Polyurethane composite material for automobile seat as well as preparation method and application of polyurethane composite material

Abstract

The invention relates to the field of polyurethane materials, in particular to a polyurethane composite material for an automobile seat and a preparation method and application thereof, all the adopted raw materials are in a liquid state, use is convenient, blocking of a foaming machine filter by a solid adsorbent is prevented, and abrasion of a foaming machine nozzle is reduced. According to the present invention, the treatment agent does not need to be sprayed, the effect is stable, the VOC and the odor are mainly reduced from the two aspects of introduction reduction and generation control, and the introduction reduction is the selection of the specific silicone oil and the catalyst to reduce the odor generated by the volatilization of the small molecule auxiliary agent; the generation control is to reduce the generation of micromolecular volatile matters including aldehydes in the synthesis reaction by using the antioxidant, and the aldehyde treating agent directly captures the generated aldehydes, so that the effect of the antioxidant is supplemented and enhanced.

Description

Technical Field

[0001] This invention relates to the field of polyurethane materials, specifically to a low-VOC, low-aldehyde-content polyurethane composite for automotive seats, its preparation method, and its application. Background Technology

[0002] Polyurethane high-resilience foam possesses excellent flexibility, resilience, and durability, making it a core cushioning material for automotive seats. Simultaneously, with increasing demands for environmental protection and comfort, seat VOCs, mechanical properties, and lightweighting are receiving greater attention and higher requirements.

[0003] Currently, VOCs are generally considered to originate from polyols, residual low-molecular-weight aldehydes, alcohols, and carboxylic acids. Tertiary amine catalysts in the foam can volatilize when they reach the surface of the foam cells. Residual silicone oils and siloxanes in the foam increase VOCs. Odor and VOCs are typically reduced through adsorption, such as by adding activated carbon or silica as adsorbents. However, in practical use, the addition of solid materials inevitably increases wear on the foaming equipment, reducing its precision and lifespan. Another method involves spraying formaldehyde-removing agents onto the product to reduce VOCs and odors, but this increases the production process, and the inability to spray the agent onto the inside of the product leads to unstable treatment results and uneven treatment effects inside and outside the product. Summary of the Invention

[0004] To address the issues of high VOC and aldehyde content, odor, and wear and tear on foaming equipment during the preparation of polyurethane, this invention provides a polyurethane composite for automotive seats, its preparation method, and its applications. This composite can be used to prepare polyurethane foam for automotive seats, resulting in foams with excellent mechanical properties, low VOC content, and minimal odor. All raw materials used are in liquid form, facilitating use and preventing clogging of the foaming machine filter by solid adsorbents, thus reducing wear on the foaming machine nozzles. This invention eliminates the need for external treatment agents, ensuring stable performance. Specifically, it reduces VOCs and odors through two aspects: "reducing introduction" and "controlling generation." "Reducing introduction" involves using specific silicone oils and catalysts to reduce odors generated by the volatilization of small-molecule additives. "Controlling generation" uses antioxidants to reduce the generation of small-molecule volatiles, including aldehydes, during the synthesis reaction. The aldehyde treatment agent directly captures the generated aldehydes, supplementing and enhancing the effect of the antioxidant.

[0005] The specific technical solution of the present invention is as follows: A polyurethane composite material for automotive seats, comprising component A and component B, wherein the weight ratio of component A to component B is 100:38-48; By weight percentage, Component A comprises 40-60% polyether polyol, 30-50% grafted polyether polyol, 0.5-3% crosslinking agent, 0.5-3% silicone oil, 0.3-2% amine catalyst, 3-3.5% water, 0.5-4% open-cell polyether, 0.1-0.3% antioxidant and 0.1-0.8% aldehyde treatment agent; Component B comprises 40-90% toluene diisocyanate (TDI) and 10-60% polymethylene polyphenyl isocyanate (PAPI).

[0006] Furthermore, the polyether polyol is a polypropylene triol with a functionality of 3, a molecular weight of 4000-6000, a hydroxyl value of 27-42 mgKOH / g, and ethylene oxide end-capped.

[0007] Furthermore, the polyoxypropylene triol has a molecular weight of 4500-5500 and a hydroxyl value of 33-36 mgKOH / g.

[0008] In some embodiments of the present invention, the polyether polyol used is 10LD76EK from Shandong Lanxing Dongda Co., Ltd.

[0009] Furthermore, the grafted polyether polyol is a polyether polyol grafted with styrene or acrylonitrile, with a functionality of 3, a molecular weight of 6000-8000, and a solid content of 30-45wt%.

[0010] In some embodiments of the present invention, the grafted polyether polyol is HPOP-40 from Shandong Lanxing Dongda Co., Ltd.

[0011] Furthermore, the crosslinking agent has a functionality of 3 and a hydroxyl value of 1000-1830 mgKOH / g; even further, the crosslinking agent is at least one of diethanolamine, triethanolamine, and glycerol.

[0012] Furthermore, the silicone oil is a Si-C (silicon-carbon chain) type polysiloxane-olefin oxide block copolymer; the amine catalyst is a hydroxyl-containing tertiary amine; it is a reactive catalyst that can be incorporated into the polyurethane molecular structure to adjust the foaming and gelation reaction rates.

[0013] In some embodiments of the present invention, the silicone oil is Evonik Industries' TEGOSTAB B8734 LF2 and / or TEGOSTAB B8736 LF2.

[0014] In some embodiments of the present invention, the amine catalyst is two or three of Huntsman Polyurethanes (China) Co., Ltd., namely LE-503, ZR-50, Z-130, and ZF-10.

[0015] This invention selects specific types of silicone oil and amine catalysts to control the content of volatiles and other pollutants in the composite material from the perspective of "reducing introduction", thereby reducing the odor of the product. When used in combination with specific types of antioxidants and aldehyde treatment agents, the odor of seats made from this composite material and the content and emission of various volatile pollutants can be significantly reduced.

[0016] Furthermore, the open-cell polyether is a polyol of epoxy-ethylene and epoxy-propylene co-ether with a functionality of 3, a molecular weight of 4000-7000, a hydroxyl value of 25-35 mgKOH / g, and epoxy-terminated.

[0017] In some embodiments of the present invention, the open-cell polyether is JQN-3611 from Nanjing Jinqi Chemical Group Co., Ltd.

[0018] The antioxidant is a free radical chain blocker, which is easy to use in liquid form and has little impact on the reaction rate; however, excessive use can affect the odor, so its dosage is limited to 0.1-0.3%.

[0019] In some embodiments of the present invention, the antioxidant is one or both of BASF's Irgastab® PUR-70 and Irganox® 1135. The aldehyde treatment agent is an aldehyde scavenger that can react with aldehydes to generate stable new substances. In some embodiments of the present invention, the aldehyde treatment agent is JEFFADD® AS 76 from Huntsman Polyurethanes (China) Co., Ltd., and excessive use will increase costs.

[0020] Antioxidants reduce the production of small volatile molecules such as aldehydes during the reaction, while aldehyde treatment agents capture and treat the aldehydes produced. The two have combined value, and when used together, they can achieve better results in reducing VOCs and odors.

[0021] In some embodiments of the present invention, the TDI is preferably BASF's T-80; the PAPI is preferably BASF's M20S.

[0022] The present invention further provides a method for preparing the above-mentioned polyurethane composite material for automotive seats, the steps of which are as follows: Preparation of Component A: Add the polyether polyol and grafted polyether polyol to the reactor according to the specified ratio and stir at 30-60 rpm for 0.5-1 hour. Then, add the crosslinking agent, silicone oil, amine catalyst, open-cell polyether, antioxidant, aldehyde treatment agent, and water in sequence. Close the feed line and open the circulation line from the bottom to the top of the reactor. Continue stirring for 1.5-2 hours to obtain Component A. Preparation of S2.B component: Add TDI and PAPI into the reactor according to the ratio, seal the liquid surface with dry nitrogen to prevent moisture in the air from reacting with the mixture, stir at room temperature for 0.5-1 hour, and seal and store after discharge; Furthermore, when storing component B in a sealed container, dry nitrogen gas is introduced into the container for sealing. S3. Preparation of polyurethane composite material for automotive seats: The polyurethane composite material for automotive seats is obtained by uniformly mixing components A and B at a mass ratio of 100:38-48.

[0023] The present invention further provides an application of the aforementioned polyurethane composite material for automotive seats in the preparation of automotive seats.

[0024] Specifically, the application of the polyurethane composite material for automotive seats in the preparation of automotive seats involves injecting the polyurethane composite material for automotive seats into a seat mold, closing the mold, controlling the mold temperature at 60-75℃, and opening the mold after 4-6 minutes to obtain a polyurethane automotive seat.

[0025] Compared with the prior art, the present invention has achieved the following beneficial effects: The seat formulation provided by this invention uses polyether triol and isocyanate as the main ingredients. By adding low-emission silicone oils TEGOSTAB B8734 LF2 and TEGOSTAB B8736 LF2, using a low-emission, reactive amine catalyst, and adding antioxidants and aldehyde treatment agents to synergistically treat the odor and VOC generated in the reaction, the resulting seat foam has low VOC and odor, stable performance, and eliminates the need for external aldehyde treatment agents, reducing product manufacturing steps. Furthermore, all components are in liquid state, avoiding the problems of filter and nozzle clogging that may occur when using solid adsorbents. Detailed Implementation

[0026] The technical solution of the present invention will be further described below with reference to specific embodiments. These embodiments are only used to illustrate the technical solution of the present invention in more detail and should not be construed as limiting the scope of protection of the present invention.

[0027] Unless otherwise specified, all substances and reagents used in the following examples are commercially available products.

[0028] In the following examples, the polyether polyol used is 10LD76EK from Shandong Lanxing Dongda Co., Ltd., with a functionality of 3, a molecular weight of 5000, and a hydroxyl value of 32.5-35.5 mgKOH / g.

[0029] The grafted polyether polyol is HPOP-40 from Shandong Lanxing Dongda Co., Ltd., with a functionality of 3, a molecular weight of 8000, a hydroxyl value of 20-22 mgKOH / g, and a solid content of 39-41%.

[0030] The silicone oil used is Evonik Industries' TEGOSTAB B8734 LF2 and / or TEGOSTAB B8736 LF2.

[0031] The amine catalyst is one or more of the following: LE-503, ZR-50, Z-130, and ZF-10 from Huntsman Polyurethanes (China) Co., Ltd.

[0032] The crosslinking agent is at least one of diethanolamine, triethanolamine, and glycerol. Diethanolamine has a functionality of 3, a molecular weight of 105, and a hydroxyl value of 1600 mgKOH / g. Triethanolamine has a functionality of 3, a molecular weight of 149, and a hydroxyl value of 1130 mgKOH / g. Glycerol has a functionality of 3, a molecular weight of 92, and a hydroxyl value of 1830 mgKOH / g.

[0033] The open-cell polyether is JQN-3611 from Nanjing Jinqi Chemical Group Co., Ltd., with a functionality of 3, a molecular weight of 6000, and a hydroxyl value of 26-32 mgKOH / g.

[0034] The antioxidant is one or both of BASF's Irgastab® PUR-70 and Irganox® 1135.

[0035] The aldehyde treatment agent is JEFFADD® AS 76 from Huntsman Polyurethanes (China) Co., Ltd.

[0036] The TDI is preferably BASF's T-80; the PAPI is preferably BASF's M20S.

[0037] The components, weights, and foaming conditions of the following examples and comparative examples are shown in Table 1. Polyurethane composites for automotive seats were prepared in the following manner, and polyurethane foam products for automotive seats were prepared by reacting the polyurethane composites for automotive seats: S1. According to the components and proportions shown in Table 1, add the polyether polyol and grafted polyether polyol into the reactor and stir at 50 rpm for 0.5 hours. Add the crosslinking agent, silicone oil, amine catalyst, open-cell polyether, antioxidant, aldehyde treatment agent, and water in sequence. Close the feed pipeline and open the circulation pipeline from the bottom to the top of the reactor. Continue stirring for 1.5 hours to obtain component A, which can be stored in a sealed galvanized iron drum.

[0038] S2. Weigh TDI and PAPI according to the weight and ratio shown in Table 1 and put them into the reactor. Use dry nitrogen to seal the liquid surface to prevent moisture in the air from reacting with the mixture. Stir at 30 rpm for 0.5 hours at room temperature to obtain component B. After discharge, seal and store. S3. Preparation of polyurethane composite material for automotive seats: According to the mass ratio of component A to component B shown in Table 1, component A and component B are mixed uniformly to obtain polyurethane composite material for automotive seats. S4. Preparation of polyurethane car seats: Heat the mold to the temperature shown in Table 1, inject the polyurethane composite material for car seats obtained in S3 into the mold, and the time after mold closing is shown in Table 1 (the content of each component in Table 1 is by weight). After mold opening, polyurethane foam products are obtained.

[0039] The components and foaming conditions of the examples and comparative examples are described below in tabular form: Table 1. Component content and foaming conditions of Examples 1-4 and Comparative Examples 1-5 Note: BHT was purchased from Wuhan Mengqi Technology Co., Ltd.; activated carbon was 100 mesh and purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; B4113 was purchased from Evonik Industries, Y-10366 was purchased from Momentive Advanced Materials Group, catalyst A-1 was purchased from Dongguan Guangsiyuan Polyurethane Materials Co., Ltd., and catalyst A33 was purchased from Dongguan Guangsiyuan Polyurethane Materials Co., Ltd.

[0040] The polyurethane foam products prepared in Examples 1-4 and Comparative Examples 1-5 were tested according to the standards "ISO 12219-2-2012 Highway vehicle interior air - Part 2: Screening method for determining the amount of volatile organic compounds in vehicle interior parts and materials - bag method" and "PV3900-2000 Odor detection of automotive interior components". The test results are shown in Table 2.

[0041] Table 2. Detection results of Examples 1-4 and Comparative Examples 1-5 Note: ND indicates not detected (below the detection limit).

[0042] The results in Table 2 show that the embodiments of the present invention can reduce odor VOCs by optimizing the types of raw materials, thereby reducing the introduction of odor VOCs. A small amount of antioxidant combined with a formaldehyde remover can greatly reduce odor VOCs, but excessive amounts will increase the odor. Comparative Examples 1-4 have high levels of formaldehyde, acetaldehyde, toluene, and TVOC. Comparative Example 1 used a small amount of activated carbon, which had insufficient adsorption capacity for small molecule volatiles, and the use of a solid adsorbent caused significant wear on the foaming equipment. Comparative Example 2 used the antioxidant BHT, resulting in high TVOCs. Comparative Example 3 used a conventional organic amine catalyst, and the catalyst free in the foam led to high odors and VOCs. Comparative Example 4 used ordinary silicone oil, and the volatilization of the silicone oil led to high odors and VOCs. Comparative Example 5 had an increased odor due to the excessive addition of antioxidants.

[0043] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Any equivalent substitutions or modifications made by those skilled in the art within the spirit and principle of the present invention without any creative effort should be included within the protection scope of the present invention.

Claims

1. A polyurethane composite material for automotive seats, characterized in that: It consists of component A and component B, with a weight ratio of 100:38-48. By weight percentage, component A includes 40-60% polyether polyol, 30-50% grafted polyether polyol, 0.5-3% crosslinking agent, 0.5-3% silicone oil, 0.3-2% amine catalyst, 3-3.5% water, 0.5-4% open-cell polyether, 0.1-0.3% antioxidant and 0.1-0.8% aldehyde treatment agent. Component B includes 40-90% toluene diisocyanate and 10-60% polymethylene polyphenyl isocyanate. The antioxidant is a free radical chain blocking agent; The aldehyde treatment agent is an aldehyde scavenging agent; The silicone oil is a silicon-carbon chain type polysiloxane-oxidized olefin block copolymer; The amine catalyst is a tertiary amine containing hydroxyl groups.

2. The polyurethane composite material for automotive seats according to claim 1, characterized in that: The antioxidant is one or both of BASF's Irgastab® PUR-70 and Irganox® 1135; The aldehyde treatment agent is JEFFADD® AS 76 from Huntsman Polyurethanes (China) Co., Ltd. The silicone oil used is Evonik Industries' TEGOSTAB B8734 LF2 and / or TEGOSTAB B8736 LF2; The amine catalyst is two or three of the following: LE-503, ZR-50, Z-130, and ZF-10 from Huntsman Polyurethanes (China) Co., Ltd. The crosslinking agent has a functionality of 3 and a hydroxyl value of 1000-1830 mgKOH / g; The open-cell polyether is a polyol of epoxy-ethylene and epoxy-propylene co-ether with a functionality of 3, a molecular weight of 4000-7000, a hydroxyl value of 25-35 mgKOH / g, and epoxy-terminated.

3. The polyurethane composite material for automotive seats according to claim 1 or 2, characterized in that: The polyether polyol is a polyoxypropylene triol with a functionality of 3, a molecular weight of 4000-6000, a hydroxyl value of 27-42 mgKOH / g, and ethylene oxide-terminated. The grafted polyether polyol is a polyether polyol grafted with styrene or acrylonitrile, with a functionality of 3, a molecular weight of 6000-8000, and a solid content of 30-45%.

4. The polyurethane composite material for automotive seats according to claim 3, characterized in that: The polyether polyol is a polyoxypropylene triol with a functionality of 3, a molecular weight of 4500-5500, a hydroxyl value of 33-36 mgKOH / g, and ethylene oxide-terminated.

5. The polyurethane composite material for automotive seats according to claim 4, characterized in that: The polyether polyol used is 10LD76EK from Shandong Lanxing Dongda Co., Ltd. The grafted polyether polyol is HPOP-40 from Shandong Lanxing Dongda Co., Ltd.

6. The polyurethane composite material for automotive seats according to claim 2, characterized in that: The crosslinking agent is at least one of diethanolamine, triethanolamine, and glycerol; The open-cell polyether is JQN-3611 from Nanjing Jinqi Chemical Group Co., Ltd.

7. The polyurethane composite material for automotive seats according to claim 1 or 2, characterized in that: The toluene diisocyanate used is BASF's T-80; the polymethylene polyphenyl isocyanate used is BASF's M20S.

8. A method for preparing the polyurethane composite material for automotive seats according to any one of claims 1-7, characterized in that, Includes the following steps: Preparation of component S1.A: Add polyether polyol and grafted polyether polyol into the reactor according to the proportion and stir at 30-60 rpm for 0.5-1 hour. Then add crosslinking agent, silicone oil, amine catalyst, open-cell polyether, antioxidant, aldehyde treatment agent and water in sequence. Close the feed pipeline and open the circulation pipeline from the bottom to the top of the reactor. Continue stirring for 1.5-2 hours to obtain component A. Preparation of S2.B component: Add TDI and PAPI into the reactor according to the ratio, seal the liquid surface with dry nitrogen to prevent moisture in the air from reacting with the mixture, stir at room temperature for 0.5-1 hour, and seal and store after discharge; S3. Preparation of polyurethane composite material for automotive seats: The polyurethane composite material for automotive seats is obtained by uniformly mixing components A and B at a mass ratio of 100:38-48.

9. The use of the polyurethane composition for automotive seats according to any one of claims 1-7 in the manufacture of automotive seats.

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