CN113462054A - Preparation method of heat-resistant glass fiber reinforced PE composite material - Google Patents
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
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- C08J2481/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2481/06—Polysulfones; Polyethersulfones
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/34—Silicon-containing compounds
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Abstract
The invention provides a preparation method of a heat-resistant glass fiber reinforced PE composite material, and belongs to the technical field of modification of polyethylene composite materials. The components of the composition by weight portion are as follows: 55-70 parts of high-density polyethylene, 12-16 parts of mica filling modified PSF, 35-42 parts of glass fiber, 6-8 parts of compatilizer, 5-6 parts of antioxidant, 3-8 parts of flame retardant and 0.5-1.2 parts of sodium stearate. The invention adopts mica powder to fill and modify PSF, and the modified PSF and glass fiber are compounded, blended and modified for high-density polyethylene. The glass fiber reinforced PE composite material prepared by the invention overcomes the defect of poor heat-resistant aging resistance of PE, and the prepared composite material has excellent mechanical properties and meets the use conditions of multiple fields.
Description
Technical Field
The invention belongs to the technical field of polyethylene composite material modification, and particularly relates to a preparation method of a heat-resistant glass fiber reinforced PE composite material.
Background
Polyethylene (PE) is a high molecular thermoplastic resin obtained by polymerizing ethylene, and the actual molecular weight varies from ten thousand to several million according to the polymerization conditions. The polyethylene is white wax-like translucent material, is soft and tough, lighter than water, odorless and nontoxic, has wax-like hand feeling, excellent electrical insulation performance and excellent dielectric property. Easy to burn and continue burning after leaving fire, low water permeability, small water absorption and larger organic vapor permeability. The polyethylene has excellent chemical stability, can resist most of acid and alkali erosion, and has excellent low temperature resistance (the lowest use temperature can reach-70 to-100 ℃). Because of its excellent performance, polyethylene has wide application, and is mainly used for manufacturing films, containers, pipelines, monofilaments, electric wires and cables, daily necessities and the like, and can be used as high-frequency insulating materials of televisions, radars and the like.
However, polyethylene is very sensitive to environmental stresses (chemical and mechanical effects), has insufficient strength, toughness, etc., and particularly has poor heat aging resistance, thus limiting its application in certain high temperature fields. In the prior art, heat-resistant plastics are often adopted to carry out blending modification on polyethylene so as to enhance the heat resistance of the polyethylene, but the composite material obtained by modifying low-cost low-heat-resistant plastics has small heat resistance improvement range, the obtained PE composite material still does not meet the use condition, and the modification of PE by using high-heat-resistant or ultrahigh-heat-resistant plastics can greatly increase the modification cost.
Therefore, the preparation of polyethylene composite materials with high heat resistance and low cost by reinforcing and modifying polyethylene becomes the focus of research.
Disclosure of Invention
Aiming at the problems in the background art, the invention provides a preparation method of a heat-resistant glass fiber reinforced PE composite material, wherein the PSF is filled and modified by mica powder, and the modified PSF and glass fiber are used for compounding, blending and modifying high-density polyethylene, so that the defects of poor heat aging resistance and insufficient strength toughness of polyethylene are effectively overcome, the modification cost is low, and the preparation method is realized by the following technical scheme:
the heat-resistant glass fiber reinforced PE composite material comprises the following components in parts by weight:
55-70 parts of high-density polyethylene;
12-16 parts of mica filling modified PSF;
35-42 parts of glass fiber;
6-8 parts of a compatilizer;
5-6 parts of an antioxidant;
3-8 parts of a flame retardant;
0.5-1.2 parts of sodium stearate.
Further, the high-density polyethylene has a molecular weight of 30-60 ten thousand and a melt index MFI of not more than 5g/10min under a test condition of 5kg at 280 ℃.
Further, the preparation method of the mica filled and modified PSF comprises the following steps: sequentially putting mica powder, a silane coupling agent, PSF, a compatilizer and an antioxidant into a stirrer, stirring at the high speed of 1000r/min for 4-8min at the temperature of 90-120 ℃, then transferring into a double-screw extruder for extrusion granulation, and cooling to obtain the mica filled modified PSF.
Further, the usage amount of the mica powder is 5-12g, the usage amount of the silane coupling agent is 8-15g, the usage amount of the compatilizer is 3-5g, and the usage amount of the antioxidant is 2-3g, relative to 100g of PSF.
Further, the particle size of the mica powder is 200-400 meshes.
Further, the PSF has a melt index MFI of more than 8.5g/10min at 280 ℃ under 5kg test conditions.
Further, the silane coupling agent is KH 550.
The mica powder is a nonmetallic mineral and contains multiple components, wherein SiO is the main component2The mica powder has the characteristics of good elasticity, toughness, insulativity, high temperature resistance and the like, and is an excellent additive. The maximum use temperature of the mica powder can reach 1000 ℃, the mica powder is a high-efficiency heat-resistant modified filler, and the smaller the granularity is, the better the heat-resistant modified effect is.
The silane coupling agent KH550 (gamma-aminopropyltriethoxysilane) is used for coupling organic polymers and inorganic fillers, so that the cohesiveness of the organic polymers and the inorganic fillers is enhanced, and the mechanical, water-resistant, ageing-resistant and other performances of the product are improved.
PSF (polysulfone) is thermoplastic resin containing sulfonyl and arylene in a molecular main chain, has excellent mechanical property, high rigidity, wear resistance and high strength, belongs to middle-low heat-resistant plastics, and has lower cost.
A preparation method of a heat-resistant glass fiber reinforced PE composite material comprises the following steps:
1) sequentially adding high-density polyethylene, mica filling modified PSF, a compatilizer, an antioxidant, a flame retardant and sodium stearate into a stirrer according to formula components, and stirring for 3-5min at 8000r/min of 5000-;
2) and (3) transferring the obtained mixture and the glass fiber into a double-screw extruder for extrusion granulation, cooling, and drying at the temperature of 80-100 ℃ for 8-12h to obtain the heat-resistant glass fiber reinforced PE composite material.
Further, the compatilizer is maleic anhydride grafted polyethylene.
Further, the antioxidant is one or more of antioxidant 1076, antioxidant DNP and antioxidant 168.
The compatilizer is a stable blend obtained by combining incompatible two substances together by virtue of intermolecular bonding force; the maleic anhydride grafted polyethylene adopted by the invention can improve the compatibility of the inorganic filler and the PSF/modified PSF or polyethylene, improve the tensile strength and the impact strength, reduce the resin consumption by high filling, and improve the processing rheological property.
For plastic processing, the antioxidant can prevent thermal oxidation decomposition in the polymer processing process, so that the processing can be smoothly carried out, and according to the processing method of the PE composite material, the invention adopts one or more of the antioxidant 1076, the antioxidant DNP and the antioxidant 168.
Further, the flame retardant is prepared from tribromobenzene and octabromoether according to a mass ratio of 1: (1.7-2).
Further, the glass fiber is a short fiber having a length in the range of 0.2 to 6 mm.
Tribromobenzene and octabromoether are better additive flame retardants, and according to the preparation process of the PE composite material, tribromobenzene and octabromoether are mixed according to a certain proportion for use, so that a better flame retardant effect is obtained.
Glass fibers, an inorganic non-metallic material with excellent properties, are widely used as a reinforcing material in composite materials to reinforce the strength, rigidity and stability of plastics.
Further, the screw rotating speed of the double-screw extruder is controlled at 450-550r/min, and the temperature of each zone of the extruder is controlled at 160-280 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the invention firstly adopts mica powder to fill and modify PSF, the modified PSF is mixed with the compatilizer, antioxidant, flame retardant and the like selected by the invention and the high-density polyethylene, and then the modified PSF is compositely modified by glass fiber, so that the heat aging resistance of the prepared PE composite material is obviously improved. The invention uses low-cost medium-low heat-resistant resin PSF, inorganic mineral filler and glass fiber, but obtains heat-resistant modification effect similar to high-cost high-heat-resistant or ultrahigh-heat-resistant plastic. The PE composite material prepared by the invention can meet the use requirement in a heat-resistant manner, has excellent mechanical property, greatly reduces the production cost, widens the high-temperature application field of polyethylene, and has wide market prospect.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be described more clearly and completely with reference to the following embodiments. The examples do not show the specific conditions, and the reagents or apparatuses used are not shown in the manufacturers, and all of them are conventional products commercially available.
Example 1
A heat-resistant glass fiber reinforced PE composite material:
1) sequentially putting 8g of mica powder, 10g of KH550, 100g of PSF, 4g of maleic anhydride grafted polyethylene and 2g of antioxidant 168 into a stirrer, stirring at 110 ℃ for 5min at a high speed of 900r/min, then transferring into a double-screw extruder to carry out extrusion granulation, and cooling to obtain the mica filled modified PSF.
2) 65 parts of high-density polyethylene, 15 parts of mica filling modified PSF, 8 parts of maleic anhydride grafted polyethylene, 5 parts of antioxidant 1076, and 6 parts of flame retardant (prepared by mixing tribromobenzene and octabromoether in a mass ratio of 1: 2 component) and 0.8 part of sodium stearate are added into a stirrer in sequence according to the formula components and stirred for 5min at 7000 r/min.
3) And (3) transferring the obtained mixture and 40 parts of glass fiber into a double-screw extruder for extrusion granulation, cooling, and drying at 100 ℃ for 10 hours to obtain the heat-resistant glass fiber reinforced PE composite material.
The performance of the glass fiber reinforced PE composite material sample prepared by the embodiment is detected, and the measured result is as follows: tensile strength of 22.41MPa, elongation at break of 350.22%, Vicat softening point of 248 ℃, 100 ℃ air oven aging for 10 d: the tensile strength after aging is 19.63MPa, and the elongation at break after aging is 549.75%.
Example 2
A heat-resistant glass fiber reinforced PE composite material:
1) sequentially putting 8g of mica powder, 10g of KH550, 100g of PSF, 4g of maleic anhydride grafted polyethylene and 2g of antioxidant 168 into a stirrer, stirring at 110 ℃ for 5min at a high speed of 900r/min, then transferring into a double-screw extruder to carry out extrusion granulation, and cooling to obtain the mica filled modified PSF.
2) 55 parts of high-density polyethylene, 16 parts of mica filling modified PSF, 8 parts of maleic anhydride grafted polyethylene, 5 parts of antioxidant 1076, and 6 parts of flame retardant (prepared by mixing tribromobenzene and octabromoether in a mass ratio of 1: 2 component) and 0.8 part of sodium stearate are added into a stirrer in sequence according to the formula components and stirred for 5min at 7000 r/min.
3) And (3) transferring the obtained mixture and 40 parts of glass fiber into a double-screw extruder for extrusion granulation, cooling, and drying at 100 ℃ for 10 hours to obtain the heat-resistant glass fiber reinforced PE composite material.
The performance of the glass fiber reinforced PE composite material sample prepared by the embodiment is detected, and the measured result is as follows: tensile strength 23.25MPa, elongation at break 375.06%, Vicat softening point 244 ℃, 100 ℃ air oven aging for 10 d: the tensile strength after aging is 20.96MPa, and the elongation at break after aging is 588.60%.
Example 3
A heat-resistant glass fiber reinforced PE composite material:
1) sequentially putting 8g of mica powder, 10g of KH550, 100g of PSF, 4g of maleic anhydride grafted polyethylene and 2g of antioxidant 168 into a stirrer, stirring at 110 ℃ for 5min at a high speed of 900r/min, then transferring into a double-screw extruder to carry out extrusion granulation, and cooling to obtain the mica filled modified PSF.
2) 70 parts of high-density polyethylene, 12 parts of mica filling modified PSF, 8 parts of maleic anhydride grafted polyethylene, 5 parts of antioxidant 1076, and 6 parts of flame retardant (prepared by mixing tribromobenzene and octabromoether in a mass ratio of 1: 2 component) and 0.8 part of sodium stearate are added into a stirrer in sequence according to the formula components and stirred for 5min at 7000 r/min.
3) And (3) transferring the obtained mixture and 40 parts of glass fiber into a double-screw extruder for extrusion granulation, cooling, and drying at 100 ℃ for 10 hours to obtain the heat-resistant glass fiber reinforced PE composite material.
The performance of the glass fiber reinforced PE composite material sample prepared by the embodiment is detected, and the measured result is as follows: tensile strength 20.62MPa, elongation at break 344.10%, Vicat softening point 233 ℃, 100 ℃ air oven aging for 10 d: the tensile strength after aging is 18.44MPa, and the elongation at break after aging is 540.68%.
Example 4
A heat-resistant glass fiber reinforced PE composite material:
1) sequentially putting 8g of mica powder, 10g of KH550, 100g of PSF, 4g of maleic anhydride grafted polyethylene and 2g of antioxidant 168 into a stirrer, stirring at 110 ℃ for 5min at a high speed of 900r/min, then transferring into a double-screw extruder to carry out extrusion granulation, and cooling to obtain the mica filled modified PSF.
2) According to the mass parts, 65 parts of high-density polyethylene, 15 parts of mica filling modified PSF, 6 parts of maleic anhydride grafted polyethylene, 6 parts of antioxidant DNP, and 6 parts of flame retardant (prepared by mixing tribromobenzene and octabromoether according to the mass ratio of 1: 1.7), 0.8 portion of sodium stearate is added into a stirrer in turn according to the formula components and stirred for 5min at 7000 r/min.
3) And (3) transferring the obtained mixture and 35 parts of glass fiber into a double-screw extruder for extrusion granulation, cooling, and drying at 100 ℃ for 10 hours to obtain the heat-resistant glass fiber reinforced PE composite material.
The performance of the glass fiber reinforced PE composite material sample prepared by the embodiment is detected, and the measured result is as follows: tensile strength of 22.55MPa, elongation at break of 347.02%, Vicat softening point of 241 ℃, 100 ℃ air oven aging for 10 d: the tensile strength after aging is 19.98MPa, and the elongation at break after aging is 545.87%.
Comparative example 1
1) According to the mass portion, 65 portions of high-density polyethylene, 15 portions of unmodified PSF, 8 portions of maleic anhydride grafted polyethylene, 5 portions of antioxidant 1076, 6 portions of flame retardant (prepared by mixing tribromobenzene and octabromoether according to the mass ratio of 1: 2 component) and 0.8 part of sodium stearate are added into a stirrer in sequence according to the formula components and stirred for 5min at 7000 r/min.
2) And transferring the obtained mixture and 40 parts of glass fiber into a double-screw extruder for extrusion granulation, cooling, and drying at 100 ℃ for 10 hours to obtain the PE composite material.
The PE composite material sample prepared by the comparative example is subjected to performance detection, and the detection result is as follows: tensile strength of 17.44MPa, elongation at break of 283.55%, Vicat softening point of 163 ℃, 100 ℃ air oven aging for 10 d: the tensile strength after aging is 11.93MPa, and the elongation at break after aging is 468.13%.
As can be seen from examples 1-4 and comparative example 1, the glass fiber reinforced PE composite material prepared by filling and modifying the PSF with the mica powder and then performing composite blending and modification on the high-density polyethylene with the modified PSF and the glass fiber has good thermal aging resistance, while the PE composite material prepared by performing composite blending and modification on the high-density polyethylene with unmodified PSF and the glass fiber has improved thermal aging resistance, but is still poor and does not meet the use requirement in the high-temperature field.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solutions of the present application and not to limit them; although the present application has been described in detail with reference to preferred embodiments, those of ordinary skill in the art will understand that: modifications to the embodiments of the present application or equivalent replacements of some technical features may still be made, which should all be covered by the scope of the technical solution claimed in the present application.
Claims (10)
1. The heat-resistant glass fiber reinforced PE composite material is characterized by comprising the following components in parts by weight:
55-70 parts of high-density polyethylene;
12-16 parts of mica filling modified PSF;
35-42 parts of glass fiber;
6-8 parts of a compatilizer;
5-6 parts of an antioxidant;
3-8 parts of a flame retardant;
0.5-1.2 parts of sodium stearate.
2. The heat-resistant glass fiber reinforced PE composite material as claimed in claim 1, wherein the high density polyethylene has a molecular weight of 30-60 ten thousand and a melt index MFI of not more than 5g/10min under a test condition of 5kg at 280 ℃.
3. The heat-resistant glass fiber reinforced PE composite material as claimed in claim 1, wherein the mica-filled modified PSF is prepared by a method comprising the following steps: sequentially putting mica powder, a silane coupling agent, PSF, a compatilizer and an antioxidant into a stirrer, stirring at the high speed of 1000r/min for 4-8min at the temperature of 90-120 ℃, then transferring into a double-screw extruder for extrusion granulation, and cooling to obtain the mica filled modified PSF.
4. The heat-resistant glass fiber reinforced PE composite material as claimed in claim 3, wherein the mica powder is used in an amount of 5-12g, the silane coupling agent is used in an amount of 8-15g, the compatibilizer is used in an amount of 3-5g, and the antioxidant is used in an amount of 2-3g per 100g of PSF.
5. The heat-resistant glass fiber reinforced PE composite material as recited in claim 4, wherein the mica powder has a particle size of 200-400 mesh.
6. The heat-resistant glass fiber reinforced PE composite material as claimed in claim 4, wherein the PSF has a melt index MFI of more than 8.5g/10min at 280 ℃ under a test condition of 5 kg.
7. The method for preparing the heat-resistant glass fiber reinforced PE composite material as claimed in any one of claims 1 to 6, comprising the steps of:
1) sequentially adding high-density polyethylene, mica filling modified PSF, a compatilizer, an antioxidant, a flame retardant and sodium stearate into a stirrer according to formula components, and stirring for 3-5min at 8000r/min of 5000-;
2) and (3) transferring the obtained mixture and the glass fiber into a double-screw extruder for extrusion granulation, cooling, and drying at the temperature of 80-100 ℃ for 8-12h to obtain the heat-resistant glass fiber reinforced PE composite material.
8. The preparation method of the heat-resistant glass fiber reinforced PE composite material according to claim 7, wherein the flame retardant is prepared from tribromobenzene and octabromoether in a mass ratio of 1: (1.7-2).
9. The method of claim 7, wherein the glass fiber is short fiber having a length in the range of 0.2-6 mm.
10. The method for preparing the heat-resistant glass fiber reinforced PE composite material as claimed in claim 7, wherein the screw rotation speed of the twin-screw extruder is controlled at 450-550r/min, and the temperatures of the zones of the extruder are controlled at 160-280 ℃.
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CN115029946A (en) * | 2022-06-29 | 2022-09-09 | 界首市宏利塑料股份有限公司 | Wear-resistant PE plastic rope and production process thereof |
CN115304852A (en) * | 2022-10-12 | 2022-11-08 | 山东寿光鲁清石化有限公司 | Preparation method of high-density polyethylene composition |
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CN115029946A (en) * | 2022-06-29 | 2022-09-09 | 界首市宏利塑料股份有限公司 | Wear-resistant PE plastic rope and production process thereof |
CN115029946B (en) * | 2022-06-29 | 2024-03-22 | 界首市宏利塑料股份有限公司 | Wear-resistant PE plastic rope and production process thereof |
CN115304852A (en) * | 2022-10-12 | 2022-11-08 | 山东寿光鲁清石化有限公司 | Preparation method of high-density polyethylene composition |
CN116162301A (en) * | 2022-12-28 | 2023-05-26 | 江苏中通管业有限公司 | Reinforced polyethylene pipe and production method thereof |
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