A heat-resistant flame-retardant material and a preparation method and application thereof

Abstract

The application discloses a kind of heat-resistant flame-retardant materials and its preparation method and application, belong to the technical field of automotive interior materials.The preparation method of the heat-resistant flame-retardant material includes the following steps: filler is added to deionized water under 30-50 ℃ ultrasonic treatment 1-2h, obtain suspension;Drop silicate aqueous solution in suspension until reach gel point, and constant temperature treatment 20-40min under 25-35 ℃, again 70-90 ℃ aging treatment 2-5h, wash, dry, obtain modified silica gel;Hydroxypropyl-β-cyclodextrin is dissolved in acetone under 32-45 ℃, add RDP, stir 3-8h, filter, wash, obtain modified resorcinol bis (diphenyl phosphate) ;Modified silica gel is pretreated, then add modified resorcinol bis (diphenyl phosphate) And adjuvant, and stir evenly at room temperature, obtain heat-resistant flame-retardant material.The heat-resistant flame-retardant material and its preparation method and application can effectively balance the flame retardancy and heat resistance of material, improve the safety and stability of automotive interior during use.

Description

TECHNICAL FIELD

[0001] The application relates to a heat-resistant flame-retardant material and a preparation method and application thereof, and belongs to the technical field of automotive interior materials. BACKGROUND

[0002] With the progress and development of society and the improvement of people's living standards, automobiles have become very common means of transportation, bringing us convenience and playing a very important role in transportation storage. Automotive interior mainly refers to automobile products used for automotive interior modification, involving all aspects of the automotive interior, such as steering wheel covers, seat cushions, floor mats, sealing strips, ornaments, storage boxes and the like. Among them, the steering wheel cover made of silica gel material has good grip and anti-slip properties, strong comfort, and can provide additional shock absorption and noise reduction effects.

[0003] In order to improve the safety performance of the automobile, it is usually required that the automotive interior has a flame-retardant effect. Although silica gel has a high ignition point, it may still burn under certain conditions, so additional flame retardants are usually added in actual applications to ensure its flame-retardant effect. Resorcinol bis(diphenyl phosphate), referred to as RDP, can improve the flame-retardant properties of silica gel as a flame retardant. However, the addition of resorcinol bis(diphenyl phosphate) will also cause the heat distortion temperature of silica gel to decrease, because resorcinol bis(diphenyl phosphate) decomposes and releases heat at high temperatures, causing the silica gel material to soften or even melt. Therefore, after the automobile is exposed to the sun for a long time in hot summer, the steering wheel cover will soften and deform, directly affecting the user's experience. SUMMARY

[0004] In order to solve the above problems, a heat-resistant flame-retardant material and a preparation method and application thereof are provided, which can effectively balance the flame-retardant property and heat resistance of the material, and improve the safety and stability of the automotive interior during use.

[0005] The application is realized by the following technical solutions:

[0006] According to one aspect of the application, a preparation method of a heat-resistant flame-retardant material is provided, comprising the following steps:

[0007] (1) adding a filler to deionized water, and ultrasonically treating at 30-50 DEG C for 1-2 h to obtain a suspension;

[0008] (2) adding a silicate aqueous solution dropwise to the suspension of step (1) until the gel point is reached, and treating at 25-35 DEG C for 20-40 min, and then aging at 70-90 DEG C for 2-5 h, washing, and drying to obtain modified silica gel;

[0009] (3) dissolving hydroxypropyl-beta-cyclodextrin in acetone at 32-45℃, adding resorcinol bis(diphenyl phosphate), stirring for 3-8h, filtering, washing, to obtain modified resorcinol bis(diphenyl phosphate);

[0010] (4) after pretreating the modified silica gel, adding the modified resorcinol bis(diphenyl phosphate) and the additive, and stirring uniformly at room temperature, to obtain the heat-resistant and flame-retardant material.

[0011] Optionally, the filler is composed of vermiculite, illite and kaolin with a mass ratio of 1:(0.5-1.5):(0.8-2).

[0012] Optionally, in step (1), the content of the filler in the deionized water is 15-28wt%.

[0013] The ultrasonic power is 300-600w, and the ultrasonic frequency is 20-50KHz.

[0014] Optionally, in step (2), the volume ratio of the suspension to the aqueous silicate solution is 1:(0.1-3).

[0015] Optionally, in step (3), the content of the hydroxypropyl-beta-cyclodextrin in the acetone is 35-50wt%.

[0016] The mass ratio of the hydroxypropyl-beta-cyclodextrin to the resorcinol bis(diphenyl phosphate) is (20-40):1.

[0017] Optionally, in step (4), the pretreatment of the modified silica gel is: irradiating the modified silica gel under ultraviolet light with a wavelength of 300-400nm for 40-60min under the action of a photoinitiator.

[0018] The addition amount of the photoinitiator is 3-7wt% of the modified silica gel.

[0019] Optionally, the photoinitiator is one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxy-cyclohexyl phenyl ketone, benzoin n-butyl ether, and diethoxyphenyl ethanone.

[0020] Optionally, in step (4), the mass ratio of the modified silica gel, the modified resorcinol bis(diphenyl phosphate) and the additive is 1:(0.3-0.8):(0.05-0.1).

[0021] The additive is sodium dodecyl sulfate, octylphenol polyoxyethylene ether or polyethylene glycol.

[0022] According to another aspect of the present application, a heat-resistant and flame-retardant material prepared by the method for preparing the heat-resistant and flame-retardant material according to any one of the above aspects is provided.

[0023] According to yet another aspect of the present application, there is provided a use of the heat-resistant flame-retardant material as described above in the preparation of an automotive interior.

[0024] In the present application, "room temperature" refers to 20-30°C.

[0025] The beneficial effects of the present application include, but are not limited to:

[0026] 1. The heat-resistant flame-retardant material of the present application can not only reduce the amount of resorcinol bis(diphenyl phosphate) by uniformly dispersing the filler in the silica gel, but also improve the heat resistance and flame retardance of the material, so that it can maintain stable structure and performance under high temperature environment, thereby improving the durability and reliability of the material; through constant temperature and aging treatment, the modified silica gel has a good three-dimensional network structure and pore structure, which is not only beneficial to improving the mechanical strength and porosity of the material, but also plays an important role in improving the heat resistance and flame retardance of the material.

[0027] 2. The heat-resistant flame-retardant material of the present application, in which the high-phosphorus resorcinol bis(diphenyl phosphate) is wrapped by hydroxypropyl-β-cyclodextrin, weakens the plasticizing effect of resorcinol bis(diphenyl phosphate), reduces the possibility of deformation of the material under high temperature conditions, and effectively improves the dispersity of resorcinol bis(diphenyl phosphate) in the heat-resistant flame-retardant material, while fully utilizing the excellent carbon-forming property of hydroxypropyl-β-cyclodextrin, so that the flame-retardant performance of the prepared heat-resistant flame-retardant material is more excellent.

[0028] 3. The heat-resistant flame-retardant material of the present application, in which the combination of vermiculite, illite and kaolin can maintain the structural stability and strength of the material under high temperature conditions, and reduce the possibility of thermal decomposition and deformation of the material; after the modified silica gel is irradiated by ultraviolet light, the number of hydroxyl groups on the surface of the modified silica gel for chemical bonding increases, which can form hydrogen bonds with the hydroxyl groups in the hydroxypropyl-β-cyclodextrin, thereby helping to improve the strength and thermal stability of the heat-resistant flame-retardant material; by controlling the conditions and parameters in the preparation method, the performance of the material can be adjusted, and the balance between flame retardance and heat resistance is achieved. DETAILED DESCRIPTION

[0029] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The ranges and values should be interpreted as being approximate. The endpoints of the ranges and values are provided as exemplifications of the ranges and values. Other values within the ranges and values are neither practical nor are they to be excluded from the ranges or values. Various selective ranges and values thereof for Ranges and Values are each combinable with each other to create further Ranges and Values which are also contemplated herein.

[0030] Unless otherwise specified in the examples, the procedures were carried out under conventional conditions or under the conditions recommended by the manufacturer. Unless otherwise specified, the raw materials or instruments used were conventional products available on the market.

[0031] Example 1

[0032] A method for preparing a heat-resistant flame-retardant material, comprising the following steps:

[0033] (1) Vermiculite, illite and kaolin with a mass ratio of 1:0.5:0.8 were added to deionized water, the content of the fillers in the deionized water was 15wt%, and ultrasonic treatment was carried out at 30℃ for 2h, the ultrasonic power was 300w, and the ultrasonic frequency was 50KHz, to obtain a suspension;

[0034] (2) A silicate aqueous solution was added dropwise to the suspension of step (1) until the gel point was reached, the volume ratio of the suspension to the silicate aqueous solution was 1:0.1, and constant temperature treatment was carried out at 25℃ for 40min, and then aging treatment was carried out at 70℃ for 5h, followed by washing, drying, to obtain modified silica gel;

[0035] (3) Hydroxypropyl-β-cyclodextrin was dissolved in acetone at 32℃, the content of hydroxypropyl-β-cyclodextrin in acetone was 35wt%, resorcinol bis(diphenyl phosphate) was added, the mass ratio of hydroxypropyl-β-cyclodextrin to resorcinol bis(diphenyl phosphate) was 20:1, stirring was carried out for 8h, filtration was carried out, and washing was carried out, to obtain modified resorcinol bis(diphenyl phosphate);

[0036] (4) The modified silica gel was irradiated under ultraviolet light with a wavelength of 300nm for 60min under the action of 2-hydroxy-2-methyl-1-phenyl-1-propanone, the addition amount of 2-hydroxy-2-methyl-1-phenyl-1-propanone was 3wt% of the modified silica gel, modified resorcinol bis(diphenyl phosphate) and polyethylene glycol were added, the mass ratio of the modified silica gel to the modified resorcinol bis(diphenyl phosphate) and polyethylene glycol was 1:0.3:0.05, and uniform stirring was carried out at room temperature, to obtain the heat-resistant flame-retardant material.

[0037] Example 2

[0038] A method for preparing a heat-resistant flame-retardant material, comprising the following steps:

[0039] (1) Vermiculite, illite and kaolin with a mass ratio of 1:1:1.5 were added to deionized water, the content of the fillers in the deionized water was 20wt%, and ultrasonic treatment was carried out at 40℃ for 1.5h, the ultrasonic power was 500w, and the ultrasonic frequency was 30KHz, to obtain a suspension;

[0040] (2) to the suspension of step (1) dropwise add silicate aqueous solution until the gel point is reached, the volume ratio of the suspension to the silicate aqueous solution is 1:2, and treat at constant temperature of 30℃ for 30 min, then aging treatment at 80℃ for 3h, wash, dry, to obtain modified silica gel;

[0041] (3) dissolve hydroxypropyl-β-cyclodextrin in acetone at 38℃, the content of hydroxypropyl-β-cyclodextrin in acetone is 45wt%, add resorcinol bis(diphenyl phosphate), the mass ratio of hydroxypropyl-β-cyclodextrin to resorcinol bis(diphenyl phosphate) is 30:1, stir for 5h, filter, wash, to obtain modified resorcinol bis(diphenyl phosphate);

[0042] (4) under the action of 1-hydroxy-cyclohexyl phenyl ketone and diethoxyphenylacetophenone, irradiate the modified silica gel under ultraviolet light with wavelength of 365nm for 50min, the addition amount of 1-hydroxy-cyclohexyl phenyl ketone and diethoxyphenylacetophenone is 5wt% of the modified silica gel, add modified resorcinol bis(diphenyl phosphate) and octylphenol polyoxyethylene ether, the mass ratio of the modified silica gel, the modified resorcinol bis(diphenyl phosphate) and the octylphenol polyoxyethylene ether is 1:0.6:0.08, and stir uniformly at room temperature, to obtain the heat-resistant and flame-retardant material.

[0043] Example 3

[0044] A preparation method of a heat-resistant and flame-retardant material, comprising the following steps:

[0045] (1) add vermiculite, illite and kaolin with mass ratio of 1:1.5:2 into deionized water, the content of the fillers in the deionized water is 28wt%, ultrasonic treatment at 50℃ for 1h, the ultrasonic power is 600w, and the ultrasonic frequency is 20KHz, to obtain a suspension;

[0046] (2) to the suspension of step (1) dropwise add silicate aqueous solution until the gel point is reached, the volume ratio of the suspension to the silicate aqueous solution is 1:3, and treat at constant temperature of 35℃ for 20 min, then aging treatment at 90℃ for 2h, wash, dry, to obtain modified silica gel;

[0047] (3) dissolve hydroxypropyl-β-cyclodextrin in acetone at 45℃, the content of hydroxypropyl-β-cyclodextrin in acetone is 50wt%, add resorcinol bis(diphenyl phosphate), the mass ratio of hydroxypropyl-β-cyclodextrin to resorcinol bis(diphenyl phosphate) is 40:1, stir for 3h, filter, wash, to obtain modified resorcinol bis(diphenyl phosphate);

[0048] (4) under the action of benzoin n-butyl ether, the modified silica gel is irradiated under ultraviolet light with a wavelength of 400 nm for 40 min, the addition amount of benzoin n-butyl ether is 7wt% of the modified silica gel, modified resorcinol bis(diphenyl phosphate) and sodium dodecyl sulfate are added, and the mass ratio of the modified silica gel, the modified resorcinol bis(diphenyl phosphate) and the sodium dodecyl sulfate is 1:0.8:0.1, and then the mixture is stirred uniformly at room temperature to obtain the heat-resistant and flame-retardant material.

[0049] Comparative Example 1

[0050] A preparation method of a heat-resistant and flame-retardant material, comprising the following steps:

[0051] (1) adding vermiculite, illite and kaolin with a mass ratio of 1:0.1:3 into deionized water, the content of the fillers in the deionized water is 10wt%, ultrasonic treatment is carried out at 20℃ for 3h, the ultrasonic power is 200w, and the ultrasonic frequency is 60KHz to obtain a suspension;

[0052] (2) adding a silicate aqueous solution dropwise into the suspension of step (1) until the gel point is reached, the volume ratio of the suspension to the silicate aqueous solution is 1:0.05, constant temperature treatment is carried out at 20℃ for 50min, aging treatment is carried out at 50℃ for 1h, then washing, drying to obtain modified silica gel;

[0053] (3) dissolving hydroxypropyl-β-cyclodextrin in acetone at 25℃, the content of the hydroxypropyl-β-cyclodextrin in the acetone is 20wt%, adding resorcinol bis(diphenyl phosphate), the mass ratio of the hydroxypropyl-β-cyclodextrin to the resorcinol bis(diphenyl phosphate) is 10:1, stirring for 1h, filtering, washing to obtain modified resorcinol bis(diphenyl phosphate);

[0054] (4) under the action of 1-hydroxy-cyclohexyl phenyl ketone and diethoxyphenylacetophenone, the modified silica gel is irradiated under ultraviolet light with a wavelength of 254nm for 30min, the addition amount of 1-hydroxy-cyclohexyl phenyl ketone and diethoxyphenylacetophenone is 1wt% of the modified silica gel, adding modified resorcinol bis(diphenyl phosphate) and octylphenol polyoxyethylene ether, the mass ratio of the modified silica gel, the modified resorcinol bis(diphenyl phosphate) and the octylphenol polyoxyethylene ether is 1:1:0.02, and then the mixture is stirred uniformly at room temperature to obtain the heat-resistant and flame-retardant material.

[0055] Comparative Example 2

[0056] The difference from Example 2 is that step (2) is: adding a silicate aqueous solution dropwise into the suspension of step (1) until the gel point is reached, the volume ratio of the suspension to the silicate aqueous solution is 1:2, constant temperature treatment is carried out at 50℃ for 6h, washing, drying to obtain modified silica gel.

[0057] Comparative Example 3

[0058] The difference from Example 2 is that step (4) is that the modified silica gel, modified resorcinol bis(diphenyl phosphate) and octylphenol polyoxyethylene ether with a mass ratio of 1:0.6:0.08 are stirred uniformly at room temperature to obtain the heat-resistant and flame-retardant material.

[0059] Comparative Example 4

[0060] The difference from Example 2 is that in step (3), the hydroxypropyl-β-cyclodextrin is replaced by β-cyclodextrin.

[0061] Comparative Example 5

[0062] The difference from Example 2 is that in step (1), the vermiculite, illite and kaolin with a mass ratio of 1:1:1.5 are replaced by clay.

[0063] Test Example

[0064] The flame retardancy, heat resistance and mechanical properties of the heat-resistant and flame-retardant materials of Examples 1-3 and Comparative Examples 1-5 are tested according to the standards of UL94, TG method and ASTM D412, and the results are shown in Table 1.

[0065] Table 1

[0066]

[0067] As can be seen from Table 1, the heat-resistant and flame-retardant materials in Examples 1-3 and Comparative Examples 1-5 all have excellent flame retardant properties. Compared with Comparative Examples 1-5, the heat-resistant and flame-retardant materials in Examples 1-3 have better heat resistance and mechanical properties, achieving a balance between flame retardancy and heat resistance.

[0068] The above is only an embodiment of the present application, and the protection scope of the present application is not limited by these specific embodiments, but is determined by the claims of the present application. The present application can have various modifications and changes for those skilled in the art. Any modification, equivalent replacement, improvement, etc. within the technical idea and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a heat-resistant and flame-retardant material, characterized in that, Includes the following steps: (1) Add the filler to deionized water and sonicate at 30-50℃ for 1-2 hours to obtain a suspension; (2) Add silicate aqueous solution dropwise to the suspension in step (1) until the gel point is reached, and keep it at 25-35℃ for 20-40 min, then age it at 70-90℃ for 2-5 h, wash and dry to obtain modified silica gel. (3) Hydroxypropyl-β-cyclodextrin was dissolved in acetone at 32-45℃, resorcinol bis(diphenyl phosphate) was added, stirred for 3-8h, filtered, and washed to obtain modified resorcinol bis(diphenyl phosphate). (4) After pretreating the modified silica gel, add modified resorcinol bis(diphenyl phosphate) and additives, and stir evenly at room temperature to obtain a heat-resistant and flame-retardant material. The filler is composed of vermiculite, illite, and kaolin in a mass ratio of 1:(0.5-1.5):(0.8-2). The pretreatment steps for modified silicone are as follows: under the action of a photoinitiator, the modified silicone is irradiated under ultraviolet light with a wavelength of 300-400nm for 40-60 minutes.

2. The method for preparing the heat-resistant and flame-retardant material as described in claim 1, characterized in that, In step (1), the content of the filler in deionized water is 15-28 wt%. The ultrasonic power is 300-600W, and the ultrasonic frequency is 20-50KHz.

3. The method for preparing the heat-resistant and flame-retardant material as described in claim 1, characterized in that, In step (2), the volume ratio of the suspension to the silicate aqueous solution is 1:(0.1-3).

4. The method for preparing the heat-resistant and flame-retardant material as described in claim 1, characterized in that, In step (3), the content of hydroxypropyl-β-cyclodextrin in acetone is 35-50 wt%. The mass ratio of hydroxypropyl-β-cyclodextrin to resorcinol bis(diphenyl phosphate) is (20-40):

1.

5. The method for preparing the heat-resistant and flame-retardant material as described in claim 1, characterized in that, The amount of photoinitiator added is 3-7 wt% of the modified silica gel.

6. The method for preparing the heat-resistant and flame-retardant material as described in claim 5, characterized in that, The photoinitiator is one or more of 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxy-cyclohexylbenzophenone, benzoin n-butyl ether, and diethoxyacetophenone.

7. The method for preparing the heat-resistant and flame-retardant material as described in claim 1, characterized in that, In step (4), the mass ratio of modified silica gel, modified resorcinol bis(diphenyl phosphate) and additives is 1:(0.3-0.8):(0.05-0.1); The additives are sodium dodecyl sulfate, octylphenol polyoxyethylene ether, or polyethylene glycol.

8. A heat-resistant and flame-retardant material prepared by the method for preparing a heat-resistant and flame-retardant material as described in any one of claims 1-7.

9. The application of the heat-resistant and flame-retardant material as described in claim 8 in the preparation of automotive interior materials.

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