Low-odor flame-retardant polyurethane foam material for vehicle-mounted refrigerator and preparation method thereof

Abstract

The invention discloses a low-odor flame-retardant polyurethane foam material for a vehicle-mounted refrigerator and a preparation method of the low-odor flame-retardant polyurethane foam material, and relates to the technical field of polyurethane. The specific polyether polyol A, polyether polyol B, polyether polyol C, the reaction type and low-odor catalyst, the formaldehyde removing agent, the antioxidant and the like are adopted, so that the prepared polyurethane foam material meets the automotive odor test requirement, the amount of aldehyde ketone emitted by foam is small, the flame retardant property is good, meanwhile, the specific heat conductivity coefficient is low, and demolding is rapid; and the high-temperature and low-temperature dimensional stability is good, so that the vehicle-mounted refrigerator can meet the functions of refrigerating and heating at the same time.

Description

Technical Field

[0001] The invention relates to the technical field of polyurethane, and in particular to a low-odor flame-retardant polyurethane foam material for a vehicle refrigerator and a preparation method thereof. Background Art

[0002] Since entering the Chinese market around 2000, car refrigerators have experienced more than 20 years of development and have now become an important part of the automotive supplies market. The participation of more than 500 companies has made the market competition more intense, while also promoting the continuous advancement of product technology. Faced with the increase in consumer demand and awareness of car refrigerators, the issue of insulation materials for car refrigerators has received increasing attention.

[0003] Rigid polyurethane foam materials have the characteristics of low thermal conductivity, low foam density and high strength. They are ideal filling materials for products such as refrigerators and freezers, and have been widely used in refrigerators, freezers and other fields. However, in the field of car refrigerators, the problems of this material cannot be ignored. First, the additives (such as catalysts, flame retardants, foam stabilizers, etc.) used in the production process of polyurethane foam materials and the volatiles (amines, aldehydes, alcohol ethers, alkanes, etc.) produced by side reactions will have an adverse effect on the air quality in the car and may even cause potential harm to human health. Secondly, the flame retardant properties of polyurethane foam materials are poor, which can easily cause fires and bring hidden dangers to driving safety. In this case, it is particularly important to develop a polyurethane foam material for car refrigerators with low odor and good flame retardancy. Summary of the invention

[0004] The technical problem to be solved by the present invention is: to overcome the shortcomings of the prior art, to provide a low-odor flame-retardant polyurethane foam material for a car refrigerator and a preparation method thereof, to meet the requirements of a vehicle odor test, to have a small amount of aldehyde and ketone emitted by the foam, and to have good flame retardant properties, and at the same time to have the characteristics of low thermal conductivity, rapid demoulding, and good high and low temperature dimensional stability, so that the car refrigerator can simultaneously meet the functions of cooling and heating.

[0005] The technical solution of the present invention is: In one aspect, the present invention provides a low-odor flame-retardant polyurethane foam material for a vehicle refrigerator, which is composed of a component A and a component B, wherein the mass ratio of the component A to the component B is 1:(1.1-1.3); wherein, in parts by weight, the component A includes the following components: Polyether polyol 45-52.5 parts; 10-16 parts of polyester polyol; Flame retardant 17-21 parts; 1.6-1.9 parts of deionized water; 11.3-15 parts of foaming agent; Foam stabilizer 1.6-2.5 parts; Catalyst 1.1-2.1 parts; 0.05-0.2 parts of formaldehyde remover; Antioxidant 0.05-0.3 parts; The polyether polyol comprises 27-39.5 parts of polyether polyol A, 9-15 parts of polyether polyol and 3-5 parts of polyether polyol C, wherein the polyether polyol A is prepared by using sucrose or sorbitol and one or two of glycerol, propylene glycol and ethylene glycol as composite initiators and propylene oxide as polymerization monomers, and is preferably one or more of R8315, R6048 and R6207 of Shandong Yinuowei New Materials Co., Ltd.; the polyether polyol B is prepared by using toluene diamine as initiator and propylene oxide as polymerization monomers. The polyol C is prepared from a polymerized monomer, with a hydroxyl value of 360-460 mgKOH / g and a viscosity of 12000-30000 mPa·s, preferably one or two of R4560 and R440T produced by Shandong Yinuowei New Materials Co., Ltd.; the polyether polyol C is prepared from propylene glycol or glycerol as an initiator and propylene oxide as a polymerized monomer, with a hydroxyl value of 100-500 mgKOH / g, preferably one or two of C305, C307 and C204 produced by Shandong Yinuowei New Materials Co., Ltd.; The catalyst is one or more of PT303, PT306, BX405, 2,4,6-tris(dimethylaminomethyl)phenol and trimethylhydroxyethylpropylenediamine; Component B is polymethyl polyphenyl polyisocyanate.

[0006] Preferably, the polyester polyol is a phthalic anhydride series polyol with a viscosity of 5000-12000 mPa·s at 25°C and an acid value of ≤1 mgKOH / g; preferably, the polyester polyol is one or both of PE-B175 (Shandong Yinuowei Polyurethane Co., Ltd.) and PS-3158 (Stepan (Nanjing) Chemical Co., Ltd.).

[0007] Preferably, the flame retardant is one or both of tris(2-chloropropyl) phosphate (TCPP) and triethyl phosphate (TEP).

[0008] Preferably, the foaming agent is LBA and cyclopentane (CP).

[0009] Preferably, the foam stabilizer is one or both of B84823 and B84813.

[0010] Preferably, the formaldehyde remover is one or two of ethylene urea, sodium bisulfite and biuret.

[0011] Preferably, the antioxidant is one or both of antioxidant 1135 and antioxidant CCHICNOX341.

[0012] On the other hand, the present invention provides a method for preparing the low-odor flame-retardant polyurethane foam material for a vehicle refrigerator, comprising the following steps: S1: prepare component A: evenly mix the flame retardant, deionized water and formaldehyde remover, add them to polyether polyol, polyester polyol, foam stabilizer, catalyst and antioxidant, add foaming agent after cooling, stir and put into barrel for later use; S2: Mixing and foaming the components A and B through a foaming machine to obtain a low-odor flame-retardant polyurethane foam material for a car refrigerator.

[0013] Preferably, in step S1, the stirring time is 0.5-1.5h.

[0014] Compared with the prior art, the present invention has the following beneficial effects: 1. The present invention adopts specific polyether polyol A, polyether polyol B and polyether polyol C, which have water addition and dehydration operations in the production process, so that the small molecular aldehydes and alcohols therein are removed, and the generation of odor is greatly reduced from the raw material aspect. At the same time, the present invention adopts a reactive and low-odor catalyst, which participates in the reaction and is connected to the macromolecular polyurethane chain during the reaction process, avoiding the strong irritating odor caused by the use of tertiary amine catalysts. At the same time, the catalytic process reduces the occurrence of side reactions and reduces the generation of small molecular aldehydes and ketones. In addition, the present invention adopts an aldehyde removal agent to further reduce the trace aldehyde substances in the foam, and adds an antioxidant to greatly reduce the odor generated by the foam during long-term use due to aging and oxidation. The polyurethane foam material prepared by the present invention meets the requirements of the automotive odor test, the odor is less than 3, the foam emits a small amount of aldehydes and ketones, and has good flame retardant properties. At the same time, it has the characteristics of low thermal conductivity and rapid demoulding, and good high and low temperature dimensional stability, so that the car refrigerator can simultaneously meet the functions of refrigeration and heating.

[0015] 2. The polyester polyol and flame retardant used in the present invention are both processed low-VOC products, which further reduce the generation of odor from the raw material aspect; at the same time, the flame retardant used in the present invention has good flame retardant effect and a light aromatic smell, which reduces the generation of irritating odor. DETAILED DESCRIPTION

[0016] In order to enable persons skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention.

[0017] Ethylene urea, Mitsui Chemicals (Shandong) Co., Ltd.; Sodium bisulfite, Jinan Jiayang Chemical Co., Ltd.; Biuret, Shandong Xiangzhao New Materials Co., Ltd.; TCPP, Zhejiang Wansheng Chemical Co., Ltd.; TEP, Xuzhou Yongli Fine Chemical Co., Ltd.; LBA, Honeywell; Cyclopentane, Shandong Jingbo Petrochemical Co., Ltd.; Catalysts PT303, PT306, BX405, 2,4,6-tris(dimethylaminomethyl)phenol, Evonik Specialty Chemicals (Shanghai) Co., Ltd.; Trimethylolethylpropylenediamine, Xindian Chemical Materials (Shanghai) Co., Ltd.

[0018] Example 1 The method for preparing the low-odor flame-retardant polyurethane foam material for a vehicle refrigerator of this embodiment comprises the following steps: S1: Prepare component A: weigh 0.15 parts of ethylene urea, 1.8 parts of deionized water, 17 parts of TCPP and 2 parts of TEP, mix well, add 25 parts of R6048, 14.5 parts of R6207, 10 parts of R4560, 3 parts of C305, 10 parts of PS-3158, 0.3 parts of PT303, 1.2 parts of BX405, 2.5 parts of B84823 and 0.05 parts of antioxidant 1135, cool to 22°C, add 10 parts of CP and 2.5 parts of LBA, stir for 1.2 hours and then put into barrel for use; S2: Mix and foam component A and component B in a mass ratio of 1:1.2 through a foaming machine, wherein component B is polymethyl polyphenyl polyisocyanate, to obtain a low-odor flame-retardant polyurethane foam material for a car refrigerator.

[0019] Example 2 The method for preparing the low-odor flame-retardant polyurethane foam material for a vehicle refrigerator of this embodiment comprises the following steps: S1: Prepare component A: weigh 0.1 parts of sodium bisulfite, 0.1 parts of biuret, 1.6 parts of deionized water, 10 parts of TCPP and 7 parts of TEP, mix well, add 25 parts of R8315, 10 parts of R6207, 11 parts of R440T, 4 parts of C307, 16 parts of PE-B175, 0.2 parts of PT303, 0.9 parts of PT306, 0.7 parts of 2,4,6-tris(dimethylaminomethyl)phenol, 2 parts of B84813 and 0.1 parts of antioxidant CHICNOX341, cool to 22°C, add 9 parts of CP and 2.3 parts of LBA, stir for 1 hour and then put into barrel for use; S2: Mix and foam component A and component B in a mass ratio of 1:1.1 through a foaming machine, wherein component B is polymethyl polyphenyl polyisocyanate, to obtain a low-odor flame-retardant polyurethane foam material for a car refrigerator.

[0020] Example 3 The method for preparing the low-odor flame-retardant polyurethane foam material for a vehicle refrigerator of this embodiment comprises the following steps: S1: Prepare component A: weigh 0.18 parts of biuret, 1.9 parts of deionized water and 18 parts of TEP, mix well, add 20 parts of R6048, 11 parts of R6207, 5 parts of R440T, 8 parts of R4560, 3 parts of C307, 2 parts of C204, 14 parts of PE-B175, 0.3 parts of PT303, 0.9 parts of BX405, 0.9 parts of trimethylolethylpropylenediamine, 1 part of B84813, 0.6 parts of B84823, 0.1 parts of antioxidant CHICNOX341 and 0.08 parts of antioxidant 1135, cool to 22°C, add 10 parts of CP and 3.1 parts of LBA, stir for 1.5 hours and then put into barrel for use; S2: Mix and foam component A and component B in a mass ratio of 1:1.3 through a foaming machine, wherein component B is polymethyl polyphenyl polyisocyanate, to obtain a low-odor flame-retardant polyurethane foam material for a car refrigerator.

[0021] Example 4 The method for preparing the low-odor flame-retardant polyurethane foam material for a vehicle refrigerator of this embodiment comprises the following steps: S1: Prepare component A: weigh 0.05 parts of ethylene urea, 1.8 parts of deionized water, 17 parts of TCPP and 4 parts of TEP, mix well, add 20 parts of R6048, 7 parts of R8315, 5 parts of R440T, 10 parts of R4560, 3 parts of C305, 2 parts of C204, 13 parts of PS-3158, 0.9 parts of PT303, 0.2 parts of trimethylolethylpropylenediamine, 1.75 parts of B84813, 0.1 parts of antioxidant CHICNOX341 and 0.2 parts of antioxidant 1135, cool to 22°C, add 12 parts of CP and 2 parts of LBA, stir for 0.5h and then put into barrel for use; S2: Mix and foam component A and component B in a mass ratio of 1:1.2 through a foaming machine, wherein component B is polymethyl polyphenyl polyisocyanate, to obtain a low-odor flame-retardant polyurethane foam material for a car refrigerator.

[0022] Example 5 The method for preparing the low-odor flame-retardant polyurethane foam material for a vehicle refrigerator of this embodiment comprises the following steps: S1: Prepare component A: weigh 0.03 parts of ethylene urea, 0.09 parts of sodium bisulfite, 1.6 parts of deionized water, 13 parts of TCPP and 6 parts of TEP, mix well, add 16 parts of R6048, 12 parts of R6207, 14 parts of R440T, 3 parts of C305, 9 parts of PS-3158, 6 parts of PE-B175, 1 part of PT303, 0.75 parts of 2,4,6-tris(dimethylaminomethyl)phenol, 2.3 parts of B84823 and 0.23 parts of antioxidant 1135, cool to 22°C, add 12 parts of CP and 3 parts of LBA, stir for 1.5 hours and then put into barrel for use; S2: Mix and foam component A and component B in a mass ratio of 1:1.2 through a foaming machine, wherein component B is polymethyl polyphenyl polyisocyanate, to obtain a low-odor flame-retardant polyurethane foam material for a car refrigerator.

[0023] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that in step S1, the catalyst PC-8 is used to replace the catalyst PT303, BX405 and dimethyldiethanolamine in Example 1 in equal amounts.

[0024] Comparative Example 2 The difference between Comparative Example 2 and Example 2 is that in step S1, the formaldehyde removal agents sodium bisulfite and biuret are not added.

[0025] Comparative Example 3 The difference between Comparative Example 3 and Example 2 is that in step S1, the flame retardants TCPP and TEP are not added.

[0026] Comparative Example 4 The difference between Comparative Example 4 and Example 2 is that in step S1, polyether polyol R5118G is used to replace polyether polyol R8315 in Example 1.

[0027] Comparative Example 5 The difference between Comparative Example 5 and Example 2 is that in step S1, an equal amount of polyether polyol C307 is used to replace polyether polyol R440T.

[0028] The polyurethane foam materials prepared in Examples 1-5 and Comparative Examples 1-5 were tested for performance, and the test results are shown in Table 1-2. The core density of the polyurethane foam material was tested with reference to GB / T6343, the compressive strength was tested with reference to GB / T8813-2020, the closed cell rate was tested with reference to GB / T 10799-2008, the thermal conductivity was tested with reference to GB / T 10295-2008, the dimensional stability was tested with reference to GB / T 8811-2008, the combustion performance was tested with reference to GB / T 8332-2008, and the odor was tested with reference to QC / T 703-2004; the specific test method for demoulding is as follows: in a 30cm×30cm×10cm mold, according to the overall density of 35kg / m 3 Add materials, demould at the specified demoulding time, and test the foam thickness and size expansion.

[0029] Table 1 Performance test results of polyurethane foam materials prepared in Examples 1-5

[0030] Table 2 Performance test results of polyurethane foam materials prepared in Comparative Examples 1-5

[0031] It can be seen from Table 1-2 that the low-odor flame-retardant polyurethane foam materials for car refrigerators prepared in Examples 1-5 of the present invention have the characteristics of low odor, good flame retardancy, low thermal conductivity, and good high and low temperature dimensional stability. In combination with Example 1 and Comparative Example 1, it can be seen that when the conventional catalyst PC8 is replaced in the combined polyether, the odor of the foam becomes larger and cannot meet the requirement of odor <3, indicating that the reactive catalyst used in the present invention plays a key role in reducing the odor of the foam. In combination with Example 2 and Comparative Example 2, it can be seen that when no formaldehyde removal agent is added to the combined polyether, the odor of the foam cannot meet the requirement of <3, indicating that the formaldehyde removal agent can play a role in reducing the odor of the foam. In combination with Example 2 and Comparative Example 3, it can be seen that not adding a flame retardant will cause the combustion performance of the material to not meet the requirements. In combination with Example 2 and Comparative Example 4, it can be seen that when conventional rigid foam polyether is used, the odor will also exceed the standard. Combining Example 2 and Comparative Example 5, it can be seen that when polyether polyol R440T is not added but polyether polyol C307 is added, although the odor and flame retardancy meet the requirements, the thermal conductivity and demoulding performance are greatly affected. In summary, the formaldehyde removal agent and catalyst used in the present invention have a significant improvement in the odor of the polyurethane foam material. Under the premise of controlling the odor of the polyether and the flame retardant, the odor of the polyurethane foam material can be reduced to less than 3.

Claims

1. A low-odor flame-retardant polyurethane foam material for a car refrigerator, characterized in that: It is composed of component A and component B, and the mass ratio of component A to component B is 1: (1.1-1.3); wherein, in parts by weight, component A includes the following components: 45-52.5 parts of polyether polyol; 10-16 parts of polyester polyol; Flame retardant 17-21 parts; 1.6-1.9 parts of deionized water; 11.3-15 parts of foaming agent; Foam stabilizer 1.6-2.5 parts; Catalyst 1.1-2.1 parts; 0.05-0.2 parts of formaldehyde remover; Antioxidant 0.05-0.3 parts; The polyether polyol comprises 27-39.5 parts of polyether polyol A, 9-15 parts of polyether polyol and 3-5 parts of polyether polyol C, wherein polyether polyol A is one or more of R8315, R6048 and R6207, polyether polyol B is one or two of R4560 and R440T, and polyether polyol C is one or two of C305, C307 and C204; The catalyst is one or more of PT303, PT306, BX405, 2,4,6-tris(dimethylaminomethyl)phenol and trimethylhydroxyethylpropylenediamine; Component B is polymethyl polyphenyl polyisocyanate.

2. The low-odor flame-retardant polyurethane foam material for a vehicle refrigerator according to claim 1, characterized in that: The polyester polyol is a phthalic anhydride series polyol with a viscosity of 5000-12000 mpa·s at 25° C. and an acid value of ≤1 mgKOH / g; preferably, the polyester polyol is one or both of PE-B175 and PS-3158.

3. The low-odor flame-retardant polyurethane foam material for a vehicle refrigerator according to claim 1, characterized in that: The flame retardant is one or both of tris(2-chloropropyl) phosphate and triethyl phosphate.

4. The low-odor flame-retardant polyurethane foam material for a vehicle refrigerator according to claim 1, characterized in that: The foaming agents are LBA and cyclopentane.

5. The low-odor flame-retardant polyurethane foam material for a vehicle refrigerator according to claim 1, characterized in that: The foam stabilizer is one or both of B84823 and B84813.

6. The low-odor flame-retardant polyurethane foam material for a vehicle refrigerator according to claim 1, characterized in that: The formaldehyde remover is one or two of ethylene urea, sodium bisulfite and biuret.

7. The low-odor flame-retardant polyurethane foam material for a vehicle refrigerator according to claim 1, characterized in that: The antioxidant is one or both of antioxidant 1135 and antioxidant CCHICNOX341.

8. The method for preparing the low-odor flame-retardant polyurethane foam material for a vehicle refrigerator according to any one of claims 1 to 7, characterized in that: The following steps are involved: S1: prepare component A: evenly mix the flame retardant, deionized water and formaldehyde remover, add them to polyether polyol, polyester polyol, foam stabilizer, catalyst and antioxidant, add foaming agent after cooling, stir and put into barrel for later use; S2: Mixing and foaming the components A and B through a foaming machine to obtain a low-odor flame-retardant polyurethane foam material for a car refrigerator.

9. The method for preparing the low-odor flame-retardant polyurethane foam material for a vehicle refrigerator according to claim 8, characterized in that: In step S1, the stirring time is 0.5-1.5h.

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