Automobile interior material and method for manufacturing the same

Abstract

This invention relates to the field of polymer materials, specifically to an automotive interior material and its preparation method, comprising PVC resin and a composite heat stabilizer; the composite heat stabilizer comprises a calcium-zinc heat stabilizer, a polyol phosphate ester, and amino POSS, wherein the mass ratio of the PVC resin to the composite heat stabilizer is 20-40:1, and the mass ratio of the calcium-zinc heat stabilizer, the polyol phosphate ester, and the amino POSS is 1-5:1-5:1-5. The automotive interior material prepared by this invention has good thermal stability and mechanical properties, and excellent heat aging resistance.

Description

Technical Field

[0001] This invention relates to the field of polymer materials, specifically to an automotive interior material and its preparation method. Background Technology

[0002] The automotive interior system is an important component of the car body, and the design workload of the interior system accounts for more than 60% of the total design workload of the car styling, far exceeding that of the car exterior, making it one of the most important parts of the car body.

[0003] Traditional automotive interior materials are mostly made of PVC, but PVC has poor stability to light and heat. It will degrade and age under light or high temperature environments, resulting in a decline in mechanical properties. Although the impact of light can be reduced by applying film, in summer, when cars are exposed to the outdoors for a long time, the interior temperature can often reach over 70°C. This will undoubtedly accelerate the degradation and aging of PVC materials, causing a decline in the performance of automotive interior materials. Summary of the Invention

[0004] Purpose of the invention: To address the above-mentioned technical problems, this invention proposes an automotive interior material and its preparation method.

[0005] The technical solution adopted is as follows:

[0006] An automotive interior material comprising PVC resin and a composite heat stabilizer;

[0007] The composite heat stabilizer includes calcium-zinc heat stabilizer, polyol phosphate ester, and aminoPOSS.

[0008] Furthermore, the mass ratio of the PVC resin to the composite heat stabilizer is 20-40:1.

[0009] Furthermore, the mass ratio of the calcium-zinc heat stabilizer, polyol phosphate ester, and amino POSS is 1-5:1-5:1-5.

[0010] Furthermore, the structural formula of the polyol phosphate ester is shown below:

[0011]

[0012] Wherein, R1 and R2 are each independently a C1-C10 alkyl group or a C6-C30 aryl group. Further, R1 and R2 are each independently a C6-C10 alkyl, phenyl, or biphenyl group. Further, the polyol phosphate ester is any one or more combinations of the following compounds:

[0013]

[0014]

[0015] Furthermore, the amino POSS is octa-aminophenyl POSS and / or N-phenylamino POSS.

[0016] Furthermore, it also includes ACR, CPE, heavy calcium carbonate, titanium dioxide, polyethylene wax, and paraffin wax.

[0017] This invention also provides a method for preparing automotive interior materials:

[0018] After mixing PVC resin, composite heat stabilizer, ACR, CPE, heavy calcium carbonate, titanium dioxide, polyethylene wax and paraffin wax, the mixture is plasticized on a two-roll plasticizer, and then demolded and cut after hot pressing in a flat vulcanizing machine.

[0019] Furthermore, the hot-pressing temperature is 170-190℃, the hot-pressing pressure is 5-15MPa, and the hot-pressing time is 5-10min.

[0020] The beneficial effects of this invention are:

[0021] This invention provides an automotive interior material. PVC molecules have some unstable defect structures. It is precisely because of the existence of these defect structures that PVC materials are prone to degradation at high temperatures. In this invention, the calcium-zinc heat stabilizer can replace the unstable structures of allyl chloride, tertiary chloride, secondary chloride, etc., reduce unstable factors, solve the heat stability problem from the root, and also reduce autocatalysis by absorbing and neutralizing HCl generated in the system.

[0022] In this invention, polyol phosphate ester is used as an auxiliary heat stabilizer. The hydroxyl groups in its structure can coordinate with the metal ions in the calcium-zinc heat stabilizer, neutralize or complex some byproducts produced by the stabilizer, and play a stabilizing role. It can effectively improve the static heat stabilization time. The phosphite structure can replace the chlorine atom at the allyl position or combine with the generated conjugated diene structure to destroy its conjugation effect, which can effectively improve the initial whiteness and thermal stability of the product.

[0023] The Si-O and Si-C inorganic cores in the amino POSS structure of this invention have excellent heat resistance and flame retardancy, and play a positive role in improving the thermal stability and mechanical properties of PVC. This may be because amino groups can form chelates with zinc ions, inhibiting "zinc burning" and thus maintaining long-term thermal stability.

[0024] The automotive interior material prepared by this invention has good thermal stability and mechanical properties, and excellent heat aging resistance. Attached Figure Description

[0025] Figure 1 The image shows a SEM image of the automotive interior material prepared in Example 1, which reveals that its surface is uniform and dense. Detailed Implementation

[0026] Unless otherwise specified in the examples, the conditions were performed under standard conditions or as recommended by the manufacturer. Reagents or instruments whose manufacturers are not specified are all commercially available products. Techniques not mentioned in this invention refer to existing technologies. Unless otherwise specified, the following examples and comparative examples are parallel experiments, using the same processing steps and parameters.

[0027] PVC resin: QS-1000F, Sinopec;

[0028] Calcium-zinc heat stabilizer: STA-102CA, Qingyang Ruiying Plastic & Chemical Sales Co., Ltd.;

[0029] Polyol phosphates: self-made;

[0030] Octaaminophenyl POSS: CAS 518359-82-5, Shanghai Shiyang Chemical Co., Ltd.;

[0031] N-Phenylano POSS: CAS1708993-28-5, Forsmann Technology (Beijing) Co., Ltd.;

[0032] ACR: Kanekachi PA20 (Japan);

[0033] CPE: Runfeng Synthetic Technology;

[0034] Heavy calcium carbonate: Guangdong Yongfeng Chemical Co., Ltd.;

[0035] Titanium dioxide: Guangdong Yongfeng Chemical Co., Ltd.;

[0036] Polyethylene wax: Dongguan Dingxin Plastic Raw Materials Co., Ltd.;

[0037] Paraffin wax: Dongguan Dingxin Plastic Raw Materials Co., Ltd.

[0038] Example 1:

[0039] This embodiment provides an automotive interior material, the specific formula of which is as follows (by weight):

[0040] 100 parts PVC resin, 2 parts calcium-zinc heat stabilizer, 1 part polyol phosphate, 1 part octa-aminophenyl POSS, 5 parts ACR, 5 parts CPE, 25 parts heavy calcium carbonate, 5 parts titanium dioxide, 0.5 parts polyethylene wax, and 0.5 parts paraffin wax.

[0041] The structural formula of the polyol phosphate ester is shown below:

[0042]

[0043] The preparation method of polyol phosphate esters is as follows:

[0044]

[0045] In a four-necked flask equipped with a powerful stirrer, condenser, and thermometer, add 75g of toluene and 101g of epoxidized glycerol hydrolysed castor oil polyol, mix well, and heat to 40°C. Then, slowly add a mixed solution (composed of 75g toluene, 95g didecyl phosphate, and 0.5g triphenylphosphine) dropwise over 0.5 hours. After the addition is complete, raise the temperature to 75°C and react for 5 hours. After the reaction is complete, return to room temperature, neutralize the pH of the reaction system to 7 with 1mol / L sodium hydroxide solution, and then remove small molecules by vacuum distillation.

[0046] The preparation method of the above-mentioned automotive interior materials is as follows:

[0047] After mixing PVC resin, calcium-zinc heat stabilizer, polyol phosphate, octa-aminophenyl POSS, ACR, CPE, heavy calcium carbonate, titanium dioxide, polyethylene wax and paraffin wax, the mixture is plasticized at 160°C for 5 minutes on a two-roll plasticizer. Then, it is hot-pressed at 180°C and 15MPa for 10 minutes on a flat vulcanizing machine. After cooling to room temperature, it is demolded and cut.

[0048] Example 2:

[0049] This embodiment provides an automotive interior material, the specific formula of which is as follows (by weight):

[0050] 100 parts PVC resin, 2 parts calcium-zinc heat stabilizer, 1 part polyol phosphate, 1 part octa-aminophenyl POSS, 5 parts ACR, 5 parts CPE, 25 parts heavy calcium carbonate, 5 parts titanium dioxide, 0.5 parts polyethylene wax, and 0.5 parts paraffin wax.

[0051] The structural formula of the polyol phosphate ester is shown below:

[0052]

[0053] The preparation method of polyol phosphate esters is as follows:

[0054]

[0055] In a four-necked flask equipped with a powerful stirrer, condenser, and thermometer, add 75g of toluene and 101g of epoxidized glycerol hydrolysed castor oil polyol, mix well, and heat to 40°C. Then, slowly add a mixed solution (composed of 75g of toluene, 78.5g of monodecylphenyl phosphate, and 0.5g of triphenylphosphine) dropwise over 0.5h. After the addition is complete, raise the temperature to 75°C and react for 5h. After the reaction is complete, return to room temperature, neutralize the pH of the reaction system to 7 with 1mol / L sodium hydroxide solution, and then remove small molecules by vacuum distillation.

[0056] The preparation method of the above-mentioned automotive interior materials is as follows:

[0057] After mixing PVC resin, calcium-zinc heat stabilizer, polyol phosphate, octa-aminophenyl-POSS, ACR, CPE, heavy calcium carbonate, titanium dioxide, polyethylene wax and paraffin wax, the mixture is plasticized at 160°C for 5 minutes on a two-roll plasticizer. Then, it is hot-pressed at 180°C and 15MPa for 10 minutes on a flat vulcanizing machine. After cooling to room temperature, it is demolded and cut.

[0058] Example 3:

[0059] This embodiment provides an automotive interior material, the specific formula of which is as follows (by weight):

[0060] 100 parts PVC resin, 2 parts calcium-zinc heat stabilizer, 2 parts polyol phosphate, 1 part octa-aminophenyl POSS, 5 parts ACR, 5 parts CPE, 25 parts heavy calcium carbonate, 5 parts titanium dioxide, 0.5 parts polyethylene wax, and 0.5 parts paraffin wax.

[0061] The structural formula of the polyol phosphate ester is shown below:

[0062]

[0063] The preparation method of polyol phosphate is the same as in Example 1.

[0064] The preparation method of the above-mentioned automotive interior materials is as follows:

[0065] After mixing PVC resin, calcium-zinc heat stabilizer, polyol phosphate, octa-aminophenyl POSS, ACR, CPE, heavy calcium carbonate, titanium dioxide, polyethylene wax and paraffin wax, the mixture is plasticized at 160°C for 5 minutes on a two-roll plasticizer. Then, it is hot-pressed at 180°C and 15MPa for 10 minutes on a flat vulcanizing machine. After cooling to room temperature, it is demolded and cut.

[0066] Example 4:

[0067] This embodiment provides an automotive interior material, the specific formula of which is as follows (by weight):

[0068] 100 parts PVC resin, 2 parts calcium-zinc heat stabilizer, 1 part polyol phosphate, 2 parts octa-aminophenyl POSS, 5 parts ACR, 5 parts CPE, 25 parts heavy calcium carbonate, 5 parts titanium dioxide, 0.5 parts polyethylene wax, and 0.5 parts paraffin wax.

[0069] The structural formula of the polyol phosphate ester is shown below:

[0070]

[0071] The preparation method of polyol phosphate is the same as in Example 1.

[0072] The preparation method of the above-mentioned automotive interior materials is as follows:

[0073] After mixing PVC resin, calcium-zinc heat stabilizer, polyol phosphate, octa-aminophenyl POSS, ACR, CPE, heavy calcium carbonate, titanium dioxide, polyethylene wax and paraffin wax, the mixture is plasticized at 160°C for 5 minutes on a two-roll plasticizer. Then, it is hot-pressed at 180°C and 15MPa for 10 minutes on a flat vulcanizing machine. After cooling to room temperature, it is demolded and cut.

[0074] Example 5:

[0075] This embodiment provides an automotive interior material, the specific formula of which is as follows (by weight):

[0076] 100 parts PVC resin, 2 parts calcium-zinc heat stabilizer, 1 part polyol phosphate, 1 part N-phenylamino POSS, 5 parts ACR, 5 parts CPE, 25 parts heavy calcium carbonate, 5 parts titanium dioxide, 0.5 parts polyethylene wax, and 0.5 parts paraffin wax.

[0077] The structural formula of the polyol phosphate ester is shown below:

[0078]

[0079] The preparation method of polyol phosphate is the same as in Example 1.

[0080] The preparation method of the above-mentioned automotive interior materials is as follows:

[0081] After mixing PVC resin, calcium-zinc heat stabilizer, polyol phosphate, N-phenylamino POSS, ACR, CPE, heavy calcium carbonate, titanium dioxide, polyethylene wax and paraffin wax, the mixture is plasticized at 160°C for 5 minutes on a two-roll plasticizer. Then, it is hot-pressed at 180°C and 15MPa for 10 minutes on a flat vulcanizing machine. After cooling to room temperature, it is demolded and cut.

[0082] Comparative Example 1:

[0083] It is basically the same as Example 1, except that no polyol phosphate is added.

[0084] Comparative Example 2:

[0085] It is basically the same as Example 1, except that phenyl diisooctyl phosphite (CAS: 522-21-1) is used instead of polyol phosphate.

[0086] Comparative Example 3:

[0087] It is basically the same as Example 1, except that trinonyl phosphite (CAS: 26569-53-9) is used instead of polyol phosphate.

[0088] Comparative Example 4:

[0089] It is basically the same as Example 1, except that trioctyl phosphite (CAS: 3028-88-4) is used instead of polyol phosphate.

[0090] Comparative Example 5:

[0091] It is basically the same as Example 1, except that octa-aminophenyl POSS is not added.

[0092] Comparative Example 6:

[0093] It is basically the same as Example 1, except that octa-epoxysilsesquioxane (CAS: 68611-45-0) is used instead of octa-aminophenyl POSS.

[0094] Performance testing:

[0095] The automotive interior materials from Examples 1-5 and Comparative Examples 1-6 were prepared into corresponding samples for performance testing.

[0096] The thermal stability test was conducted in accordance with the GB / T 2917.1-2002 method, and the time for Congo red test paper to turn blue was used to characterize the thermal stability.

[0097] The notched impact strength of the specimens was tested using a simply supported beam impact testing machine in accordance with GB / T 1043-1993. The tensile properties of the specimens were tested using an electronic tensile testing machine in accordance with GB / T 1040.1-2018. The tensile speed was 50 mm / min and the test temperature was 23℃.

[0098] Aging resistance test method: The sample is placed in a thermal aging test oven and heated in air at 120°C to test the notched impact strength and tensile strength for 144 hours. After the test, the rate of decrease in relevant mechanical properties is calculated.

[0099] The test results are shown in Table 1 below:

[0100] Table 1:

[0101]

[0102] As shown in Table 1 above, the automotive interior material prepared by this invention has good thermal stability and mechanical properties, and excellent heat aging resistance.

[0103] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. An automotive interior material, characterized in that, It is composed of PVC resin, composite heat stabilizer, ACR, CPE, heavy calcium carbonate, titanium dioxide, polyethylene wax and paraffin wax; The composite heat stabilizer is composed of calcium-zinc heat stabilizer, polyol phosphate ester and amino POSS; The mass ratio of the PVC resin to the composite heat stabilizer is 20-40:1; The mass ratio of the calcium-zinc heat stabilizer, polyol phosphate ester and amino POSS is 1-5:1-5:1-5; The polyol phosphate is any one or a combination of the following compounds: ; ； 。 2. The automotive interior material as described in claim 1, characterized in that, The amino POSS is octa-aminophenyl POSS and / or N-phenylamino POSS.

3. A method for preparing automotive interior material as described in claim 1 or 2, characterized in that, After mixing PVC resin, composite heat stabilizer, ACR, CPE, heavy calcium carbonate, titanium dioxide, polyethylene wax and paraffin wax, the mixture is plasticized on a two-roll plasticizer, and then demolded and cut after hot pressing in a flat vulcanizing machine.

4. The method for preparing automotive interior materials as described in claim 3, characterized in that, The hot pressing temperature is 170-190℃, the hot pressing pressure is 5-15MPa, and the hot pressing time is 5-10min.

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