Auxiliary agent for improving elasticity and softness of polyurethane leather, preparation method and application

Abstract

This application discloses an additive for improving the elasticity and softness of polyurethane leather, its preparation method, and its use. The additive comprises the following components, in parts by mass: 80-120 parts of a phenyl-containing polyether block silicone oil, 30-70 parts of a long-chain alkyl polyether copolymer silicone oil, and 80-100 parts of isopropyl alcohol. This additive mixture contains multiple beneficial groups, including phenyl, long-chain alkyl, and polyether long-chain groups, and can significantly enhance the elasticity and softness of polyurethane leather. This application also discloses a preparation method for the additive for improving the elasticity and softness of polyurethane leather. This preparation method utilizes a wide range of raw materials, is simple to operate, and is suitable for large-scale production.

Description

Technical Field

[0001] The present application relates to the technical field of leather auxiliaries, and in particular to an auxiliary agent for improving the elasticity and softness of polyurethane leather, a preparation method and application thereof. Background Art

[0002] Polyurethane leather (PU Leather) is a type of artificial leather that has properties similar to natural leather, including good strength, wear resistance, cold resistance, breathability, aging resistance, and solvent resistance. In addition, polyurethane leather has advantages such as soft texture and beautiful appearance, making it an ideal natural leather substitute for industries such as clothing, footwear, luggage, and furniture. Elasticity is a key indicator of leather durability. It allows the material to return to its original shape after being stretched or bent, which enables polyurethane leather to maintain its good appearance and performance under long-term use. Softness determines the comfort of polyurethane leather when touched, which is an important purchasing factor for consumers. At the same time, good elasticity and softness make the leather easier to cut, sew, and other processing operations, thereby improving production efficiency. Therefore, elasticity and softness are very important properties of polyurethane leather.

[0003] There are many additives used to improve the elasticity and softness of polyurethane leather, such as amino-modified silicone oil, dihydroxy polyether-modified siloxane, polydimethylsiloxane (PDMS), etc. However, most of these additives have problems such as single performance and small improvement in elasticity or softness, which further increases the difficulty of preparing high-quality polyurethane leather products.

[0004] Therefore, it is necessary to develop a new auxiliary agent for significantly improving the elasticity and softness of polyurethane leather to meet the needs of the market and people's use. Summary of the Invention

[0005] In view of this, the purpose of this application is to provide an auxiliary agent, preparation method and application for improving the elasticity and softness of polyurethane leather. The auxiliary agent contains multiple beneficial groups and has the function of improving the elasticity and softness of polyurethane leather.

[0006] To achieve the above objectives, this application provides the following technical solutions:

[0007] In a first aspect, the present application provides an auxiliary agent for improving the elasticity and softness of polyurethane leather, comprising the following components in parts by mass: 80 to 120 parts of a phenyl-containing polyether block silicone oil, 30 to 70 parts of a long-chain alkyl polyether copolymer silicone oil, and 80 to 100 parts of isopropyl alcohol; the phenyl-containing polyether block silicone oil has a chemical structural formula as shown in formula (1):

[0008] The monomer composition shown in FIG. has a polymerization degree of 1 to 30, wherein the chemical structure of R1 is as shown in formula (2): As shown, m is an integer of 1 to 30, n is an integer of 1 to 30, x is an integer of 1 to 50, and a, b, and c are all integers of 1 to 30; the chemical structure of the long-chain alkyl polyether copolymer silicone oil is as shown in formula (3): As shown, R2 is any one of 12-olefin, 16-olefin, and 18-olefin, R3 is EO / PO block polyether, and d, e, and f are all integers of 1 to 30.

[0009] In a second aspect, the present application provides a method for preparing an auxiliary agent for improving the elasticity and softness of polyurethane leather, comprising the following steps:

[0010] S1: Silicone oil containing phenyl groups at both ends and containing hydrogen, epoxy-terminated allyl polyether, chloroplatinic acid isopropanol solution, and isopropanol are mixed and reacted to obtain epoxy-terminated polyether-modified silicone oil;

[0011] S2: mixing the epoxy-terminated polyether-modified silicone oil obtained in S1 with polyetheramine to obtain a phenyl-containing polyether block silicone oil;

[0012] S3: The phenyl-containing polyether block silicone oil, long-chain alkyl polyether copolymer silicone oil and isopropyl alcohol obtained in step S2 are mixed to obtain an auxiliary agent for improving the elasticity and softness of polyurethane leather.

[0013] In a third aspect, the present application also provides the use of the aforementioned auxiliary agent in the preparation of polyurethane leather.

[0014] The present application provides an additive for improving the elasticity and softness of polyurethane leather, a preparation method, and an application thereof, which, compared with the prior art, have at least the following beneficial effects:

[0015] 1. The auxiliary agent mixture provided in this application includes as main components phenyl-containing polyether block silicone oil, long-chain alkyl polyether copolymer silicone oil and organic solvent isopropyl alcohol. The auxiliary agent mixture contains multiple beneficial groups, among which phenyl polyether block silicone oil contains phenyl and polyether segments. The phenyl group can give the material good thermal stability and chemical stability, while the polyether segment group can provide leather with excellent softness and smoothness; long-chain alkyl polyether silicone oil introduces long-chain alkyl and polyether groups into silicone oil molecules through molecular design principles. This structural design makes the modified silicone oil have better performance. The introduction of long-chain alkyl groups increases hydrophobic groups, reduces water solubility, and improves surface properties, which helps to improve the softness and elasticity of leather and has broad application prospects.

[0016] 2. The present application provides a method for preparing the aforementioned auxiliary agent for improving the elasticity and softness of polyurethane leather. The preparation method has a wide source of raw materials, is simple to operate, and is suitable for large-scale production and preparation. DETAILED DESCRIPTION

[0017] In order to make the purpose, technical solutions and advantages of this application more clear, the following further describes this application in detail with reference to the embodiments. It should be understood that the specific embodiments described herein are only used to explain this application and are not intended to limit this application.

[0018] Those skilled in the art will understand that, unless otherwise stated, the terms "said," "the," and "the aforementioned" used in this application may include plural forms. It should be further understood that the term "comprising" used in the specification of this application refers to the presence of the stated features, steps, or operations, but does not exclude the presence or addition of one or more other features, steps, or operations.

[0019] In this application text, the term "normal temperature" refers to room temperature or general temperature, for example, the temperature range can be 15 to 25°C.

[0020] In response to the defects of the auxiliary agents used in the prior art to improve the elasticity and softness of polyurethane leather, the embodiments of the present application combine organic compounds containing multiple beneficial groups such as phenyl, polyether segments, long-chain alkyl groups in a certain proportion to form a new auxiliary agent, which can fully exert the role of each group in improving the elasticity and softness of leather.

[0021] Based on this, the embodiment of the present application provides an auxiliary agent for improving the elasticity and softness of polyurethane leather, comprising the following components calculated by mass: 80-120 parts of phenyl-containing polyether block silicone oil, 30-70 parts of long-chain alkyl polyether copolymer silicone oil, and 80-100 parts of isopropyl alcohol; the phenyl-containing polyether block silicone oil has a chemical structural formula as shown in formula (1):

[0022] The monomer composition shown in FIG. has a polymerization degree of 1 to 30, wherein the chemical structure of R1 is as shown in formula (2): As shown, m is an integer of 1 to 30, n is an integer of 1 to 30, x is an integer of 1 to 50, y is an integer of 1 to 100, and a, b, and c are all integers of 1 to 30; the chemical structure of the long-chain alkyl polyether copolymer silicone oil is as shown in formula (3): As shown, R2 is any one of 12-olefin, 16-olefin, and 18-olefin, R3 is EO / PO block polyether, and d, e, and f are all integers of 1 to 30.

[0023] In certain preferred embodiments, the auxiliary agent, calculated by weight, includes 100 parts of phenyl-containing polyether block silicone oil, 50 parts of long-chain alkyl polyether copolymer silicone oil, and 50 parts of isopropyl alcohol.

[0024] In certain preferred embodiments, the molecular weight of the long-chain alkyl polyether copolymer silicone oil is 2000-8000.

[0025] The embodiments of the present application also provide a method for preparing an auxiliary agent for improving the elasticity and softness of polyurethane leather, comprising the following steps: S1: mixing and reacting a phenyl-containing hydrogen-containing silicone oil at both ends, an epoxy-terminated allyl polyether, a chloroplatinic acid isopropyl alcohol solution, and isopropyl alcohol to obtain an epoxy-terminated polyether-modified silicone oil; S2: mixing and reacting the epoxy-terminated polyether-modified silicone oil obtained in S1 with a polyetheramine to obtain a phenyl-containing polyether block silicone oil; S3: mixing the phenyl-containing polyether block silicone oil, the long-chain alkyl polyether copolymer silicone oil, and isopropyl alcohol obtained in step S2 to obtain an auxiliary agent for improving the elasticity and softness of polyurethane leather.

[0026] In the embodiment of the present application, in S1, the chemical structural formula of the phenyl-containing hydrogen-containing silicone oil is as shown in Formula (4): As shown, wherein x is an integer of 1 to 50, and y is an integer of 1 to 100; the chemical structure of the epoxy-terminated allyl polyether is as shown in formula (5): As shown, wherein m and n are both integers of 1 to 30, and the two generate a chemical structure as shown in formula (6) under the catalytic action of chloroplatinic acid isopropanol solution: The end-epoxy polyether modified silicone oil shown.

[0027] In certain embodiments, in S1, the mixing reaction temperature is 70-80° C., and the reaction time is 4-8 h.

[0028] In the embodiment of the present application, in S2, the chemical structural formula of the polyetheramine is as shown in Formula (7): As shown, wherein a, b, and c are all integers of 1 to 30. The epoxy-terminated polyether-modified silicone oil reacts with the polyetheramine to generate the phenyl-containing polyether block silicone oil, and the phenyl-containing polyether block silicone oil has a chemical structure as shown in Formula (1): wherein the chemical structure of R1 is as shown in formula (2): As shown, m is an integer of 1 to 30, n is an integer of 1 to 30, x is an integer of 1 to 50, y is an integer of 1 to 100, and a, b, and c are all integers of 1 to 30.

[0029] In certain embodiments, the temperature of the mixing reaction in S2 is 40-60° C., and the reaction time is 3-6 h.

[0030] In the embodiment of the present application, in S3, the chemical structural formula of the long-chain alkyl polyether copolymer silicone oil is as shown in Formula (3): As shown, R2 is any one of 12-olefin, 16-olefin, and 18-olefin, R3 is EO / PO block polyether, and d, e, and f are all integers of 1 to 30.

[0031] In some embodiments, in S3, the obtained auxiliary agent includes the following components in parts by mass: 80-120 parts of phenyl-containing polyether block silicone oil, 30-70 parts of long-chain alkyl polyether copolymer silicone oil, 80-100 parts of isopropyl alcohol

[0032] The following is a detailed description of the technical solution and the technical effects achieved by the present application through more specific examples. The raw material compounds involved in the examples of the present application can be purchased from the regular commodity market or obtained by chemical synthesis in the laboratory.

[0033] Example 1

[0034] This embodiment provides a method for preparing an additive for improving the elasticity and softness of polyurethane leather, and the specific steps are:

[0035] Weigh the following substances separately: Silicone oil containing phenyl groups and hydrogen at both ends (chemical structure is as follows: As shown) and epoxy-terminated allyl polyether (chemical structure as follows: As shown), 10 mol each of the above, 0.2% chloroplatinic acid isopropanol solution of the mass of phenyl-containing hydrogen-containing silicone oil at both ends, and the same mass of isopropanol as the mass of phenyl-containing hydrogen-containing silicone oil at both ends, the above substances are added to a reactor and mixed and stirred at 70 ° C for 5 hours until clear and transparent, and then cooled to room temperature to obtain end-epoxy polyether modified silicone oil; 10 mol of CAED600 polyetheramine is added to the reactor, the reactor temperature is raised to 40 ° C, the reaction is carried out for 4 hours, the temperature is lowered and purified to obtain phenyl-containing polyether block silicone oil; by mass, 100 parts of the phenyl-containing polyether block silicone oil obtained in the previous step, 50 parts of long-chain alkyl polyether copolymer silicone oil, and 100 parts of isopropanol are taken and stirred at room temperature for 1 hour to mix evenly to obtain auxiliary agent A1.

[0036] Example 2

[0037] This embodiment provides a method for preparing an additive for improving the elasticity and softness of polyurethane leather, and the specific steps are:

[0038] Weigh the following substances separately: Silicone oil containing phenyl groups and hydrogen at both ends (chemical structure is as follows: As shown) and epoxy-terminated allyl polyether (chemical structure as follows: As shown), 2 mol each, 0.2% chloroplatinic acid isopropanol solution containing phenyl ends and hydrogen silicone oil containing phenyl ends, and the same mass of isopropanol as the hydrogen silicone oil containing phenyl ends, the above substances are added to a reactor and stirred at 75 ° C for 4 hours until clear and transparent, and then cooled to room temperature to obtain end-epoxy polyether modified silicone oil; 2 mol of CAED900 polyetheramine is added to the reactor, the reactor temperature is raised to 50 ° C, the reaction is carried out for 6 hours, the temperature is lowered and purified to obtain phenyl-containing polyether block silicone oil; by mass, 80 parts of the phenyl-containing polyether block silicone oil obtained in the previous step, 70 parts of long-chain alkyl polyether copolymer silicone oil, and 80 parts of isopropanol are taken and stirred at room temperature for 1 hour to mix evenly to obtain auxiliary agent A2.

[0039] Example 3

[0040] This embodiment provides a method for preparing an additive for improving the elasticity and softness of polyurethane leather, and the specific steps are:

[0041] Weigh the following substances separately: Silicone oil containing phenyl groups and hydrogen at both ends (chemical structure is as follows: As shown) and epoxy-terminated allyl polyether (chemical structure as follows: As shown), 1 mol each of the above, 0.2% chloroplatinic acid isopropanol solution of the mass of phenyl-containing hydrogen-containing silicone oil at both ends, and the same mass of isopropanol as the mass of phenyl-containing hydrogen-containing silicone oil at both ends, the above substances are added to a reactor and mixed and stirred at 80 ° C for 8 hours until clear and transparent, and then cooled to room temperature to obtain end-epoxy polyether modified silicone oil; 1 mol of CAED2000 polyetheramine is added to the reactor, the reactor temperature is raised to 60 ° C, the reaction is carried out for 3 hours, the temperature is lowered and purified to obtain phenyl-containing polyether block silicone oil; by mass, 120 parts of the phenyl-containing polyether block silicone oil obtained in the previous step, 30 parts of long-chain alkyl polyether copolymer silicone oil, and 90 parts of isopropanol are taken and stirred at room temperature for 1 hour to obtain auxiliary agent A3.

[0042] Comparative Example 1

[0043] This comparative example provides a polyurethane leather auxiliary agent, the preparation method of which is as follows: prepare a phenyl-containing polyether block silicone oil according to steps S1 and S2 of Example 1; then, stir 100 parts by mass of the phenyl-containing polyether block silicone oil and 100 parts of isopropyl alcohol at room temperature for 1 hour to obtain auxiliary agent A4.

[0044] Comparative Example 2

[0045] This comparative example provides a polyurethane leather auxiliary agent, the preparation method of which is as follows: by weight, 50 parts of long-chain alkyl polyether copolymer silicone oil and 100 parts of isopropyl alcohol are stirred at room temperature for 1 hour to mix uniformly to obtain auxiliary agent A5.

[0046] Comparative Example 3

[0047] Polydimethylsiloxane (PDMS) (product source: Shanghai Dingfen Chemical Technology Co., Ltd., CAS: 9016-00-6) was purchased from the market as auxiliary agent A6.

[0048] Comparative Example 4

[0049] Amino-modified silicone oil purchased from the market (product source: Shanghai Longxu Silicone Technology Co., Ltd., product number: LX0208) was used as auxiliary agent A7.

[0050] Comparative Example 5

[0051] Dihydroxy polyether modified silicone oil (product source: Dow Corning, USA, product number: SF-8427) was purchased from the market as auxiliary agent A8.

[0052] The additives A1 to A8 prepared in Examples 1 to 3 and Comparative Examples 1 to 5 were respectively used to prepare polyurethane leather. The specific preparation method is as follows:

[0053] The following raw materials were prepared by weight: 50 parts of polyurethane (PU) resin, 60 parts of N,N-dimethylformamide (DMF), 20 parts of light calcium carbonate, and 2 parts of additives; the raw materials were stirred and mixed at 800 rpm in a stirrer for 20 minutes to obtain a uniform mixed solution; the mixed solution was coated on a glass plate with a film thickness of 1 mm, and then immersed in a 25% DMF aqueous solution for 5 minutes, taken out and washed with clean water 5 times; the glass plate covered with the film was placed in a 120°C oven for 15 minutes and dried to obtain polyurethane leather samples P1 to P8 containing additives A1 to A8, respectively.

[0054] Elasticity tests were performed on the polyurethane leather samples A1 to A8 obtained above. The test method was based on the standard GB / T528 / 2008 "Rubber, vulcanized or thermoplastic — Determination of tensile stress-strain properties." The elongation at break was selected as the evaluation index of the elasticity of the polyurethane leather. The elongation at break was calculated as follows: elongation at break (%) = (elongation at break - original gauge length) / original gauge length × 100%.

[0055] The softness of the polyurethane leather samples A1 to A8 was tested using a leather softness tester (source: Kunshan Xiangke Testing Instrument Co., Ltd., model: XK-3050). The leather softness tester complies with ISO 17235-2002: Leather. Physical and mechanical properties - Determination of stiffness and EN ISO 17235-2002: Leather. Physical and mechanical testing: Determination of softening. The specific test steps are as follows: A test ring with a diameter of 35 mm was selected for the test seat of the softness tester. The metal plate provided with the machine was used to reset the machine scale. The polyurethane leather samples A1 to A8 were respectively pressed into the test seat of the tester. After the polyurethane leather samples were pressed in, the pointer of the testing machine would change. After the pointer stabilized, the corresponding value was recorded.

[0056] The results of the elasticity test and the softness test are shown in Table 1 below.

[0057] Table 1

[0058]

[0059]

[0060] Among them, the elasticity and softness evaluation standards are divided into:

[0061] Good (5 points): Elasticity: Elongation at break is more than 350%; Softness: Pointer change is more than 0.35mm;

[0062] Good (4 points): Elasticity: Elongation at break is 300% to 350%, excluding 350%; Softness: The pointer range is 0.30 to 0.35 mm, excluding 0.35 mm;

[0063] General (3 points): Elasticity: Elongation at break is 250% to 300%, excluding 300%; Softness: The pointer range is 0.25 to 0.30 mm, excluding 0.30 mm;

[0064] Poor (2 points): Elasticity: Elongation at break is 200% to 250%, excluding 250%; Softness: The pointer range is 0.20 to 0.25 mm, excluding 0.25 mm;

[0065] Poor (1 point), elasticity: elongation at break is less than 200%; softness: pointer variation range is less than 0.20 mm.

[0066] According to the results in Table 1, the elasticity and softness properties of the polyurethane leather prepared by the additives prepared in Examples 1 to 3 are both the best, indicating that the examples of the present application, by using an additive mixture consisting of a phenyl-containing polyether block silicone oil, a long-chain alkyl polyether copolymer silicone oil, and an organic solvent, isopropyl alcohol, and optimizing the mass ratio of each component of the additive mixture, can significantly improve the elasticity and softness properties of the polyurethane leather. However, the polyurethane leather prepared by the additives prepared in Comparative Examples 1 to 5, except for individual formulas that can improve its single property (such as the softness of Comparative Example 1 and the elasticity of Comparative Example 5, both rated 4), cannot simultaneously ensure the effect of excellent elasticity and softness.

[0067] The present application has been described in detail above. Specific examples have been used herein to illustrate the principles and implementation methods of the present application. The description of the above embodiments is intended only to facilitate understanding of the present application and its core concepts. It should be noted that, without departing from the principles of the present application, a number of improvements and modifications may be made to the present application by a person skilled in the art, and such improvements and modifications shall fall within the scope of protection of the claims of the present application.

Claims

1. An auxiliary agent for improving the elasticity and softness of polyurethane leather, characterized in that: The invention comprises the following components calculated by mass: 80-120 parts of phenyl-containing polyether block silicone oil, 30-70 parts of long-chain alkyl polyether copolymer silicone oil, and 80-100 parts of isopropyl alcohol; the phenyl-containing polyether block silicone oil has a chemical structural formula as shown in formula (1): The monomer composition shown in FIG. has a polymerization degree of 1 to 30, wherein the chemical structure of R1 is as shown in formula (2): As shown, m is an integer of 1 to 30, n is an integer of 1 to 30, x is an integer of 1 to 50, y is an integer of 1 to 100, and a, b, and c are all integers of 1 to 30; the chemical structure of the long-chain alkyl polyether copolymer silicone oil is as shown in formula (3): As shown, R2 is any one of 12-olefin, 16-olefin, and 18-olefin, R3 is EO / PO block polyether, and d, e, and f are all integers of 1 to 30.

2. The auxiliary agent for improving the elasticity and softness of polyurethane leather according to claim 1, characterized in that Calculated by mass, it includes 100 parts of phenyl-containing polyether block silicone oil, 50 parts of long-chain alkyl polyether copolymer silicone oil, and 50 parts of isopropyl alcohol.

3. The auxiliary agent for improving the elasticity and softness of polyurethane leather according to claim 1, characterized in that The molecular weight of the long-chain alkyl polyether copolymer silicone oil is 2000-8000.

4. The method for preparing the auxiliary agent for improving the elasticity and softness of polyurethane leather according to claim 1, characterized in that: The following steps are involved: S1: Silicone oil containing phenyl groups at both ends and containing hydrogen, epoxy-terminated allyl polyether, chloroplatinic acid isopropanol solution, and isopropanol are mixed and reacted to obtain epoxy-terminated polyether-modified silicone oil; S2: mixing the epoxy-terminated polyether-modified silicone oil obtained in S1 with polyetheramine to obtain a phenyl-containing polyether block silicone oil; S3: The phenyl-containing polyether block silicone oil, long-chain alkyl polyether copolymer silicone oil and isopropyl alcohol obtained in step S2 are mixed to obtain an auxiliary agent for improving the elasticity and softness of polyurethane leather.

5. The preparation method according to claim 4, characterized in that In S1, the chemical structural formula of the phenyl-containing hydrogen-containing silicone oil is as shown in Formula (4): As shown; the chemical structure of the epoxy-terminated allyl polyether is as shown in formula (5): shown.

6. The preparation method according to claim 4, characterized in that In S1, the mixed reaction temperature is 70-80° C., and the reaction time is 4-8 h.

7. The preparation method according to claim 4, characterized in that In S2, the chemical structural formula of the polyetheramine is as shown in Formula (7): As shown, wherein a, b, and c are all integers from 1 to 30.

8. The preparation method according to claim 4, characterized in that The temperature of the mixed reaction in S2 is 40-60° C., and the reaction time is 3-6 hours.

9. Use of the auxiliary agent for improving the elasticity and softness of polyurethane leather according to any one of claims 1 to 3 and / or the preparation method according to any one of claims 4 to 8 in the preparation of polyurethane leather.

Images