Metallic texture enhanced polypropylene material and preparation method thereof

Abstract

The application relates to a metal texture enhanced polypropylene material and a preparation method, and belongs to the technical field of polypropylene material preparation. The polypropylene material comprises the following raw materials in parts by weight: 100 parts of PP base material, 15-25 parts of texture aid, 15-30 parts of modified glass fiber, 0.1-0.5 parts of ultraviolet light absorber and 0.5-1.5 parts of lubricant; the texture aid is metal powder modified by double bond silane coupling agent; the modified glass fiber is glass fiber modified by crosslinking promoting silane coupling agent; and the crosslinking promoting silane coupling agent is prepared by the reaction of an epoxy silane coupling agent, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical and dibenzoyl peroxide. The obtained composite material has excellent metal texture, hardness, heat resistance and mechanical properties.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of polypropylene material preparation, and particularly relates to a metal texture enhanced polypropylene material and a preparation method. BACKGROUND

[0002] The competition in the automobile field is increasingly fierce, and the pursuit of automobile interior decoration materials is increasingly quality-oriented, such as the requirement of metal texture appearance. However, the automobile interior decoration materials are generally made of polypropylene materials (hereinafter referred to as PP). The traditional automobile interior decoration materials are generally made by melting and mixing polypropylene and additional fillers or reinforcing materials. Among them, the current automobile pedal material is realized by adding long fibers to the polypropylene system to enhance the PP material to meet the requirements of wear resistance and mechanical strength of the automobile pedal. However, the texture of the PP material enhanced by long fibers is still the general plastic feel, and cannot achieve the metal texture. To meet the requirement of metal texture, the existing processing method is a secondary processing method, which sprays paint on the PP material enhanced by long fibers to give the final product a metal texture. This method has the disadvantages of prolonged production line, short duration of metal texture, and environmental pollution.

[0003] Therefore, it is necessary to provide a metal texture enhanced polypropylene material and a preparation method. SUMMARY

[0004] The application aims to provide a metal texture enhanced polypropylene material and a preparation method.

[0005] One object of the application can be achieved by the following technical scheme:

[0006] A metal texture enhanced polypropylene material, comprising the following raw materials by weight: 100 parts of PP base material, 15-25 parts of texture aid, 15-30 parts of modified glass fiber, 0.1-0.5 parts of ultraviolet light absorber, and 0.5-1.5 parts of lubricant.

[0007] The texture aid is a metal powder modified by a double bond silane coupling agent.

[0008] The modified glass fiber is a glass fiber modified by a cross-linking promoting silane coupling agent.

[0009] The cross-linking promoting silane coupling agent is an epoxy silane coupling agent, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl radical, and dibenzoyl peroxide.

[0010] The inventors chose to introduce metal powder into the PP base material to impart the texture of the resulting composite material when developing the present technical solution, but found that the addition of metal powder not only improved the texture of the composite material, but also reduced the performance of the composite material in all aspects. At the same time, the metal powder is not easy to disperse when mixed with other base materials, and is prone to agglomeration. At the same time, the metal particles on the surface of the formed material are not resistant to corrosion, resulting in the metal texture of the resulting composite material not being durable. The foregoing technical solution of directly introducing metal powder is improved, and is combined with the long fiber modification in the fiber modified polypropylene technology to develop a metal powder modified by a double bond silane coupling agent and a glass fiber modified by a cross-linking silane coupling agent. The simultaneous introduction not only solves the dispersion problem of metal powder and fiber in the base material through the silane coupling agent, but also makes the two mutually synergistic, forming an interpenetrating network in the resulting composite material, with the three-dimensional structure of metal powder and fiber as the skeleton and the base material as the ramming material. Not only does it impart the metal texture of the resulting composite material, but it also greatly improves the hardness, heat resistance and mechanical properties of the resulting composite material.

[0011] Further, the double bond silane coupling agent is 6-13% of the mass of the metal powder.

[0012] Further, the texture aid is prepared by the following steps:

[0013] The metal powder is added to the modification liquid, heated to the modification temperature under stirring, and reacted for a reaction time, then treated to obtain the texture aid.

[0014] Further, the modification temperature is 25-35°C, and the reaction time is 1-3h.

[0015] Further, the modification liquid is formed by hydrolysis reaction of the double bond silane coupling agent in a mixed solution of water and ethanol.

[0016] Further, the amount ratio of the double bond silane coupling agent to the mixed solution is 1g:15-20mL; the volume ratio of water to ethanol in the mixed solution is 1:4-5.

[0017] Further, the hydrolysis reaction conditions are: pH 4-5, reaction temperature 20-40°C, reaction time 20-30min.

[0018] Further, the cross-linking silane coupling agent is prepared by the following steps:

[0019] The epoxy silane coupling agent, 4-hydroxy-2, 2, 6, 6-tetramethylpiperidine-1-oxyl radical and tetrahydrofuran are mixed uniformly, the pH is adjusted to 10-11, heated to 60-70 DEG C, and incubated with stirring for 2-5h, reduced to room temperature, added with a solution of dibenzoyl peroxide in tetrahydrofuran, stirred at room temperature under nitrogen protection for 4-8h, and after-treatment to obtain the cross-linking promoting silane coupling agent.

[0020] Further, the molar ratio of the epoxy silane coupling agent, 4-hydroxy-2, 2, 6, 6-tetramethylpiperidine-1-oxyl radical and dibenzoyl peroxide is 1:1-1.2:1.1-1.3.

[0021] Further, the modified glass fiber is prepared by the following steps:

[0022] The glass fiber is ultrasonically dispersed in a mixed solution of the cross-linking promoting silane coupling agent, water and ethanol, heated to 50-70 DEG C with stirring, incubated with stirring for 3-6h, the reaction is stopped, and after-treatment to obtain the modified glass fiber.

[0023] Further, the mass ratio of the glass fiber and the cross-linking promoting silane coupling agent is 1:0.08-0.13.

[0024] Further, the ultraviolet light absorber is an ultraviolet light absorber well known in the art, such as ultraviolet absorber UV-O, ultraviolet absorber UV-9, ultraviolet absorber UV-531, ultraviolet absorber UVP-327.

[0025] Preferably, the ultraviolet light absorber is ultraviolet absorber UVP-327.

[0026] Further, the lubricant is a processing lubricant well known in the art, which is not limited in specific types herein.

[0027] Another object of the present application can be achieved by the following technical solutions:

[0028] A preparation method of a metal texture enhanced polypropylene material, characterized in that, comprising:

[0029] The PP base material, texture aid, modified glass fiber, ultraviolet light absorber and lubricant are mixed, extruded through an extruder and formed to obtain the metal texture enhanced polypropylene.

[0030] Further, the extrusion temperature range of the extruder is set to 195-240 DEG C.

[0031] The present application has the following beneficial effects:

[0032] The application provides a metal texture enhanced polypropylene material and a preparation method thereof. The metal powder modified by a double bond silane coupling agent and modified glass fiber are introduced. The metal powder modified by the double bond silane coupling agent serves as a texture aid to give the metal texture of the obtained composite material. The metal powder modified by the double bond silane coupling agent and the modified glass fiber are synergistic with each other. In the obtained composite material, an interpenetrating network is formed, taking the three-dimensional structure of the metal powder and the fiber as a skeleton and taking the base material as ramming material. The obtained composite material is not only given the metal texture, but also has improved hardness, heat resistance and mechanical properties. The explanation is as follows:

[0033] The metal powder modified by the double bond silane coupling agent improves the dispersion performance of the metal powder in the base material and improves the interface performance between the metal powder and the base material. Most importantly, the silane chain double bond on the surface of the metal powder can be crosslinked with the PP base material.

[0034] The surface of the modified glass fiber is grafted with a nitroxide bond (4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl radical and benzoyl peroxide reaction). The nitroxide bond is easy to break under high temperature or light radiation to generate a nitroxide radical, and then high-temperature crosslinking occurs. The generated nitroxide radical can capture active radicals generated by the crosslinking network of the double bond and PP, thereby preventing the collapse of the crosslinking network of the double bond and PP, and improving the hardness, heat resistance and mechanical properties of the obtained composite material. DETAILED DESCRIPTION

[0035] The technical solutions in the embodiments of the application will be clearly and completely described below in combination with the embodiments of the application. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the application.

[0036] Embodiment 1

[0037] Preparation of modified glass fiber:

[0038] A1, 0.1 mol of epoxy silane coupling agent (exemplarily KH560), 0.1 mol of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl radical and 60 mL of tetrahydrofuran are uniformly mixed, the pH is adjusted to 10-11, heated to 60 DEG C and kept stirring for 5 h, cooled to room temperature, 30 mL of tetrahydrofuran solution containing 0.11 mol of diphenylboron oxide is added, stirred at room temperature under nitrogen protection for 4 h, separated, and the oil phase is separated and purified to obtain a crosslinking-promoting silane coupling agent;

[0039] A2, 100 g glass fiber was dispersed in 13 g cross-linking promoting silane coupling agent, 20 mL water and 50 mL ethanol, heated to 70°C under stirring, and reacted for 3 h under stirring at 70°C. The reaction was stopped, the precipitate was obtained by centrifugation, repeatedly washed, and dried to obtain modified glass fiber.

[0040] Example 2

[0041] Preparation of modified glass fiber:

[0042] A1, 0.1 mol epoxy silane coupling agent (exemplarily KH560), 0.12 mol 4-hydroxy-2, 2, 6, 6-tetramethylpiperidine-1-oxyl and 60 mL tetrahydrofuran were uniformly mixed, the pH was adjusted to 10-11, heated to 70°C, and reacted for 2 h under stirring at 70°C. The temperature was lowered to room temperature, 30 mL tetrahydrofuran solution containing 0.14 mol dibenzoyl peroxide was added, and the reaction was carried out under stirring at room temperature for 8 h under nitrogen protection. The reaction was stopped, the oil phase was separated and chromatographed to obtain cross-linking promoting silane coupling agent.

[0043] A2, 100 g glass fiber was dispersed in 13 g cross-linking promoting silane coupling agent, 20 mL water and 50 mL ethanol, heated to 70°C under stirring, and reacted for 3 h under stirring at 70°C. The reaction was stopped, the precipitate was obtained by centrifugation, repeatedly washed, and dried to obtain modified glass fiber.

[0044] Example 3

[0045] Preparation of texture aid:

[0046] B1, 6 g double bond silane coupling agent (exemplarily KH570), 15 mL water and 75 mL ethanol were uniformly mixed, the pH was adjusted to 4-5, heated to 20°C under stirring, and reacted for 30 min under stirring at 20°C. The stirring and heating were stopped, and the temperature was lowered to room temperature to obtain modified liquid.

[0047] B2, 100 g metal powder (nanometer aluminum flake powder, particle size 200-300 nm) was added to the modified liquid, heated to 25°C under stirring, and reacted for 3 h under stirring at 25°C. The heating was stopped, centrifuged, the precipitate was obtained, repeatedly washed, and dried to obtain texture aid.

[0048] Example 4

[0049] Preparation of texture aid:

[0050] B1, 6 g double bond silane coupling agent (exemplarily KH570), 15 mL water and 75 mL ethanol were uniformly mixed, the pH was adjusted to 4-5, heated to 20°C under stirring, and reacted for 30 min under stirring at 20°C. The stirring and heating were stopped, and the temperature was lowered to room temperature to obtain modified liquid.

[0051] B2, 100 g of metal powder (nanometer aluminum flake powder, particle size 200-300 nm) was added into the modified liquid, heated to 35°C under stirring, and kept for 1 h, the heating was stopped, centrifuged, the precipitate was taken, repeatedly washed, dried, and the texture aid was obtained.

[0052] Example 5

[0053] Preparation of polypropylene material:

[0054] First step, the following weight parts of raw materials were prepared: PP base material 100 parts, texture aid prepared in Example 3 15 parts, modified glass fiber prepared in Example 1 30 parts, ultraviolet light absorber (ultraviolet absorber UVP-327) 0.1 part, lubricant 0.5 part (polypropylene wax);

[0055] Second step, after mixing the PP base material, the texture aid, the modified glass fiber, the ultraviolet light absorber and the lubricant, extruding through an extruder, and then irradiation molding, a metal texture enhanced polypropylene was obtained, wherein the extrusion temperature range of the extruder was set to 195-240°C.

[0056] Example 6

[0057] Preparation of polypropylene material:

[0058] First step, the following weight parts of raw materials were prepared: PP base material 100 parts, texture aid prepared in Example 3 20 parts, modified glass fiber prepared in Example 1 20 parts, ultraviolet light absorber (ultraviolet absorber UVP-327) 0.3 part, lubricant (polypropylene wax) 1 part;

[0059] Second step, after mixing the PP base material, the texture aid, the modified glass fiber, the ultraviolet light absorber and the lubricant, extruding through an extruder, and then irradiation molding, a metal texture enhanced polypropylene was obtained, wherein the extrusion temperature range of the extruder was set to 195-240°C.

[0060] Example 7

[0061] Preparation of polypropylene material:

[0062] First step, the following weight parts of raw materials were prepared: PP base material 100 parts, texture aid prepared in Example 3 25 parts, modified glass fiber prepared in Example 1 15 parts, ultraviolet light absorber (ultraviolet absorber UVP-327) 0.5 part, lubricant (polypropylene wax) 1.5 parts;

[0063] Second step, after mixing the PP base material, the texture aid, the modified glass fiber, the ultraviolet light absorber and the lubricant, extruding through an extruder, and then irradiation molding, a metal texture enhanced polypropylene was obtained, wherein the extrusion temperature range of the extruder was set to 195-240°C.

[0064] Comparative Example 1

[0065] Preparation of polypropylene material:

[0066] Comparing with Example 5, the modified glass fiber was replaced by glass fiber in equal parts, and the rest was the same.

[0067] Comparative Example 2

[0068] Preparation of polypropylene material:

[0069] Comparing with Example 5, the modified glass fiber was replaced by KH560 modified glass fiber in equal parts, and the rest was the same, wherein the KH560 modified glass fiber was obtained by the following steps:

[0070] 100g glass fiber was ultrasonically dispersed in a mixed solution of 8g KH560, 15mL water and 45mL ethanol, heated to 50℃ with stirring, and reacted for 6h with stirring. After stopping the reaction, the precipitate was obtained by centrifugation, washed repeatedly, and dried to obtain KH560 modified glass fiber.

[0071] Comparative Example 3

[0072] Comparing with Example 5, the texture aid was replaced by metal powder in equal parts, and the rest was the same.

[0073] Comparative Example 4

[0074] Comparing with Example 5, the texture aid was deleted, and the rest was the same.

[0075] The polypropylene materials obtained in Examples 5-7 and Comparative Examples 1-4 were subjected to physical property testing, and the results are shown in Table 1.

[0076] Table 1

[0077]

[0078]

[0079] As can be seen from the data in Table 1, the composite materials obtained in Examples 5-7 have excellent gloss, mechanical properties and heat resistance.

[0080] In the description of the specification, the description of the terms "one embodiment", "example", "specific example" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the present specification, the illustrative description of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0081] The above merely illustrates and describes the present application, and those skilled in the art can make various modifications or supplements to the described specific embodiments or adopt similar ways to replace, as long as the modifications or supplements do not deviate from the present application or exceed the scope defined by the present claims, and should belong to the protection scope of the present application.

Claims

1. A metal-gloss-enhanced polypropylene material, characterized by, The composition comprises the following raw materials by weight: 100 parts of PP base material, 15-25 parts of texture aid, 15-30 parts of modified glass fiber, 0.1-0.5 parts of ultraviolet light absorber, and 0.5-1.5 parts of lubricant; The texture aid is metal powder modified by double-bond silane coupling agent; The modified glass fiber is glass fiber modified by cross-linking promoting silane coupling agent; The cross-linking promoting silane coupling agent is prepared by the reaction of epoxy silane coupling agent, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl radical, and dibenzoyl peroxide; The cross-linking promoting silane coupling agent is prepared by the following steps: After the epoxy silane coupling agent, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl radical, and tetrahydrofuran are uniformly mixed, the pH is adjusted to 10-11, heated to 60-70℃, and incubated and stirred for 2-5h, then cooled to room temperature, and a tetrahydrofuran solution containing dibenzoyl peroxide is added, and stirred at room temperature for 4-8h, and then treated to obtain the cross-linking promoting silane coupling agent; The modified glass fiber is prepared by the following steps: The glass fiber is ultrasonically dispersed in a mixed solution of cross-linking promoting silane coupling agent, water, and ethanol, heated to 50-70℃ with stirring, incubated and stirred for 3-6h, then the reaction is stopped, and then treated to obtain the modified glass fiber; The double-bond silane coupling agent is 6-13% of the mass of the metal powder; The texture aid is prepared by the following steps: The metal powder is added to the modified liquid, heated to the modification temperature with stirring, and incubated and reacted until the reaction time is reached, then treated to obtain the texture aid; The modified liquid is formed by the hydrolysis reaction of the double-bond silane coupling agent in a mixed solution of water and ethanol; The molar ratio of the epoxy silane coupling agent, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl radical, and dibenzoyl peroxide is 1:1-1.2:1.1-1.

3.

2. The metal-gloss enhanced polypropylene material according to claim 1, wherein, The modification temperature is 25-35℃, and the reaction time is 1-3h.

3. The metal-gloss enhanced polypropylene material according to claim 2, wherein, The amount ratio of the double-bond silane coupling agent to the mixed solution is 1g:15-20mL; the volume ratio of water to ethanol in the mixed solution is 1:4-5.

4. The metal-gloss enhanced polypropylene material of claim 2, wherein, The hydrolysis reaction conditions are: pH 4-5, reaction temperature 20-40℃, and reaction time 20-30min.

5. The method for preparing a metallic-textured reinforced polypropylene material according to claim 1, characterized in that, The composition comprises the following raw materials by weight: 100 parts of PP base material, 15-25 parts of texture aid, 15-30 parts of modified glass fiber, 0.1-0.5 parts of ultraviolet light absorber, and 0.5-1.5 parts of lubricant; After the PP base material, texture aid, modified glass fiber, ultraviolet light absorber, and lubricant are mixed, they are extruded through an extruder and molded to obtain metal texture enhanced polypropylene.

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