High-strength and high-weather-resistance polyvinyl chloride composite material and preparation method thereof

Abstract

The invention discloses a high-strength and high-weather-resistance polyvinyl chloride composite material and a preparation method thereof, and relates to the technical field of high polymer materials. The preparation method comprises the following steps: reacting a 4-aminobenzoate compound with polyvinyl chloride to obtain graft-modified polyvinyl chloride, and fully mixing the graft-modified polyvinyl chloride with an inorganic filling material, a plasticizer, a stabilizer, a lubricant and an antioxidant according to a certain formula and process to prepare the high-strength and high-weather-resistance polyvinyl chloride composite material. The polyvinyl chloride composite material has high strength and excellent weather resistance, can cope with various application environments with high requirements, and has rich application prospects.

Description

Technical Field

[0001] The present application relates to the technical field of polymer materials, and in particular to a high-strength and high-weatherability polyvinyl chloride composite material and a preparation method thereof. Background Art

[0002] As one of the five general-purpose plastics, polyvinyl chloride (PVC) has been widely used in many fields such as construction, automobiles, packaging, and electrical appliances due to its many advantages such as low cost, strong plasticity, and good chemical stability. With the increasing complexity and diversity of application scenarios, especially in some environments with stringent requirements on material performance, the limitations of traditional PVC materials have become increasingly prominent. On the one hand, in terms of mechanical properties, the tensile strength and bending strength of ordinary PVC materials are relatively limited, and it is difficult to meet the high strength requirements of certain application scenarios. On the other hand, weather resistance has become a key bottleneck restricting the outdoor application of PVC. In outdoor environments, PVC materials are continuously exposed to the interaction of multiple factors such as ultraviolet radiation, temperature changes, humidity fluctuations, and erosion by atmospheric pollutants (such as acid rain and ozone). They often need to be replaced in a short period of time due to poor weather resistance, resulting in huge waste of resources and maintenance costs.

[0003] Therefore, developing a polyvinyl chloride composite material that has both high strength and high weather resistance and a reasonable and feasible preparation process has become a key technical challenge that needs to be urgently solved in the current plastic materials field. It is of great significance to promote the upgrading of the PVC industry and expand its application scope.

[0004] A Chinese patent application with publication number CN115612224A discloses a polyvinyl chloride composite material and a preparation method thereof. The polyvinyl chloride composite material is prepared by weight from 100 to 200 parts of polyvinyl chloride, 50 to 100 parts of high-density polyethylene, 10 to 30 parts of maleic anhydride grafted high-density polyethylene, 5 to 15 parts of a first weathering agent and 0.5 to 1 part of a second weathering agent, wherein the first weathering agent is carbon black and the second weathering agent is an antioxidant ZKF.

[0005] However, the above technical solution does not modify or optimize the polyvinyl chloride as the main body, but simply and directly physically compound the components. Moreover, there is still much room for improvement in the strength and weather resistance of the obtained polyvinyl chloride composite material. Summary of the invention

[0006] In view of the shortcomings of the prior art, the present application provides a high-strength and high-weather-resistant polyvinyl chloride composite material and a preparation method thereof. The graft-modified polyvinyl chloride is obtained by reacting a 4-aminobenzoic acid ester compound with polyvinyl chloride, and then the graft-modified polyvinyl chloride is fully mixed with an inorganic filler material, a plasticizer, a stabilizer, a lubricant, and an antioxidant under a certain formula and process to obtain a high-strength and high-weather-resistant polyvinyl chloride composite material.

[0007] To achieve the above object, the present application adopts the following technical solutions:

[0008] In a first aspect, the present application provides a high-strength and high-weather-resistant polyvinyl chloride composite material, including graft-modified polyvinyl chloride; the graft-modified polyvinyl chloride is obtained by reacting a 4-aminobenzoate compound with polyvinyl chloride; the 4-aminobenzoate compound includes any one of n-propyl 4-aminobenzoate, isopropyl 4-aminobenzoate, n-butyl 4-aminobenzoate, isobutyl 4-aminobenzoate, and 2-ethylhexyl 4-aminobenzoate.

[0009] In a second aspect, the present application provides a method for preparing a high-strength and high-weather-resistant polyvinyl chloride composite material, including the following steps:

[0010] Add polyvinyl chloride to DMF, under nitrogen protection, heat up to 70-90 °C, then add a 4-aminobenzoate compound and a Lewis acid, stir and react for 4-6 h, and obtain graft-modified polyvinyl chloride after the product is precipitated, washed, and dried.

[0011] Weigh the graft-modified polyvinyl chloride, inorganic filler, plasticizer, stabilizer, lubricant, and antioxidant, add them to a high-speed mixer, mix at 80-100 °C for 10-20 min, and cool and discharge to obtain a premix.

[0012] Add the premix to an internal mixer, mix at 160-180 °C and an internal mixer speed of 30-50 rpm for 5-15 min to obtain a mixed material.

[0013] The mixed material is calendered by a four-roll calender at a roll temperature of 160-170 °C and a pressure of 10-15 MPa to obtain a high-strength and high-weather-resistant polyvinyl chloride composite material.

[0014] Beneficial technical effects:

[0015] In the present application, graft-modified polyvinyl chloride is obtained by reacting a 4-aminobenzoate compound with polyvinyl chloride, and then the graft-modified polyvinyl chloride is fully mixed with an inorganic filler, a plasticizer, a stabilizer, a lubricant, and an antioxidant under a certain formula and process to prepare a high-strength and high-weather-resistant polyvinyl chloride composite material.

[0016] The applicant found that when preparing graft-modified polyvinyl chloride, the chlorine atoms on the polyvinyl chloride molecular chain are replaced by amino groups in 4-aminobenzoate compounds to form a graft copolymer bonded by chemical bonds. The introduced amino and ester groups can form hydrogen bonds, enhancing the interaction between the graft-modified polyvinyl chloride molecular chains and improving the strength of the polyvinyl chloride composite material. At the same time, the flexible chain segments of the ester groups can increase the mobility of local chain segments, and cooperate with the polarity of the amino groups to enhance the interfacial compatibility between the graft-modified polyvinyl chloride molecular chains and inorganic filler materials and other components, thereby further improving the strength of the polyvinyl chloride composite material. In addition, a larger conjugated system is formed by the conjugation of the benzene ring, amino group, and ester group in the 4-aminobenzoate compound. This larger conjugated system enhances the ultraviolet absorption efficiency of the graft-modified polyvinyl chloride. At the same time, the conjugated system in the above polyvinyl chloride composite material is generated by chemical bond bonding, and is not prone to migration or change. Therefore, the finally prepared polyvinyl chloride composite material has very good weather resistance. Brief Description of the Drawings

[0017] Figure 1 It is a schematic diagram of the chemical reaction for preparing graft-modified polyvinyl chloride.

[0018] Figure 2 It is a schematic diagram of the process for preparing a high-strength and high-weather-resistant polyvinyl chloride composite material. Detailed Description of the Embodiments

[0019] In order to make the technical problems, technical solutions, and beneficial effects to be solved by this application clearer, the following further details this application in conjunction with the embodiments. However, this should not be construed as limiting the scope of this application to the following examples. Without departing from the above method concept of this application, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of this application.

[0020] The terms used in this application are only for the purpose of describing specific embodiments and are not intended to limit this application.

[0021] The singular forms of "is", "a", "any one", and "the" used in this application are intended to include the plural forms unless the context clearly indicates otherwise.

[0022] In addition, if the terms "first" and "second" appear in this application, they are only for descriptive purposes and cannot be construed as indicating or implying relative importance.

[0023] In a first aspect, the present application provides a high-strength and high-weather-resistant polyvinyl chloride composite material, including graft-modified polyvinyl chloride; the graft-modified polyvinyl chloride is obtained by reacting a 4-aminobenzoate compound with polyvinyl chloride, and the reaction process is as Figure 1 shown; the 4-aminobenzoate compound includes any one of n-propyl 4-aminobenzoate, isopropyl 4-aminobenzoate, n-butyl 4-aminobenzoate, isobutyl 4-aminobenzoate, and 2-ethylhexyl 4-aminobenzoate.

[0024] In a feasible embodiment, the structure of the graft-modified polyvinyl chloride includes:

[0025]

[0026] wherein, R includes any one of propyl, isopropyl, butyl, isobutyl, and 2-ethylhexyl.

[0027] In a feasible embodiment, the high-strength and high-weather-resistant polyvinyl chloride composite material further includes an inorganic filler, a plasticizer, a stabilizer, a lubricant, and an antioxidant.

[0028] In a feasible embodiment, in the high-strength and high-weather-resistant polyvinyl chloride composite material, the mass ratio of the graft-modified polyvinyl chloride, the inorganic filler, the plasticizer, the stabilizer, the lubricant, and the antioxidant is (50-60):(10-15):(20-30):(2-5):(1-3):(0.5-1).

[0029] In a feasible embodiment, the inorganic filler includes at least one of light calcium carbonate, talcum powder, wollastonite, kaolin, and mica powder.

[0030] In a feasible embodiment, the plasticizer includes at least one of tributyl acetylcitrate, epoxidized soybean oil, diisononyl adipate, and dioctyl terephthalate.

[0031] In a feasible embodiment, the stabilizer includes at least one of calcium laurate / zinc ricinoleate complex, calcium stearate / zinc stearate complex, lanthanum stearate, tributyltin oxide, and pentaerythritol diphosphite.

[0032] In a feasible embodiment, the lubricant includes at least one of oxidized polyethylene wax, ethylene bisstearamide, and silicone masterbatch.

[0033] In a feasible embodiment, the antioxidant includes at least one of bis(2,2,6,6-tetramethylpiperidyl) sebacate, 2,6-di-tert-butyl-p-cresol, and dilauryl thiodipropionate.

[0034] In a second aspect, the present application provides a method for preparing a high-strength and high-weather-resistant polyvinyl chloride composite material, as Figure 2 shown, which includes the following steps:

[0035] Add polyvinyl chloride into DMF, under nitrogen protection, heat up to 70 - 90 °C, then add 4-aminobenzoate compounds and Lewis acid, stir and react for 4 - 6 h, and obtain graft-modified polyvinyl chloride after the product is precipitated, washed and dried;

[0036] Weigh the graft-modified polyvinyl chloride, inorganic filler, plasticizer, stabilizer, lubricant and antioxidant in proportion, add them into a high-speed mixer, mix at 80 - 100 °C for 10 - 20 min, and cool and discharge to obtain a premix;

[0037] Add the premix into an internal mixer, mix at 160 - 180 °C and an internal mixer rotation speed of 30 - 50 rpm for 5 - 15 min to obtain a mixed material;

[0038] The mixed material passes through a four-roll calender, and is calendered and formed at a roll temperature of 160 - 170 °C and a pressure of 10 - 15 MPa to obtain a high-strength and high-weather-resistant polyvinyl chloride composite material.

[0039] For a feasible implementation, the mass ratio of the polyvinyl chloride, 4-aminobenzoate compounds and Lewis acid is (82 - 94):(5 - 16):(0.5 - 2).

[0040] For a feasible implementation, the Lewis acid includes at least one of zinc chloride and aluminum chloride.

[0041] For a feasible implementation, the mass of the DMF is 5 - 10 times that of the polyvinyl chloride.

[0042] The following will specifically describe a high-strength and high-weather-resistant polyvinyl chloride composite material and its preparation method provided by the present application in combination with different embodiments.

[0043] Example 1:

[0044] As Figure 2 shown, a method for preparing a high-strength and high-weather-resistant polyvinyl chloride composite material includes the following steps:

[0045] 1. Add polyvinyl chloride into DMF, add n-propyl 4-aminobenzoate and zinc chloride, heat up to 80 °C under nitrogen protection, stir and react for 5 h, and obtain graft-modified polyvinyl chloride after the product is precipitated, washed and dried;

[0046] In the above steps, the mass ratio of polyvinyl chloride, n-propyl 4-aminobenzoate, and zinc chloride is 88:10:2; the mass of DMF is 6 times that of polyvinyl chloride;

[0047] 2. Weigh graft-modified polyvinyl chloride, light calcium carbonate, tributyl acetylcitrate, calcium laurate / zinc ricinoleate complex, oxidized polyethylene wax, and bis(2,2,6,6-tetramethylpiperidyl) sebacate, add them to a high-speed mixer, mix at 90 °C for 15 min, and cool and discharge to obtain a premix;

[0048] In the above steps, the mass ratio of graft-modified polyvinyl chloride, light calcium carbonate, tributyl acetylcitrate, calcium laurate / zinc ricinoleate complex, oxidized polyethylene wax, and bis(2,2,6,6-tetramethylpiperidyl) sebacate is 55:12:27.5:3:2:0.5;

[0049] 3. Add the premix to an internal mixer, mix at 170 °C and an internal mixer speed of 40 rpm for 10 min to obtain a mixed material;

[0050] 4. The mixed material is calendered by a four-roll calender at a roll temperature of 165 °C and a pressure of 12 MPa to obtain a high-strength and high-weather-resistant polyvinyl chloride composite material.

[0051] Example 2:

[0052] As Figure 2 shown, a preparation method of a high-strength and high-weather-resistant polyvinyl chloride composite material includes the following steps:

[0053] 1. Add polyvinyl chloride to DMF, add isobutyl 4-aminobenzoate and aluminum chloride, heat to 90 °C under nitrogen protection, stir and react for 4 h, and obtain graft-modified polyvinyl chloride after precipitation, washing, and drying of the product;

[0054] In the above steps, the mass ratio of polyvinyl chloride, isobutyl 4-aminobenzoate, and aluminum chloride is 82:16:2; the mass of DMF is 5 times that of polyvinyl chloride;

[0055] 2. Weigh graft-modified polyvinyl chloride, talcum powder, epoxidized soybean oil, calcium stearate / zinc stearate complex, ethylene bisstearamide, and 2,6-di-tert-butyl-p-cresol, add them to a high-speed mixer, mix at 100 °C for 10 min, and cool and discharge to obtain a premix;

[0056] In the above steps, the mass ratio of graft-modified polyvinyl chloride, talcum powder, epoxidized soybean oil, calcium stearate / zinc stearate complex, ethylene bisstearamide, and 2,6-di-tert-butyl-p-cresol is 50:15:28:4:2:1;

[0057] 3. Add the premix into an internal mixer and knead for 5 min at 180 °C with the internal mixer rotating at 50 rpm to obtain a kneaded material.

[0058] 4. Pass the kneaded material through a four-roll calender and calender it into shape at a roll temperature of 160 °C and a pressure of 15 MPa to obtain a high-strength and high-weather-resistant polyvinyl chloride composite material.

[0059] Example 3:

[0060] As Figure 2 shown, a method for preparing a high-strength and high-weather-resistant polyvinyl chloride composite material includes the following steps:

[0061] 1. Add polyvinyl chloride into DMF, add 2-ethylhexyl 4-aminobenzoate and zinc chloride, heat up to 70 °C under nitrogen protection, and stir and react for 6 h. After the product is precipitated, washed, and dried, graft-modified polyvinyl chloride is obtained.

[0062] In the above steps, the mass ratio of polyvinyl chloride, 2-ethylhexyl 4-aminobenzoate, and zinc chloride is 94:5:1; the mass of DMF is 10 times that of polyvinyl chloride.

[0063] 2. Weigh the graft-modified polyvinyl chloride, wollastonite, diisononyl adipate, lanthanum stearate, silicone masterbatch, and dilauryl thiodipropionate, add them into a high-speed mixer, mix for 20 min at 80 °C, and cool and discharge to obtain a premix.

[0064] In the above steps, the mass ratio of the graft-modified polyvinyl chloride, wollastonite, diisononyl adipate, lanthanum stearate, silicone masterbatch, and dilauryl thiodipropionate is 60:12.5:22:2:3:0.5.

[0065] 3. Add the premix into an internal mixer and knead for 15 min at 160 °C with the internal mixer rotating at 30 rpm to obtain a kneaded material.

[0066] 4. Pass the kneaded material through a four-roll calender and calender it into shape at a roll temperature of 170 °C and a pressure of 10 MPa to obtain a high-strength and high-weather-resistant polyvinyl chloride composite material.

[0067] Example 4:

[0068] As Figure 2 shown, a method for preparing a high-strength and high-weather-resistant polyvinyl chloride composite material includes the following steps:

[0069] 1. Add polyvinyl chloride into DMF, add n-butyl 4-aminobenzoate and aluminum chloride, heat up to 85 °C under nitrogen protection, and stir and react for 5.5 h. After the product is precipitated, washed, and dried, graft-modified polyvinyl chloride is obtained.

[0070] In the above steps, the mass ratio of polyvinyl chloride, n-butyl 4-aminobenzoate, and aluminum chloride is 87:12:1; the mass of DMF is 9 times that of polyvinyl chloride;

[0071] 2. Weigh graft-modified polyvinyl chloride, kaolin, dioctyl terephthalate, tributyltin oxide, oxidized polyethylene wax, and bis(2,2,6,6-tetramethylpiperidinyl) sebacate, add them to a high-speed mixer, mix at 95 °C for 12 min, and cool and discharge to obtain a premix;

[0072] In the above steps, the mass ratio of graft-modified polyvinyl chloride, kaolin, dioctyl terephthalate, tributyltin oxide, oxidized polyethylene wax, and bis(2,2,6,6-tetramethylpiperidinyl) sebacate is 57:12:23:5:2.5:0.5;

[0073] 3. Add the premix to an internal mixer, mix at 175 °C and an internal mixer speed of 45 rpm for 8 min to obtain a mixed material;

[0074] 4. The mixed material is calendered by a four-roll calender at a roll temperature of 165 °C and a pressure of 13 MPa to obtain a high-strength and high-weather-resistant polyvinyl chloride composite material.

[0075] Example 5:

[0076] As Figure 2 shown, a preparation method of a high-strength and high-weather-resistant polyvinyl chloride composite material includes the following steps:

[0077] 1. Add polyvinyl chloride to DMF, add isopropyl 4-aminobenzoate and zinc chloride, heat to 75 °C under nitrogen protection, stir and react for 6 h, and obtain graft-modified polyvinyl chloride after precipitation, washing, and drying of the product;

[0078] In the above steps, the mass ratio of polyvinyl chloride, isopropyl 4-aminobenzoate, and zinc chloride is 91:8.5:0.5; the mass of DMF is 7 times that of polyvinyl chloride;

[0079] 2. Weigh graft-modified polyvinyl chloride, mica powder, epoxidized soybean oil, pentaerythritol diphosphite, ethylene bisstearamide, and dilauryl thiodipropionate, add them to a high-speed mixer, mix at 85 °C for 18 min, and cool and discharge to obtain a premix;

[0080] In the above steps, the mass ratio of graft-modified polyvinyl chloride, mica powder, epoxidized soybean oil, pentaerythritol diphosphite, ethylene bisstearamide, and dilauryl thiodipropionate is 54:14:26:3.5:1.8:0.7;

[0081] 3. Add the premix to a Banbury mixer and mix for 12 min at 170 °C with a mixer speed of 35 rpm to obtain a mixed material.

[0082] 4. The mixed material is calendered by a four-roll calender at a roll temperature of 162 °C and a pressure of 14 MPa to obtain a high-strength and high-weather-resistant polyvinyl chloride composite material.

[0083] Example 6:

[0084] As Figure 2 shown, a preparation method of a high-strength and high-weather-resistant polyvinyl chloride composite material includes the following steps:

[0085] 1. Add polyvinyl chloride to DMF, add n-propyl 4-aminobenzoate and aluminum chloride, heat to 88 °C under nitrogen protection, stir and react for 4.5 h, and obtain graft-modified polyvinyl chloride after precipitation, washing and drying.

[0086] In the above steps, the mass ratio of polyvinyl chloride, n-propyl 4-aminobenzoate and aluminum chloride is 83:15:2; the mass of DMF is 8 times that of polyvinyl chloride.

[0087] 2. Weigh the graft-modified polyvinyl chloride, talcum powder, tributyl acetylcitrate, calcium stearate / zinc stearate complex, silicone masterbatch, 2,6-di-tert-butyl-p-cresol, add them to a high-speed mixer, and mix at 100 °C for 10 min, then cool and discharge to obtain a premix.

[0088] In the above steps, the mass ratio of the graft-modified polyvinyl chloride, talcum powder, tributyl acetylcitrate, calcium stearate / zinc stearate complex, silicone masterbatch, 2,6-di-tert-butyl-p-cresol is 58:11.5:23:4.5:2.2:0.8.

[0089] 3. Add the premix to a Banbury mixer and mix for 9 min at 165 °C with a mixer speed of 48 rpm to obtain a mixed material.

[0090] 4. The mixed material is calendered by a four-roll calender at a roll temperature of 168 °C and a pressure of 11 MPa to obtain a high-strength and high-weather-resistant polyvinyl chloride composite material.

[0091] Comparative Example 1:

[0092] A preparation method of a high-strength and high-weather-resistant polyvinyl chloride composite material includes the following steps:

[0093] 1. Weigh polyvinyl chloride, light calcium carbonate, tributyl acetylcitrate, calcium laurate / calcium ricinoleate complex, oxidized polyethylene wax, bis(2,2,6,6-tetramethylpiperidyl) sebacate, add them to a high-speed mixer, and mix at 90 °C for 15 min, then cool and discharge to obtain a premix.

[0094] In the above steps, the mass ratio of polyvinyl chloride, light calcium carbonate, tributyl acetylcitrate, calcium laurate / zinc ricinoleate complex, oxidized polyethylene wax, and bis(2,2,6,6-tetramethylpiperidinyl) sebacate is 55:12:27.5:3:2:0.5;

[0095] 2. Add the premix to a Banbury mixer and knead for 10 min at 170 °C and a Banbury mixer speed of 40 rpm to obtain a kneaded material;

[0096] 3. The kneaded material is calendered by a four-roll calender at a roll temperature of 165 °C and a pressure of 12 MPa to obtain a high-strength and high-weather-resistant polyvinyl chloride composite material.

[0097] Comparative Example 2:

[0098] A method for preparing a high-strength and high-weather-resistant polyvinyl chloride composite material, comprising the following steps:

[0099] 1. Add polyvinyl chloride to DMF, add 2-ethylhexyl benzoate and zinc chloride, heat to 70 °C under nitrogen protection, and stir and react for 6 h. After the product is precipitated, washed, and dried, modified polyvinyl chloride is obtained;

[0100] In the above steps, the mass ratio of polyvinyl chloride, 2-ethylhexyl benzoate, and zinc chloride is 94:5:1; the mass of DMF is 10 times that of polyvinyl chloride;

[0101] 2. Weigh graft-modified polyvinyl chloride, wollastonite, diisononyl adipate, lanthanum stearate, silicone masterbatch, and dilauryl thiodipropionate, add them to a high-speed mixer, and mix at 80 °C for 20 min. After cooling and discharging, a premix is obtained;

[0102] In the above steps, the mass ratio of graft-modified polyvinyl chloride, wollastonite, diisononyl adipate, lanthanum stearate, silicone masterbatch, and dilauryl thiodipropionate is 60:12.5:22:2:3:0.5;

[0103] 3. Add the premix to a Banbury mixer and knead for 15 min at 160 °C and a Banbury mixer speed of 30 rpm to obtain a kneaded material;

[0104] 4. The kneaded material is calendered by a four-roll calender at a roll temperature of 170 °C and a pressure of 10 MPa to obtain a high-strength and high-weather-resistant polyvinyl chloride composite material.

[0105] Comparative Example 3:

[0106] A method for preparing a high-strength and high-weather-resistant polyvinyl chloride composite material, comprising the following steps:

[0107] 1. Add polyvinyl chloride to DMF, add 4-n-propylaniline and aluminum chloride, heat to 88 °C under nitrogen protection, stir and react for 4.5 h, and obtain graft-modified polyvinyl chloride after precipitation, washing and drying the product;

[0108] In the above steps, the mass ratio of polyvinyl chloride, 4-n-propylaniline and aluminum chloride is 83:15:2; the mass of DMF is 8 times that of polyvinyl chloride;

[0109] 2. Weigh the graft-modified polyvinyl chloride, talcum powder, tributyl acetylcitrate, calcium stearate / zinc stearate complex, silicone masterbatch, 2,6-di-tert-butyl-p-cresol, add them to a high-speed mixer, mix at 100 °C for 10 min, and cool and discharge to obtain a premix;

[0110] In the above steps, the mass ratio of the graft-modified polyvinyl chloride, talcum powder, tributyl acetylcitrate, calcium stearate / zinc stearate complex, silicone masterbatch, 2,6-di-tert-butyl-p-cresol is 58:11.5:23:4.5:2.2:0.8;

[0111] 3. Add the premix to a mixer, mix at 165 °C and a mixer speed of 48 rpm for 9 min to obtain a mixed material;

[0112] 4. The mixed material is calendered by a four-roll calender at a roll temperature of 168 °C and a pressure of 11 MPa to obtain a high-strength and high-weather-resistant polyvinyl chloride composite material.

[0113] Refer to GB / T 1040.1-2018 to test the tensile strength of the polyvinyl chloride composite material prepared in this application; refer to GB / T 9341-2008 to test the flexural strength of the prepared polyvinyl chloride composite material; use the test results of both to reflect the high strength of the polyvinyl chloride composite material prepared in this application.

[0114] Refer to GB / T16422.3-2022, age the polyvinyl chloride composite material prepared in this application under a fluorescent ultraviolet lamp, and further refer to GB / T 1040.1-2018 and GB / T 9341-2008 to test the tensile strength and flexural strength of the aged polyvinyl chloride composite material, and calculate the retention rates of both; use this to reflect the weather resistance of the polyvinyl chloride composite material prepared in this application.

[0115] Table 1 Test results of polyvinyl chloride composite materials prepared in examples and comparative examples

[0116]

[0117]

[0118] It can be seen from Table 1 that the tensile strength, flexural strength, tensile strength retention rate and flexural strength retention rate of Examples 1-6 are better than those of Comparative Examples 1-2.

[0119] This is because, when preparing graft-modified polyvinyl chloride, the chlorine atoms on the polyvinyl chloride molecular chain are replaced by the amino groups in the 4-aminobenzoic acid ester compounds to form a graft copolymer bonded by chemical bonds. The amino groups and ester groups introduced by grafting can form hydrogen bonds, enhance the interaction between the graft-modified polyvinyl chloride molecular chains, and improve the strength of the polyvinyl chloride composite material. At the same time, the flexible chain segment of the ester group can increase the mobility of the local chain segment, and the polarity of the amino group can enhance the interfacial compatibility of the graft-modified polyvinyl chloride molecular chain with the inorganic filler material and other components, thereby further improving the strength of the polyvinyl chloride composite material. In addition, the benzene ring in the 4-aminobenzoic acid ester compound forms a larger conjugated system through conjugation, and this larger conjugated system enhances the absorption efficiency of the graft-modified polyvinyl chloride to ultraviolet rays. At the same time, the conjugated system in the above-mentioned polyvinyl chloride composite material is generated by chemical bonding, and is not easy to migrate or change, so the polyvinyl chloride composite material finally obtained has very good weather resistance.

[0120] In Comparative Example 1, no graft-modified polyvinyl chloride was prepared, so hydrogen bonds between polyvinyl chloride molecular chains and conjugated systems that enhance ultraviolet absorption efficiency could not be generated, so the strength and weather resistance of the polyvinyl chloride composite material finally obtained were the worst. In Comparative Example 2, 2-ethylhexyl benzoate was used instead of 4-aminobenzoate compounds when preparing modified polyvinyl chloride, so graft-modified polyvinyl chloride bound by chemical bonds could not be obtained; the strength and weather resistance of the polyvinyl chloride composite material finally obtained were poor. In Comparative Example 3, although graft-modified polyvinyl chloride could also be obtained by reaction using 4-n-propylaniline, a conjugated system could not be generated, so the strength and weather resistance of the polyvinyl chloride composite material finally obtained were better than those of Comparative Examples 1 and 2, but still inferior to those of Examples 1 to 6.

[0121] The above results show and describe the basic principles and main features of the present application as well as the advantages of the present application.

[0122] Those skilled in the art should understand that the present application is not limited by the above embodiments, and the above embodiments and descriptions are only for explaining the principles of the present application. Without departing from the spirit and scope of the present application, the present application may have various changes and improvements, and these changes and improvements fall within the scope of the present application for which protection is sought. The scope of protection sought in the present application is defined by the equivalents of the attached claims.

Claims

1. A high-strength and high-weather-resistant polyvinyl chloride composite material, characterized in that It includes graft-modified polyvinyl chloride; the graft-modified polyvinyl chloride is obtained by reacting a 4-aminobenzoate compound with polyvinyl chloride; the 4-aminobenzoate compound includes any one of n-propyl 4-aminobenzoate, isopropyl 4-aminobenzoate, n-butyl 4-aminobenzoate, isobutyl 4-aminobenzoate, and 2-ethylhexyl 4-aminobenzoate.

2. A high-strength and high-weather-resistant polyvinyl chloride composite material according to claim 1, characterized in that The structure of the graft-modified polyvinyl chloride includes: Among them, R includes any one of propyl, isopropyl, butyl, isobutyl, and 2-ethylhexyl.

3. A high-strength and high-weather-resistant polyvinyl chloride composite material according to claim 1, characterized in that, It also includes an inorganic filler, a plasticizer, a stabilizer, a lubricant, and an antioxidant; the mass ratio of the graft-modified polyvinyl chloride, inorganic filler, plasticizer, stabilizer, lubricant, and antioxidant is (50 - 60):(10 - 15):(20 - 30):(2 - 5):(1 - 3):(0.5 - 1).

4. The high-strength and high-weather resistance polyvinyl chloride composite material according to claim 3, characterized in that The inorganic filler includes at least one of light calcium carbonate, talc powder, wollastonite, kaolin, and mica powder.

5. The high-strength and high-weather-resistant polyvinyl chloride composite material according to claim 3, wherein The plasticizer includes at least one of tributyl acetylcitrate, epoxidized soybean oil, diisononyl adipate, and dioctyl terephthalate.

6. The high-strength and high-weather-resistant polyvinyl chloride composite material according to claim 3, wherein The stabilizer includes at least one of calcium laurate / zinc ricinoleate complex, calcium stearate / zinc stearate complex, lanthanum stearate, tributyltin oxide, and pentaerythritol diphosphite.

7. The high-strength and high-weather-resistant polyvinyl chloride composite material according to claim 3, wherein, The lubricant includes at least one of oxidized polyethylene wax, ethylene bisstearamide, and silicone masterbatch.

8. The high-strength and high-weather-resistant polyvinyl chloride composite material according to claim 3, characterized in that, The antioxidant includes at least one of bis(2,2,6,6-tetramethylpiperidyl) sebacate, 2,6-di-tert-butyl-p-cresol, and dilauryl thiodipropionate.

9. The preparation method of the high-strength and high-weather-resistant polyvinyl chloride composite material according to any one of claims 3 to 8, characterized in that, It includes the following steps: Add polyvinyl chloride to DMF, under nitrogen protection, heat up to 70 - 90 °C, then add a 4-aminobenzoate compound and a Lewis acid, stir and react for 4 - 6 h, and obtain the graft-modified polyvinyl chloride after the product is precipitated, washed, and dried. Weigh the graft-modified polyvinyl chloride, inorganic filler, plasticizer, stabilizer, lubricant, and antioxidant, add them to a high-speed mixer, mix at 80 - 100 °C for 10 - 20 min, and cool and discharge to obtain a premix. Add the premix to an internal mixer, mix at 160 - 180 °C and an internal mixer speed of 30 - 50 rpm for 5 - 15 min to obtain a mixed material. The mixed material is calendered by a four-roll calender at a roll temperature of 160 - 170 °C and a pressure of 10 - 15 MPa to obtain a high-strength and high-weather-resistant polyvinyl chloride composite material.

10. The preparation method of a high-strength and high-weather-resistant polyvinyl chloride composite material according to claim 9, characterized in that, The mass ratio of the polyvinyl chloride, 4-aminobenzoate compound, and Lewis acid is (82 - 94):(5 - 16):(0.5 - 2); the Lewis acid includes at least one of zinc chloride and aluminum chloride; the mass of DMF is 5 - 10 times that of the polyvinyl chloride.

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