 3 Preferably, the synthetic leather obtained from the composition of the present invention may have a peel strength of 80 N / cm 3 or higher peel strength, more preferably 90 N / cm 3 Or higher peel strength, even 100 N / cm 3 or higher, e.g. 110N / cm 3 or higher peel strength.

[0128] According to ISO 5402, the synthetic leather obtained from the composition of the present invention can pass a flexural performance test of >200,000 times at room temperature, and can pass a flexural performance test of >30,000 times at -30°C.

[0129] The product obtained from the composition of the present invention has excellent yellowing resistance, and can achieve yellowing resistance of level 4 to 5 after 500 hours at 90-110° C. or after 72 hours of UV aging.

[0130] The synthetic leather obtained from the composition of the present invention can achieve heat aging yellowing resistance of grade 4 to 5 at 90 to 120° C. and 400 to 500 hours as measured according to ISO 105-A02.

[0131] According to HG / T 3689-2014, the synthetic leather obtained from the composition of the present invention can achieve a heat aging yellowing resistance performance of level 4 to 5 under 30W UVB 313nm for 72 hours.

[0132] The composition of the present invention also meets the dry process requirements for preparing artificial leather using a solvent-free two-component polyurethane system (i.e., the "dry processability" described in the embodiment), and thus has excellent processing characteristics. The dry process preparation generally includes the following steps:

[0133] - Apply a top coat over the release layer; then

[0134] - applying the composition to the top coating to form a PU layer; then

[0135] - Pre-curing; then

[0136] - Apply the substrate layer to the PU layer; then

[0137] - Place in oven to cure; then

[0138] - Separate the release layer from the top coating to obtain the final product.

[0139] Embodiments of the present invention

[0140] In general, the present invention may relate to the following embodiments.

[0141] 1. A composition comprising:

[0142] A. an isocyanate-reactive component comprising,

[0143] a) a difunctional polyol having a weight average molecular weight of 800 to 4000 g / mol, preferably 800 to 3000 g / mol;

[0144] b) a polyfunctional polyol having a weight average molecular weight of 2000 to 6000 g / mol, preferably 2500 to 5000 g / mol, the functionality of the polyfunctional polyol being greater than or equal to 2.4, preferably in the range of greater than 2.4 and less than or equal to 5, preferably in the range of 2.5 to 3.2, more preferably in the range of 2.5 to 3; and

[0145] c) a crosslinker having a weight average molecular weight of 90 to 1000 g / mol, preferably 100 to 800 g / mol, the functionality of the crosslinker being greater than or equal to 2.5, preferably greater than or equal to 3, for example in the range of 2.5 to 3.5 or 2.8 to 5, wherein the content of the crosslinker is 2.2 to 9% by weight, preferably 2.5 to 8% by weight, based on the total weight of component A and component C, and

[0146] B. an isocyanate prepolymer component prepared from at least one non-aromatic polyisocyanate and at least one compound containing two or more hydroxyl groups, and

[0147] C. A catalyst, wherein the catalyst is a combination of a tertiary amine catalyst and a metal catalyst, or the catalyst is a tin catalyst.

[0148] 2. A composition as described in embodiment 1, wherein the difunctional polyol component a) is a polyether diol or a polyester diol or any combination thereof, preferably the difunctional polyol component a) is selected from polyethylene oxide diol, polypropylene oxide diol, poly(ethylene oxide-propylene oxide) diol, polytetrahydrofuran diol and polycaprolactone diol, in particular polytetrahydrofuran diol.

[0149] 3. A composition as described in embodiment 1 or 2, wherein the multifunctional polyol component b) is a polyether polyol, a polyester polyol or any combination thereof, and preferably the multifunctional polyol component b) is selected from polyethylene oxide polyol, polypropylene oxide polyol, poly(ethylene oxide-propylene oxide) polyol, polytetramethylene oxide polyol and polycaprolactone polyol.

[0150] 4. A composition according to any one of embodiments 1 to 3, wherein the total amount of component a) and component b) is in the range of 80 to 99 wt %, preferably in the range of 85 to 99 wt %, more preferably in the range of 90 to 99 wt %, based on the weight of component A, for example, the weight ratio of component a) to component b) is in the range of 3:1 to 1:3, preferably in the range of 2:1 to 1:2, more preferably in the range of 1.2:1 to 1:1.2.

[0151] 5. A composition as described in any one of embodiments 1 to 4, wherein the crosslinking agent is selected from compounds having 3 to 10 carbon atoms and at least 3 hydroxyl groups and alkoxylation products thereof, preferably selected from glycerol, trimethylolpropane, butanetriol, pentaerythritol, and alkoxylation products thereof.

[0152] 6. A composition as described in any one of embodiments 1 to 5, wherein the cross-linking agent is selected from: glycerol, ethoxylated and / or propoxylated glycerol, trimethylolpropane, ethoxylated and / or propoxylated trimethylolpropane, butanetriol, ethoxylated and / or propoxylated butanetriol, pentaerythritol, ethoxylated and / or propoxylated pentaerythritol or any combination thereof; the cross-linking agent is preferably ethoxylated and / or propoxylated glycerol, ethoxylated and / or propoxylated trimethylolpropane, ethoxylated and / or propoxylated butanetriol or any combination thereof.

[0153] 7. The composition of any one of embodiments 1 to 6, wherein the isocyanate prepolymer component has an isocyanate content of 3 to 25 wt %, preferably 5 to 15 wt %.

[0154] 8. A composition as described in any one of embodiments 1 to 7, wherein the non-aromatic polyisocyanate is selected from C 4 -C 12 Aliphatic and C 6 -C 15 The alicyclic polyisocyanate, preferably the non-aromatic polyisocyanate is selected from dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, di(isocyanatomethylene)cyclohexane.

[0155] 9. A composition as described in any one of embodiments 1 to 8, wherein the compound containing two or more hydroxyl groups mentioned for the isocyanate prepolymer component B is one or more polyether polyols or polyester polyols, preferably polyether polyols, such as polyether diols, polyether polyols with a functionality greater than 2, such as in the range of 2.3 to 5, or any combination thereof.

[0156] 10. A composition as described in any one of embodiments 1 to 9, wherein the catalyst is a combination of a tertiary amine catalyst and an organometallic catalyst, more preferably the catalyst is a combination of a tertiary amine catalyst and a zinc or bismuth-based catalyst, preferably the weight ratio of the combination is in the range of 2:1 to 1:2, preferably in the range of 1.5:1 to 1:1.5, more preferably in the range of 1.2:1 to 1:1.2.

[0157] 11. The composition according to any one of embodiments 1 to 10, wherein the content of the catalyst component C is in the range of 0.02 wt % to 1 wt %, preferably in the range of 0.03 wt % to 0.1 wt %, based on the total weight of component A and component C.

[0158] 12. A composition as described in any one of embodiments 1 to 11, wherein the isocyanate-reactive component A further comprises,

[0159] d) chain extenders having difunctionality and a weight average molecular weight of less than or equal to 500 g / mol, preferably a weight average molecular weight of 60 to 400 g / mol, or 60 to 300 g / mol, such as straight and branched chain aliphatic and alicyclic diols having 2 to 14, preferably 2 to 10, more preferably 2 to 6 carbon atoms,

[0160] Preferably, the amount of the chain extender is 1 wt % to 8 wt %, more preferably 2 wt % to 6 wt %, based on the total weight of component A and component C.

[0161] 13. A composition according to any one of embodiments 1 to 12, wherein components A, B and C are present in separate forms or in a mixture, or components A and B are present in separate forms and component C is present in component A.

[0162] 14. A composition according to any one of embodiments 1 to 13, wherein the composition consists of components A, B and C.

[0163] 15. The composition of any one of embodiments 1 to 13, further comprising an antioxidant component D selected from hindered phenols and mixtures of hindered phenols and phosphites.

[0164] 16. The composition according to any one of embodiments 1 to 15, which has an isocyanate index in the range of 90 to 120, such as in the range of 100 to 120, preferably in the range of 101 to 110.

[0165] 17. A polyurethane article obtainable from the composition according to any one of embodiments 1 to 16, such as polyurethane synthetic leather.

[0166] 18. Use of the composition according to any one of embodiments 1 to 16 for producing synthetic leather.

[0167] More preferably, the present invention may relate to the following technical solutions.

[0168] 1. A composition consisting of:

[0169] A. an isocyanate-reactive component comprising,

[0170] a) a difunctional polyol having a weight average molecular weight of 800 to 4000 g / mol;

[0171] b) a multifunctional polyol having a weight average molecular weight of 2000 to 6000 g / mol, wherein the functionality of the multifunctional polyol is greater than or equal to 2.4; and

[0172] c) a crosslinker having a weight average molecular weight of 90 g / mol to 1000 g / mol, wherein the functionality of the crosslinker is greater than or equal to 2.5, wherein the crosslinker is ethoxylated and / or propoxylated glycerol, ethoxylated and / or propoxylated trimethylolpropane, ethoxylated and / or propoxylated butanetriol or any combination thereof, wherein the content of the crosslinker is 2.2 wt % to 9 wt %, based on the total weight of component A and component C, and

[0173] B. an isocyanate prepolymer component prepared from at least one non-aromatic polyisocyanate and at least one compound containing two or more hydroxyl groups, and

[0174] C. A catalyst, wherein the catalyst is a combination of a tertiary amine catalyst and a metal catalyst, or the catalyst is a tin catalyst.

[0175] 2. The composition according to claim 1, which is composed of the following:

[0176] A. an isocyanate-reactive component comprising,

[0177] a) a difunctional polyol having a weight average molecular weight of 800 to 3000 g / mol;

[0178] b) a multifunctional polyol having a weight average molecular weight of 2500 to 5000 g / mol, wherein the functionality of the multifunctional polyol is in the range of 2.5 to 3.2; and

[0179] c) a crosslinker having a weight average molecular weight of 100 to 800 g / mol, wherein the functionality of the crosslinker is in the range of 2.8 to 5, wherein the crosslinker is ethoxylated and / or propoxylated glycerol, ethoxylated and / or propoxylated trimethylolpropane, ethoxylated and / or propoxylated butanetriol or any combination thereof, wherein the content of the crosslinker is 2.5% to 8% by weight, based on the total weight of component A and component C, and

[0180] B. an isocyanate prepolymer component prepared from at least one non-aromatic polyisocyanate and at least one compound containing two or more hydroxyl groups, and

[0181] C. A catalyst, wherein the catalyst is a combination of a tertiary amine catalyst and a metal catalyst, or the catalyst is a tin catalyst.

[0182] 3. The composition according to claim 1 or 2, wherein the functionality of the crosslinking agent is in the range of 2.5 to 3.5.

[0183] 4. A composition as described in any one of technical solutions 1 to 3, wherein the difunctional polyol component a) is selected from polyethylene oxide glycol, polypropylene oxide glycol, poly(ethylene oxide-propylene oxide) glycol, polytetrahydrofuran diol and polycaprolactone diol.

[0184] 5. A composition as described in any one of technical solutions 1 to 4, wherein the difunctional polyol component a) is polytetrahydrofuran diol.

[0185] 6. The composition according to any one of technical solutions 1 to 5, wherein the multifunctional polyol component b) is selected from polyethylene oxide polyol, polypropylene oxide polyol, poly(ethylene oxide-propylene oxide) polyol, polytetramethylene oxide polyol and polycaprolactone polyol.

[0186] 7. A composition as described in any one of technical solutions 1 to 6, wherein based on the weight of component A, the total amount of component a) and component b) is in the range of 80 to 99% by weight, and / or the weight ratio of component a) to component b) is in the range of 3:1 to 1:3.

[0187] 8. A composition according to any one of technical solutions 1 to 7, wherein the total amount of component a) and component b) is in the range of 90 to 99 wt % based on the weight of component A, and / or the weight ratio of component a) to component b) is in the range of 1.2:1 to 1:1.2.

[0188] 9. A composition as described in any one of Technical Solutions 1 to 8, wherein the isocyanate prepolymer component has an isocyanate content of 3 wt % to 25 wt %.

[0189] 10. A composition as described in any one of technical solutions 1 to 9, wherein the isocyanate prepolymer component has an isocyanate content of 5 wt % to 15 wt %.

[0190] 11. A composition as described in any one of technical solutions 1 to 10, wherein the non-aromatic polyisocyanate is selected from C 4 -C 12 Aliphatic and C 6 -C 15 Cycloaliphatic polyisocyanates.

[0191] 12. A composition as described in any one of technical solutions 1 to 11, wherein the non-aromatic polyisocyanate is selected from dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and di(isocyanate methylene) cyclohexane.

[0192] 13. A composition as described in any one of technical solutions 1 to 12, wherein the compound containing two or more hydroxyl groups mentioned in the isocyanate prepolymer component B is one or more polyether polyols or polyester polyols, or any combination thereof.

[0193] 14. A composition as described in any one of technical solutions 1 to 13, wherein the compound containing two or more hydroxyl groups mentioned in the isocyanate prepolymer component B is a polyether diol, a polyether polyol having a functionality ranging from 2.3 to 5, or any combination thereof.

[0194] 15. A composition as described in any one of technical solutions 1 to 14, wherein the catalyst is a combination of a tertiary amine catalyst and a zinc or bismuth-based catalyst.

[0195] 16. A composition as described in any one of technical solutions 1 to 15, wherein the catalyst is a combination of a tertiary amine catalyst and a zinc or bismuth-based catalyst, and the weight ratio of the combination is in the range of 2:1 to 1:2.

[0196] 17. The composition according to any one of technical solutions 1 to 16, wherein the catalyst is a combination of a tertiary amine catalyst and a zinc or bismuth-based catalyst, and the weight ratio of the combination is in the range of 1.2:1 to 1:1.2.

[0197] 18. The composition according to any one of technical solutions 1 to 17, wherein the content of catalyst component C is in the range of 0.02 wt% to 1 wt% based on the total weight of component A and component C.

[0198] 19. A composition as described in any one of technical solutions 1 to 18, wherein the content of catalyst component C is in the range of 0.03% to 0.1% by weight based on the total weight of component A and component C.

[0199] 20. A composition as described in any one of technical solutions 1 to 19, wherein the isocyanate reactive component A further comprises:

[0200] d) a difunctional chain extender having a weight average molecular weight less than or equal to 500 g / mol,

[0201] The amount of the chain extender is 1 wt % to 8 wt %, based on the total weight of component A and component C.

[0202] 21. A composition as described in any one of technical solutions 1 to 20, wherein the isocyanate reactive component A further comprises:

[0203] d) a difunctional chain extender having a weight average molecular weight of 60 to 300 g / mol,

[0204] The amount of the chain extender is 1 wt % to 8 wt %, based on the total weight of component A and component C.

[0205] 22. A composition as described in any one of technical solutions 1 to 21, wherein the isocyanate reactive component A further comprises:

[0206] d) chain extenders, which are straight-chain and branched aliphatic and cycloaliphatic diols having 2 to 14 carbon atoms,

[0207] The amount of the chain extender is 2 wt % to 6 wt %, based on the total weight of component A and component C.

[0208] 23. A composition as described in any one of technical solutions 1 to 22, wherein the isocyanate-reactive component A further comprises:

[0209] d) chain extenders, which are straight-chain and branched aliphatic and cycloaliphatic diols having 2 to 6 carbon atoms,

[0210] The amount of the chain extender is 2 wt % to 6 wt %, based on the total weight of component A and component C.

[0211] 24. A composition as described in any one of technical solutions 1 to 23, wherein components A, B and C exist in separate forms or in a mixture, or components A and B exist in separate forms and component C exists in component A.

[0212] 25. The composition according to any one of claims 1 to 24, wherein the isocyanate index is in the range of 90 to 120.

[0213] 26. The composition according to any one of claims 1 to 25, wherein the isocyanate index is in the range of 101 to 110.

[0214] 27. A polyurethane product obtainable from the composition according to any one of technical solutions 1 to 26.

[0215] 28. Use of the composition described in any one of technical solutions 1 to 26 for manufacturing synthetic leather. Example

[0216] The present invention and its effects are further described by the following examples. These examples are for illustrative purposes and should not be construed as limiting the present invention. The ratios or percentages given in the examples are by weight unless otherwise specified.

[0217] Test Method

[0218] In this specification and examples, the characterization and testing methods of the performance parameters involved are described as follows.

[0219] The weight average molecular weight was determined by size exclusion chromatography (SEC) using commercially available polymethyl methacrylate (PMMA) standards. The determination was performed by gel permeation chromatography using THF as eluent (flow rate: 1 mL / min; injection volume: 100 μl).

[0220] The hydroxyl value is measured according to DIN 53240-1:2012-07.

[0221] The NCO content is determined according to the di-n-butylamine method of national standard GB / T 18446-2009.

[0222] The peel strength is measured according to ISO-11339.

[0223] UV aging performance is measured according to HG / T 3689-2014.

[0224] Flexural properties were measured according to ISO 5402.

[0225] Heat aging properties were measured according to ISO 105-A02.

[0226] The yellowing resistance is measured according to GB-T 250-2008, and the results are given in five grades from 1 to 5.

[0227] Table 1 Materials used

[0228] Materials / Components describe Polyol 1 Primary hydroxyl terminated polyether polyol (tetramethylene oxide as repeating unit) with a weight average molecular weight of ~1000 g / mol and a functionality of 2 Polyol 2 Primary hydroxyl terminated polyether polyol (ethylene oxide as repeating unit) with a weight average molecular weight of ~4000 g / mol and a functionality of 2.72 Polyol 3 A 50:50 weight ratio mixture of Polyol 1 and Polyol 2 Crosslinker 1 The polyether polyol using trimethylolpropane as the starting material has a repeating unit of propylene oxide PO, a weight average molecular weight of 280~340 g / mol, and a functionality of 3 MDI Methylene diphenyl diisocyanate HMDI 4,4-Dicyclohexylmethane diisocyanate BDO Butanediol, as a chain extender TMP Trimethylolpropane, as a crosslinking agent DBU 1,8-Diazabicyclo[5.4.0]undec-7-ene, as a catalyst

[0229] Composition

[0230] The materials used as component A, component B and component C are given in Table 2 below.

[0231] For each example, the corresponding component A (100 parts by weight), component B and component C (catalyst, 0.5 parts by weight) are given in Table 3 below to obtain a corresponding composition.

[0232] Table 2

[0233] Component A A1 97 wt% Polyol 3 + 3 wt% BDO Component A A2 97 wt% Polyol 3 + 3 wt% TMP Component A A3 97 wt% Polyol 3 + 3 wt% Crosslinker 1 Component A A4 94 wt% Polyol 3 + 3 wt% BDO + 3 wt% Crosslinker 1 Component A A5 93 wt% Polyol 3 + 7 wt% Crosslinker 1 Component B B1 50 wt% MDI + 50 wt% Polyol 3, NCO content: 13 wt% Component B B2 50 wt% HMDI + 50 wt% Polyol 3, NCO content: 13 wt% Component C C1 Metal catalyst: Bicat 8 (Zn-Bi) Component C C2 Amine catalyst: DBU Component C C3 Tin catalyst: Formaz UL-32 (di-n-octyl-bis-(2-ethylhexyl thioacetate)tin) from Galata Chemicals

[0234] Note: Component B1 is a prepolymer obtained by the reaction of MDI and polyol 3;

[0235] Component B2 is a prepolymer obtained by reacting HMDI with polyol 3.

[0236] Synthetic leather preparation scheme

[0237] For each example, the corresponding component A and component C (catalyst) were fully mixed to form a mixture of component A and component C. The mixture was then mixed with the given component B to obtain a composition as a polyurethane forming system. For each example, the isocyanate index of the obtained composition was 103, and the feed ratio (weight of component A + weight of component C): weight of component B was about 100:84.

[0238] In the process of preparing synthetic leather described below, the polyurethane forming system is stirred and coated on a release paper.

[0239] Commercial release paper (Fanvini release paper BNS B377, purchased from Fanvini Co., Ltd., Italy) with a polyurethane top coating (aqueous polyurethane dispersion white slurry) moves at a speed of 1 m / min on a continuous device for preparing synthetic leather. The top coating thickness is about 50 microns. Then, a layer of a solvent-free polyurethane forming system (i.e., a composition prepared in an embodiment of the present application or a comparative example) of about 400 microns is applied with a stirrer. Subsequently, the resulting material is introduced into an oven controlled at 140°C for precuring. After about 90 seconds, the material is taken out of the oven. Afterwards, under slight pressure (manual pressing with a pressure roller in the laboratory), a textile substrate (0.65 mercerized velvet (Adi cloth) white, Haining Anyu Textile Co., Ltd.) made mainly of polyethylene terephthalate is applied to the solvent-free polyurethane forming system layer that is still not fully cured. Thus a laminated preform is obtained. Subsequently, the obtained laminated preform is cured in an oven at 140°C. After 10 minutes, the laminate preform was taken out of the oven, and then the release paper was peeled off from the laminate preform to obtain the final synthetic leather.

[0240] The obtained synthetic leather was subjected to performance tests, and the results are provided in Table 3. Hereinafter, the "dry processability" of the composition refers to whether the synthetic leather was successfully obtained or failed in each example or comparative example according to the above preparation scheme. "G" in Table 3 indicates that the synthetic leather was successfully prepared, and "B" indicates that the synthetic leather preparation failed.

[0241] Table 3

[0242] Example Component A Component B catalyst Dry processability Peel strength (N / 3cm) Flexural properties Yellowing UVB 72H Yellowing 100°C 400H CEX 1 A1 B1 C1 / C2 (1:1) G 80 pass 2 2 CEX 2 A1 B2 C1 / C2 (1:1) G 70 pass 4-5 fail CEX 4 A2 B2 C1 / C2 (1:1) G 80 pass 4-5 4-5 EX 1 A3 B2 C1 / C2 (1:1) G 90 pass 4-5 4-5 EX 2 A4 B2 C1 / C2 (1:1) G 110 pass 4-5 4-5 EX 3 A5 B2 C1 / C2 (1:1) G 90 pass 4-5 4-5 CEX 3 A4 B2 C2 B - - - - EX 4 A4 B2 Sn G 80 pass 4-5 4-5

[0243] Note: “CEX” stands for comparative example, and “EX” stands for example.

Claims

1. A composition for forming polyurethane, consisting of: A. an isocyanate-reactive component comprising, a) a difunctional polyol having a weight average molecular weight of 800 to 1800 g / mol; b) a multifunctional polyol having a weight average molecular weight of 2000 to 6000 g / mol, wherein the functionality of the multifunctional polyol is greater than or equal to 2.4; and c) a crosslinker having a weight average molecular weight of 90 g / mol to 1000 g / mol, wherein the functionality of the crosslinker is greater than or equal to 2.5, wherein the crosslinker is ethoxylated and / or propoxylated glycerol, ethoxylated and / or propoxylated trimethylolpropane, ethoxylated and / or propoxylated butanetriol or any combination thereof, wherein the content of the crosslinker is 2.2 wt % to 9 wt %, based on the total weight of component A and component C, and B. an isocyanate prepolymer component prepared from at least one non-aromatic polyisocyanate and at least one compound containing two or more hydroxyl groups, and C. A catalyst, wherein the catalyst is a combination of a tertiary amine catalyst and a metal catalyst, or the catalyst is a tin catalyst.

2. The composition of claim 1, consisting of: A. an isocyanate-reactive component comprising, a) a difunctional polyol having a weight average molecular weight of 800 to 1800 g / mol; b) a multifunctional polyol having a weight average molecular weight of 2500 to 5000 g / mol, wherein the functionality of the multifunctional polyol is in the range of 2.5 to 3.2; and c) a crosslinker having a weight average molecular weight of 100 to 800 g / mol, wherein the functionality of the crosslinker is in the range of 2.8 to 5, wherein the crosslinker is ethoxylated and / or propoxylated glycerol, ethoxylated and / or propoxylated trimethylolpropane, ethoxylated and / or propoxylated butanetriol or any combination thereof, wherein the content of the crosslinker is 2.5% to 8% by weight, based on the total weight of component A and component C, and B. an isocyanate prepolymer component prepared from at least one non-aromatic polyisocyanate and at least one compound containing two or more hydroxyl groups, and C. A catalyst, wherein the catalyst is a combination of a tertiary amine catalyst and a metal catalyst, or the catalyst is a tin catalyst.

3. A composition as claimed in claim 1 or 2, wherein the functionality of the crosslinking agent is in the range of 2.5 to 3.

5.

4. The composition according to claim 1 or 2, wherein The difunctional polyol component a) is selected from polyethylene oxide diol, polypropylene oxide diol, poly(ethylene oxide-propylene oxide) diol, polytetramethylene oxide diol and polycaprolactone diol.

5. The composition according to claim 1 or 2, wherein The difunctional polyol component a) is polytetrahydrofuran diol.

6. The composition according to claim 1 or 2, wherein The multifunctional polyol component b) is selected from the group consisting of polyethylene oxide polyol, polypropylene oxide polyol, poly(ethylene oxide-propylene oxide) polyol, polytetramethylene oxide polyol and polycaprolactone polyol.

7. The composition of claim 1 or 2, wherein the total amount of component a) and component b) is in the range of 80 to 99 wt %, based on the weight of component A, and / or the weight ratio of component a) to component b) is in the range of 3:1 to 1:

3.

8. The composition of claim 1 or 2, wherein the total amount of component a) and component b) is in the range of 90 to 99 wt %, based on the weight of component A, and / or the weight ratio of component a) to component b) is in the range of 1.2:1 to 1:1.

2.

9. The composition according to claim 1 or 2, wherein The isocyanate prepolymer component has an isocyanate group content of 3% to 25% by weight.

10. The composition according to claim 1 or 2, wherein The isocyanate prepolymer component has an isocyanate group content of 5 to 15 wt %.

11. The composition according to claim 1 or 2, wherein The non-aromatic polyisocyanate is selected from C4-C 12 Aliphatic and C6-C 15 Cycloaliphatic polyisocyanates.

12. The composition according to claim 1 or 2, wherein The non-aromatic polyisocyanate is selected from dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and di(isocyanatomethylene)cyclohexane.

13. The composition according to claim 1 or 2, wherein The compound containing two or more hydroxyl groups mentioned for the isocyanate prepolymer component B is one or more polyether polyols or polyester polyols, or any combination thereof.

14. The composition according to claim 1 or 2, wherein The compound containing two or more hydroxyl groups mentioned for the isocyanate prepolymer component B is a polyether diol, a polyether polyol having a functionality ranging from 2.3 to 5, or any combination thereof.

15. The composition according to claim 1 or 2, wherein The catalyst is a combination of a tertiary amine catalyst and a zinc or bismuth-based catalyst.

16. The composition according to claim 1 or 2, wherein The catalyst is a combination of a tertiary amine catalyst and a zinc or bismuth-based catalyst, and the weight ratio of the combination is in the range of 2:1 to 1:

2.

17. The composition according to claim 1 or 2, wherein The catalyst is a combination of a tertiary amine catalyst and a zinc or bismuth-based catalyst, and the weight ratio of the combination is in the range of 1.2:1 to 1:1.

2.

18. The composition of claim 1 or 2, wherein the content of catalyst component C is in the range of 0.02 wt% to 1 wt% based on the total weight of component A and component C.

19. The composition of claim 1 or 2, wherein the content of catalyst component C is in the range of 0.03% to 0.1% by weight based on the total weight of component A and component C.

20. The composition of claim 1 or 2, wherein The isocyanate-reactive component A further comprises: d) a difunctional chain extender having a weight average molecular weight less than or equal to 500 g / mol, The amount of the chain extender is 1 wt % to 8 wt %, based on the total weight of component A and component C.

21. The composition of claim 1 or 2, wherein The isocyanate-reactive component A further comprises: d) a difunctional chain extender having a weight average molecular weight of 60 to 300 g / mol, The amount of the chain extender is 1 wt % to 8 wt %, based on the total weight of component A and component C.

22. The composition of claim 1 or 2, wherein The isocyanate-reactive component A further comprises: d) chain extenders, which are straight-chain and branched aliphatic and cycloaliphatic diols having 2 to 14 carbon atoms, The amount of the chain extender is 2 wt % to 6 wt %, based on the total weight of component A and component C.

23. The composition of claim 1 or 2, wherein The isocyanate-reactive component A further comprises: d) chain extenders, which are straight-chain and branched aliphatic and cycloaliphatic diols having 2 to 6 carbon atoms, The amount of the chain extender is 2 wt % to 6 wt %, based on the total weight of component A and component C.

24. The composition of claim 1 or 2, wherein components A, B and C are present in separate or mixed forms, or components A and B are present in separate forms and component C is present in component A.

25. The composition of claim 1 or 2, having an isocyanate index in the range of 90 to 120.

26. The composition of claim 1 or 2, having an isocyanate index in the range of 101 to 110.

27. Polyurethane article obtainable from the composition according to any one of claims 1 to 26.

28. Use of the composition according to any one of claims 1 to 26 for producing synthetic leather.