Low-odor gasoline-rubbing-color-fastness-resistant polypropylene composite material and preparation method thereof

Abstract

The invention relates to a low-odor polypropylene composite material with gasoline-resistant color fastness to rubbing and a preparation method of the low-odor polypropylene composite material. The low-odor polypropylene composite material resistant to gasoline rubbing color fastness is prepared from the following components in percentage by weight: 54%-85% of polypropylene, 10%-30% of glass fiber, 0.5%-3% of a deodorant, 1%-4% of an organic surface modifier, 2%-6% of a compatilizer, 0.3%-0.8% of an antioxidant, 0.4%-1.2% of a lubricant and 0.3%-1% of carbon black, the deodorant comprises a physical deodorant and / or a chemical deodorant. The physical deodorant and / or the chemical deodorant are / is introduced into the glass fiber reinforced polypropylene material, and the physical deodorant can effectively adsorb micromolecular alkane substances and aldehyde ketone substances generated in the processing process; the chemical deodorant is mainly used for carrying out esterification reaction on small molecular substances such as aldehydes, ketones, benzenes, organic sulfides and organic chlorides, so that the source of pungent smell is reduced, and the purpose of reducing the smell is achieved; by introducing the organic surface modifier, the gasoline rubbing color fastness of the glass fiber reinforced polypropylene material can be improved.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a low-odor gasoline-resistant friction color fastness polypropylene composite material and a preparation method thereof. Background Art

[0002] At present, with the increasing number of cars in use, the requirements for environmental protection of automotive materials are also getting higher and higher, and consumers are becoming more and more stringent about the odor of automotive interior parts. However, there are common problems such as heavy odor and pungent odor in automotive interior parts, which bring discomfort to people and even health risks. Therefore, the research and implementation of odor improvement of automotive interior parts is particularly important.

[0003] At present, there are many research results on the low odor research of mineral-filled modified polypropylene materials, which mainly improve the odor of materials by selecting low-odor raw materials, adding adsorption-type deodorants, and post-treatment. However, with the current trend of lightweight automobiles, glass fiber reinforced polypropylene material systems are increasingly used in automotive interiors. Among them, the glass fiber reinforced polypropylene material system will introduce PP grafted maleic anhydride to solve the compatibility problem between glass fiber and polypropylene. PP grafted maleic anhydride contains a large amount of low-molecular substances, and the odor is very strong at room temperature. Therefore, compared with mineral-filled modified polypropylene materials, it is more difficult and more urgent to improve the odor of glass fiber reinforced polypropylene materials. At the same time, conventional polypropylene materials have poor resistance to gasoline (120# gasoline, 93# gasoline, etc.). Usually after gasoline resistance testing, the surface of the parts will obviously turn white. Therefore, the gasoline friction color fastness performance of glass fiber reinforced polypropylene materials needs to be improved. Summary of the invention

[0004] Based on this, the purpose of the present invention is to provide a low-odor gasoline-resistant friction color fastness polypropylene composite material and a preparation method thereof.

[0005] To achieve the above object, the present invention adopts the following technical solutions:

[0006] The invention provides a low-odor gasoline-friction-resistant color fastness polypropylene composite material, which is prepared from the following components in percentage by weight: 54%-85% of polypropylene, 10%-30% of glass fiber, 0.5%-3% of deodorant, 1%-4% of organic surface modifier, 2%-6% of compatibilizer, 0.3%-0.8% of antioxidant, 0.4%-1.2% of lubricant and 0.3%-1% of carbon black, wherein the deodorant comprises a physical deodorant and / or a chemical deodorant.

[0007] The present invention introduces a physical deodorant and / or a chemical deodorant into the glass fiber reinforced polypropylene material. The physical deodorant can effectively adsorb small molecular alkane substances and aldehyde and ketone substances generated during the processing process. Once the small molecular substances are adsorbed, they are not easy to escape and release; the chemical deodorant mainly reacts with small molecular substances such as aldehydes, ketones, benzenes, organic sulfides and organic chlorides to produce an esterification reaction, thereby reducing the source of irritating odors and achieving the purpose of reducing odors; thereby effectively reducing the odor of the glass fiber reinforced polypropylene material. In addition, the present invention introduces an organic surface modifier into the glass fiber reinforced polypropylene material to effectively improve the gasoline friction color fastness performance of the glass fiber reinforced polypropylene material.

[0008] As a further improvement of the above solution of the present invention, the physical deodorant is a surface-modified porous silicate material, and the chemical deodorant is a monoglyceride of fatty acid;

[0009] And / or, the organic surface modifier is maleic anhydride grafted polytetrafluoroethylene.

[0010] As a further improvement of the above scheme of the present invention, the preparation method of the physical deodorant is: prepare an ethanol solution of polyether polyol, add zeolite, stir, filter, rinse, dry, grind and sieve to obtain the physical deodorant;

[0011] And / or, the monoglyceride substance is one of monostearate glyceryl, diacetyl ester, and monoglyceride polyoxyethylene ether.

[0012] As a further improvement of the above scheme of the present invention, the content of polyether polyol in the ethanol solution of polyether polyol is 5wt%-10wt%;

[0013] And / or, the specific surface area of ​​the zeolite is 300-600m 2 / g;

[0014] And / or, the mass volume ratio of the zeolite to the ethanol solution of the polyether polyol is 150-300 g:1 L.

[0015] As a further improvement of the above scheme of the present invention, the preparation method of maleic anhydride grafted polytetrafluoroethylene is as follows: polytetrafluoroethylene powder is irradiated by gamma-ray cobalt-60 at a dose rate of 60-80 Gy / min for 1-2 hours, the treated polytetrafluoroethylene powder and polypropylene grafted maleic anhydride are melt-mixed at a mass ratio of 1:4 at 170-190° C., the mixed particles are removed after being uniformly drawn, crushed, extruded into granules by a twin-screw extruder, and dried to obtain maleic anhydride grafted polytetrafluoroethylene.

[0016] As a further improvement of the above scheme of the present invention, the polypropylene is selected from at least one of copolymer polypropylene and homopolypropylene, and the melt index of the copolymer polypropylene at 230° C. and 2.16 kg is 10 to 90 g / 10 min.

[0017] As a further improvement of the above solution of the present invention, the glass fiber is chopped glass fiber with a glass fiber length of 0.5-3 mm, a diameter of 7-13 μm, and a combustible content of 0.3%-0.5%.

[0018] As a further improvement of the above solution of the present invention, the compatibilizer is at least one of epoxy, carboxylic acid, and anhydride compatibilizers;

[0019] and / or, the antioxidant is at least one of hindered phenols, thioesters, and phosphites;

[0020] And / or, the lubricant is at least one of polyethylene wax, stearate, ethylene bisstearamide, and grafted ethylene bisstearamide.

[0021] It is understandable that the selection of the above auxiliary agents is not limited to the above-mentioned ones, and any conventional ones in the art are acceptable. The present invention also provides a method for preparing the aforementioned low-odor gasoline-resistant friction color fastness polypropylene composite material, which comprises the following steps: polypropylene, organic surface modifier, physical deodorant, chemical deodorant, compatibilizer, antioxidant, lubricant and carbon black are fully mixed in proportion, and then put into the main feed port of the extruder, and glass fiber is put into the side feed port of the extruder in proportion, and the low-odor gasoline-resistant friction color fastness polypropylene composite material is obtained through melting, extrusion granulation and drying. Preferably, the barrel temperature of the extruder is 170-210°C, the screw speed is 400-600r / min, and the vacuum degree is 0.08-0.1MPa.

[0022] As a further improvement of the above scheme of the present invention, during the melting process, a supercritical fluid is introduced into the extruder and extracted by a high vacuum pump. In the production process, a supercritical fluid is introduced as a reaction carrier, and through its strong penetration and dissolving ability, it further adsorbs volatile small molecules in the melt, and finally discharges them through the vacuum exhaust port, thereby reducing the odor level of the material. Preferably, a supercritical fluid is introduced into the extruder through a high-pressure metering pump, while ensuring that the maximum bearing pressure of the barrel is greater than or equal to 7MPa; the supercritical fluid is any one of supercritical carbon dioxide, supercritical nitrogen, and supercritical water.

[0023] Compared with the prior art, the present invention has the following beneficial effects:

[0024] 1. The present invention introduces a physical deodorant and / or a chemical deodorant into the glass fiber reinforced polypropylene material. The physical deodorant can effectively adsorb small molecular alkane substances and aldehyde and ketone substances generated during the processing process. Once the small molecular substances are adsorbed, they are not easy to escape and release; the chemical deodorant mainly reacts with small molecular substances such as aldehydes, ketones, benzenes, organic sulfides and organic chlorides to produce an esterification reaction, thereby reducing the source of the irritating odor and achieving the purpose of reducing the odor; thereby effectively reducing the odor of the glass fiber reinforced polypropylene material.

[0025] 2. The present invention introduces an organic surface modifier into the glass fiber reinforced polypropylene material. Polytetrafluoroethylene is a very stable polymer material. It has good chemical corrosion resistance and good stability to a wide range of chemicals, but its compatibility with polypropylene materials is poor. The organic surface modifier used in the present invention greatly improves its compatibility with polypropylene by modifying polytetrafluoroethylene and introducing polypropylene grafted maleic anhydride. In the glass fiber reinforced polypropylene material, polytetrafluoroethylene effectively wraps the material matrix, thereby resisting the erosion of gasoline, thereby achieving the effect of improving the gasoline friction color fastness of the glass fiber reinforced polypropylene material.

[0026] 3. The present invention introduces supercritical fluid as a reaction carrier in the production process of glass fiber reinforced polypropylene material. Through its strong penetration and dissolving ability, it further adsorbs volatile small molecules in the melt and finally discharges them through the vacuum exhaust port, which can greatly reduce the odor of the material. And by adopting the supercritical process, small molecules are discharged through the vacuum exhaust port, which is non-toxic and harmless, does not pollute the environment, and has great promotion potential. DETAILED DESCRIPTION

[0027] For ease of understanding of the present invention, the present invention will be described more fully below in conjunction with specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thoroughly understood.

[0028] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0029] The raw material information used in the following examples and comparative examples is as follows:

[0030] (1) Polypropylene: SZ30S, produced by Wuhan Petrochemical;

[0031] (2) Glass fiber: 508A, produced by Jushi Fiberglass;

[0032] (3) Physical deodorant: homemade. The homemade method is as follows: prepare polyether polyol into a 10% ethanol solution, add zeolite, wherein the specific surface area of ​​zeolite is required to be 400m 2 / g, the mass volume ratio of zeolite to ethanol solution is 200g:1L, and after stirring for 3h, it is filtered. During the filtration process, it is necessary to rinse with anhydrous ethanol, dry, grind and sieve to finally obtain a physical deodorant;

[0033] (4) Chemical deodorant: glyceryl monostearate, produced by Shanghai Bangcheng;

[0034] (5) Organic surface modifier: Self-made maleic anhydride grafted polytetrafluoroethylene, the self-made method is as follows: polytetrafluoroethylene powder is irradiated by gamma-ray cobalt-60 at a dose rate of 60 Gy / min for 1 h, the treated polytetrafluoroethylene powder and polypropylene grafted maleic anhydride are melt-mixed at a mass ratio of 1:4 at 170°C, the mixed particles are pulled out after being uniformly mixed, crushed, extruded into granules by a twin-screw extruder, and dried to obtain maleic anhydride grafted polytetrafluoroethylene;

[0035] (6) Compatibilizer: CA100, produced by Arkema;

[0036] (7) Antioxidant: Ciba 1010;

[0037] (8) Lubricant: calcium stearate, produced by Farji.

[0038] The above raw materials are only for illustrating the sources and components of the reagents used in the experiments of the present invention so as to fully disclose the information, and do not mean that the present invention cannot be realized by using other similar reagents or reagents provided by other suppliers.

[0039] Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the present technical field.

[0040] Example 1

[0041] The present embodiment proposes a low-odor gasoline-friction-resistant color fastness polypropylene composite material, which includes the following component raw materials in weight percentage: 70% polypropylene, 20% glass fiber, 1% physical deodorant, 2% organic surface modifier, 5% compatibilizer CA100, 0.5% antioxidant 1010, 0.8% lubricant and 0.7% carbon black.

[0042] The preparation method of the low-odor gasoline-resistant friction color fastness polypropylene composite material of this embodiment comprises the following steps: polypropylene, deodorant, organic surface modifier, compatibilizer CA100, antioxidant 1010, lubricant and carbon black are added to a high-speed mixer and mixed at high speed for 10 minutes, and then fed into a twin-screw extruder from the main feed port, and glass fiber is fed into the twin-screw extruder through the side feed port. The materials are melted in the twin-screw extruder and passed into a 50m 3 / h of supercritical fluid, extrusion granulation, and the low molecular weight substances are removed by a high vacuum pump. Among them, the barrel temperature is 200℃, the screw speed is 500r / min, and the vacuum degree is: 0.085MPa.

[0043] Example 2

[0044] This embodiment adopts the same implementation method as Example 1, and is different from Example 1 in that the low-odor gasoline-friction-resistant color-fastness polypropylene composite material of this embodiment includes the following component raw materials in weight percentage: 67.5% polypropylene, 20% glass fiber, 1.5% physical deodorant, 4% organic surface modifier, 5% compatibilizer CA100, 0.5% antioxidant 1010, 0.8% lubricant and 0.7% carbon black.

[0045] Example 3

[0046] This embodiment adopts the same implementation method as Example 1, and is different from Example 1 in that the low-odor gasoline-resistant friction color fastness polypropylene composite material of this embodiment includes the following component raw materials in weight percentage: 70.5% polypropylene, 20% glass fiber, 0.5% chemical deodorant, 2% organic surface modifier, 5% compatibilizer CA100, 0.5% antioxidant 1010, 0.8% lubricant and 0.7% carbon black.

[0047] Example 4

[0048] This embodiment adopts the same implementation method as Example 1, and is different from Example 1 in that the low-odor gasoline-resistant friction color fastness polypropylene composite material of this embodiment includes the following component raw materials in weight percentage: 68% polypropylene, 20% glass fiber, 1% chemical deodorant, 4% organic surface modifier, 5% compatibilizer CA100, 0.5% antioxidant 1010, 0.8% lubricant and 0.7% carbon black.

[0049] Example 5

[0050] This embodiment adopts the same implementation method as Example 1, and is different from Example 1 in that the low-odor gasoline-resistant friction color fastness polypropylene composite material of this embodiment includes the following component raw materials in weight percentage: 66.5% polypropylene, 20% glass fiber, 1.5% physical deodorant, 1% chemical deodorant, 4% organic surface modifier, 5% compatibilizer CA100, 0.5% antioxidant 1010, 0.8% lubricant and 0.7% carbon black.

[0051] Comparative Example

[0052] This comparative example adopts the same implementation method as Example 1, and the difference from Example 1 is that the polypropylene composite material of this comparative example includes the following component raw materials in weight percentage: 73% polypropylene, 20% glass fiber, 5% compatibilizer CA100, 0.5% antioxidant 1010, 0.8% lubricant and 0.7% carbon black.

[0053] The amounts of various raw materials used in the polypropylene composite materials of the above embodiments and comparative examples are shown in Table 1.

[0054] Table 1 Amount of each raw material in the polypropylene composite material of the embodiment and comparative example (weight percentage %)

[0055] Recipe composition Comparative Example Example 1 Example 2 Example 3 Example 4 Example 5 Polypropylene 73 70 67.5 70.5 68 66.5 Fiberglass 20 20 20 20 20 20 Physical deodorant / 1 1.5 / / 1.5 Chemical deodorant / / / 0.5 1 1 Organic surface modifiers / 2 4 2 4 4 Compatibilizer CA100 5 5 5 5 5 5 Antioxidant 1010 0.5 0.5 0.5 0.5 0.5 0.5 Lubricant (calcium stearate) 0.8 0.8 0.8 0.8 0.8 0.8 Carbon Black 0.7 0.7 0.7 0.7 0.7 0.7

[0056] Test Case

[0057] The polypropylene composite materials of the above embodiments and comparative examples were subjected to performance tests, and the test results are shown in Table 2.

[0058] Table 2 Properties of polypropylene composite materials of the embodiments and comparative examples

[0059]

[0060]

[0061] It can be seen from the results in Table 2 that the polypropylene composite materials of Examples 1-5 of the present application have significantly improved odor and solvent performance by introducing physical deodorants and / or chemical deodorants and organic surface modifiers, thus meeting customer performance requirements and standard requirements.

[0062] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0063] The above-mentioned embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A low-odor gasoline-resistant friction color fastness polypropylene composite material, characterized in that: The invention is prepared from the following components in weight percentage: 54%-85% polypropylene, 10%-30% glass fiber, 0.5%-3% deodorant, 1%-4% organic surface modifier, 2%-6% compatibilizer, 0.3%-0.8% antioxidant, 0.4%-1.2% lubricant and 0.3%-1% carbon black. The deodorant includes a physical deodorant and / or a chemical deodorant.

2. The low-odor gasoline-resistant friction color fastness polypropylene composite material according to claim 1, characterized in that: The physical deodorant is a surface-modified porous silicate material, and the chemical deodorant is a monoglyceride of fatty acid; And / or, the organic surface modifier is maleic anhydride grafted polytetrafluoroethylene.

3. The low-odor gasoline-resistant friction color fastness polypropylene composite material according to claim 2, characterized in that: The preparation method of the physical deodorant is as follows: preparing an ethanol solution of polyether polyol, adding zeolite, stirring, filtering, rinsing, drying, grinding and sieving to obtain the physical deodorant; And / or, the monoglyceride substance is one of monostearate glyceryl, diacetyl ester, and monoglyceride polyoxyethylene ether.

4. The low-odor gasoline-resistant friction color fastness polypropylene composite material according to claim 3, characterized in that: The content of polyether polyol in the ethanol solution of polyether polyol is 5wt%-10wt%; And / or, the specific surface area of ​​the zeolite is 300-600m 2 / g; And / or, the mass volume ratio of the zeolite to the ethanol solution of the polyether polyol is 150-300 g:1 L.

5. The low-odor gasoline-resistant friction color fastness polypropylene composite material according to claim 2, characterized in that: The preparation method of maleic anhydride grafted polytetrafluoroethylene is as follows: polytetrafluoroethylene powder is irradiated by gamma-ray cobalt-60 at a dose rate of 60-80 Gy / min for 1-2 hours, the treated polytetrafluoroethylene powder and polypropylene grafted maleic anhydride are melt-mixed at a mass ratio of 1:4 at 170-190° C., the mixed particles are pulled out after being uniformly mixed, crushed, extruded into granules by a twin-screw extruder, and dried to obtain maleic anhydride grafted polytetrafluoroethylene.

6. The low-odor gasoline-resistant friction color fastness polypropylene composite material according to claim 1, characterized in that: The polypropylene is selected from at least one of copolymer polypropylene and homopolymer polypropylene, and the copolymer polypropylene has a melt index of 10 to 90 g / 10 min at 230° C. and 2.16 kg.

7. The low-odor gasoline-resistant friction color fastness polypropylene composite material according to claim 1, characterized in that: The glass fibers are short-cut glass fibers with a length of 0.5-3 mm, a diameter of 7-13 μm, and a combustible content of 0.3%-0.5%.

8. The low-odor gasoline-resistant friction color fastness polypropylene composite material according to claim 1, characterized in that: The compatibilizer is at least one of epoxy, carboxylic acid, and anhydride compatibilizers; and / or, the antioxidant is at least one of hindered phenols, thioesters, and phosphites; And / or, the lubricant is at least one of polyethylene wax, stearate, ethylene bisstearamide, and grafted ethylene bisstearamide.

9. A method for preparing a low-odor gasoline-friction-resistant color fastness polypropylene composite material according to any one of claims 1 to 8, characterized in that: It includes the following steps: Polypropylene, organic surface modifier, deodorant, compatibilizer, antioxidant, lubricant and carbon black are fully mixed in proportion and fed into the main feeding port of the extruder. Glass fiber is fed into the side feeding port of the extruder in proportion. After melting, extrusion granulation and drying, a low-odor, gasoline-resistant, friction-resistant and color-fast polypropylene composite material is obtained.

10. The method for preparing the low-odor gasoline-friction-resistant color fastness polypropylene composite material according to claim 9, characterized in that: During the melting process, a supercritical fluid is introduced into the extruder and extracted by a high vacuum pump.

Images