Auxiliary agent for improving elasticity and softness of polyurethane leather as well as preparation method and application of auxiliary agent

Abstract

The invention discloses an auxiliary agent for improving elasticity and softness of polyurethane leather as well as a preparation method and application of the auxiliary agent. The auxiliary agent comprises 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 copolymerized silicone oil and 80-100 parts of isopropanol. The additive mixture contains a plurality of beneficial groups such as phenyl, long-chain alkyl and polyether long-chain groups, and can greatly improve the elasticity and softness of the polyurethane leather. The invention further discloses a preparation method of the additive for improving the elasticity and softness of the polyurethane leather, and the preparation method is wide in raw material source, simple to operate and suitable for large-scale production and preparation.

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 kind of artificial leather, which has similar properties to natural leather, including good strength, wear resistance, cold resistance, breathability, aging resistance and solvent resistance. In addition, polyurethane leather has the advantages of soft texture and beautiful appearance, making it an ideal natural leather substitute for industries such as clothing, shoemaking, 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 allows polyurethane leather to maintain good appearance and performance under long-term use. Softness determines the comfort of polyurethane leather when it is 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 greatly 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 the present application is to provide an auxiliary agent, a preparation method and an application for improving the elasticity and softness of polyurethane leather. The auxiliary agent contains a variety of 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 the first aspect, the present application provides an auxiliary agent for improving the elasticity and softness of polyurethane leather, comprising the following components 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 isopropanol; the phenyl-containing polyether block silicone oil has a chemical structural formula as shown in formula (1):

[0008] The monomer composition shown in FIG. 1 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: Mix and react the phenyl-terminated hydrogen-containing silicone oil, epoxy-terminated allyl polyether, chloroplatinic acid isopropanol solution, and isopropanol 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: Mix the phenyl-containing polyether block silicone oil, 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.

[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, preparation method and application for improving the elasticity and softness of polyurethane leather, which, compared with the prior art, has at least the following beneficial effects:

[0015] 1. The auxiliary agent mixture provided in the present application includes main components such as phenyl-containing polyether block silicone oil, long-chain alkyl polyether copolymer silicone oil and organic solvent isopropanol. The auxiliary agent mixture contains multiple beneficial groups, among which the 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 excellent softness and smoothness to the leather; the long-chain alkyl polyether silicone oil introduces long-chain alkyl and polyether groups into the silicone oil molecules through the principle of molecular design. This structural design makes the modified silicone oil have better performance. The introduction of long-chain alkyl increases the hydrophobic group, reduces the water solubility, and improves the surface properties, which helps to improve the softness and elasticity of the 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 solution and advantages of the present application more clear, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described here are only used to explain the present application and are not used to limit the present application.

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

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

[0020] In view of the defects of the additives used in the prior art for improving the elasticity and softness of polyurethane leather, the embodiments of the present application combine organic compounds containing various beneficial groups such as phenyl, polyether segments, long-chain alkyl groups in a certain proportion to form a new additive, which can give full play to 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 isopropanol; the phenyl-containing polyether block silicone oil has a chemical structural formula as shown in formula (1):

[0022] The monomer composition shown in FIG. 1 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 isopropanol.

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

[0025] The embodiment of the present application also provides a method for preparing an auxiliary agent for improving the elasticity and softness of polyurethane leather, comprising the following steps: S1: taking a hydrogen-containing silicone oil containing phenyl groups at both ends, an epoxy-terminated allyl polyether, a chloroplatinic acid isopropanol solution, and isopropanol and mixing them to obtain an epoxy-terminated polyether-modified silicone oil; S2: mixing 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 obtained in step S2, a long-chain alkyl polyether copolymer silicone oil and isopropanol 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 follows: 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 terminal epoxy polyether modified silicone oil shown.

[0027] In certain embodiments, in S1, the mixed 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 terminal epoxy polyether modified silicone oil reacts with the polyether amine to generate the phenyl-containing polyether block silicone oil, and the phenyl-containing polyether block silicone oil has a chemical structural formula as shown in formula (1): The monomer composition is composed of, 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 mixed reaction in S2 is 40-60° C., and the reaction time is 3-6 hours.

[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 follows: 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 auxiliary agent obtained includes the following components 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 isopropanol

[0032] The technical scheme of the present application and the technical effects achieved are described in detail below through more specific examples. The raw material compounds involved in the examples of the present application can be purchased from a regular commodity market or obtained by chemical synthesis in a laboratory.

[0033] Example 1

[0034] This embodiment provides a method for preparing an auxiliary agent 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 hydrogen-containing silicone oil containing phenyl groups at both ends, and isopropanol of the same mass of hydrogen-containing silicone oil containing phenyl groups at both ends, the above substances are added to a reactor and mixed and stirred at 70°C for 5 hours until it becomes clear and transparent, and then cooled to room temperature to obtain terminal epoxy polyether modified silicone oil; 10 mol of CAED600 polyether amine is added to the reactor, the reactor temperature is raised to 40°C, reacted for 4 hours, cooled and purified to obtain phenyl-containing polyether block silicone oil; according to mass parts, 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 auxiliary agent 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 of the mass of hydrogen-containing silicone oil containing phenyl groups at both ends, and isopropanol of the same mass of hydrogen-containing silicone oil containing phenyl groups at both ends, the above substances are added to a reactor and mixed and stirred at 75°C for 4 hours until clear and transparent, and then cooled to room temperature to obtain terminal epoxy polyether modified silicone oil; 2 mol of CAED900 polyether amine is added to the reactor, the reactor temperature is raised to 50°C, reacted for 6 hours, cooled 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 auxiliary agent 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 chloroplatinic acid isopropanol solution with a mass of 0.2% hydrogen-containing silicone oil containing phenyl groups at both ends, and isopropanol with an equal mass of hydrogen-containing silicone oil containing phenyl groups at both ends, and the above substances are added to a reactor and mixed and stirred at 80°C for 8 hours until it becomes clear and transparent, and then cooled to room temperature to obtain terminal epoxy polyether modified silicone oil; 1 mol of CAED2000 polyether amine is added to the reactor, the reactor temperature is raised to 60°C, reacted for 3 hours, cooled 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 mix evenly to obtain auxiliary agent A3.

[0042] Comparative Example 1

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

[0044] Comparative Example 2

[0045] This comparative example provides a polyurethane leather auxiliary agent, and the preparation method thereof is as follows: by weight, 50 parts of long-chain alkyl polyether copolymer silicone oil and 100 parts of isopropanol are stirred at room temperature for 1 hour to mix evenly 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., item number: LX0208) was used as auxiliary agent A7.

[0050] Comparative Example 5

[0051] Dihydroxy polyether modified silicone oil (product source: Dow Corning Corporation, USA, item 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 for 20 minutes using a stirrer 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, and then 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] The polyurethane leather samples A1 to A8 obtained above were subjected to elasticity tests respectively. The test method was based on the standard GB / T528 / 2008 "Determination of tensile stress-strain characteristics of vulcanized rubber or thermoplastic rubber". The elongation at break was selected as the evaluation index of the elasticity of the polyurethane leather. The calculation formula of the elongation at break was: elongation at break (%) = (elongation at break - original gauge length) / original gauge length × 100%;

[0055] A leather softness tester (equipment source: Kunshan Xiangke Testing Instrument Co., Ltd., product model: XK-3050) was used to test the softness of the polyurethane leather samples A1 to A8. The leather softness tester implemented the standards ISO17235-2002: Leather, physical and mechanical properties test - Determination of stiffness, EN ISO17235-2002: Leather, physical and mechanical tests: Determination of softening degree. The specific test steps are as follows: A test ring with a diameter of 35 mm is selected on the test seat of the softness tester, and the metal plate equipped with the machine is used to reset the machine scale, and the polyurethane leather samples A1 to A8 are pressed into the test seat of the tester respectively. After the polyurethane leather samples are pressed in, the pointer of the testing machine will change. After the pointer stabilizes, the corresponding value is 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 criteria 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: pointer variation 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: pointer variation 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: pointer variation 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 change range is less than 0.20 mm.

[0066] According to the results in Table 1, the elasticity and softness of the polyurethane leather prepared by the additives prepared in Examples 1 to 3 are the best, indicating that the examples of the present application use an additive mixture composed of phenyl-containing polyether block silicone oil, long-chain alkyl polyether copolymer silicone oil and organic solvent isopropanol, and optimize the mass proportion of each component of the additive mixture, which can greatly improve the elasticity and softness of the additive in polyurethane leather. However, the additives prepared in Comparative Examples 1 to 5 are used to prepare polyurethane leather. Except for individual formulas that can increase their single performance (such as the softness of Comparative Example 1 and the elasticity of Comparative Example 5, both scored 4), none of them can guarantee the effect of excellent elasticity and softness at the same time.

[0067] The present application is described in detail above. Specific examples are used in this article to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the present application and its core ideas. It should be pointed out that for ordinary technicians in this technical field, without departing from the principles of the present application, several improvements and modifications can be made to the present application, and these improvements and modifications also 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 weight: 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 isopropanol; the phenyl-containing polyether block silicone oil has a chemical structural formula as shown in formula (1): The monomer composition shown in FIG. 1 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 isopropanol.

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: Mix and react the phenyl-terminated hydrogen-containing silicone oil, epoxy-terminated allyl polyether, chloroplatinic acid isopropanol solution, and isopropanol 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: Mix the phenyl-containing polyether block silicone oil, 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.

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 4-8h.

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, 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 3-6h.

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.

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