CN114524986A

CN114524986A - Environment-friendly flame-retardant PVC/PE composite material and preparation method thereof

Info

Publication number: CN114524986A
Application number: CN202210361367.0A
Authority: CN
Inventors: 从宪玲; 李其建; 高虎; 任仰省; 刘宏旭; 栾晓波
Original assignee: Graphene Polymer Composites R&d Center Shandong Lutai Holding Group Co ltd; Shandong Lutai Holding Group Co Ltd
Current assignee: Graphene Polymer Composites R&d Center Shandong Lutai Holding Group Co ltd; Shandong Lutai Holding Group Co Ltd
Priority date: 2022-04-07
Filing date: 2022-04-07
Publication date: 2022-05-24
Anticipated expiration: 2042-04-07
Also published as: CN114524986B

Abstract

The invention relates to an environment-friendly flame-retardant PVC/PE composite material and a preparation method thereof, belonging to the technical field of macromolecules. The paint specifically comprises the following components in parts by weight: 55-75 parts of polyethylene; 25-45 parts of polyvinyl chloride; 0.2-1 part of a lubricant; 2-5 parts of a compatilizer; 0.6-3 parts of a stabilizer; 2-6 parts of a plasticizer; 10100.1-0.3 part of antioxidant; 1-10 parts of flame-retardant filler; 2-10 parts of chlorinated polyethylene; 0-1 part of ACR resin. The PVC flame-retardant PE is used, the raw material cost is low, the comprehensive economic cost performance is high, and the flame-retardant performance of the material meets the market demand.

Description

Environment-friendly flame-retardant PVC/PE composite material and preparation method thereof

Technical Field

The invention belongs to the technical field of macromolecules, and particularly relates to an environment-friendly flame-retardant PVC/PE composite material and a preparation method thereof.

Background

As a synthetic resin used in the largest amount in the world, Polyethylene (PE) has characteristics of no toxicity, no odor, light weight, low water absorption, and the like, and also has excellent low-temperature toughness, electrical insulation, chemical stability, and processability, and thus is widely used in the fields of chemical industry, electrical industry, machinery, food, packaging, agriculture, and the like. However, polyethylene only contains carbon and hydrogen, has an oxygen index of 17-18, is extremely easy to burn under the action of oxygen and heat, has high burning speed and much heat release, is accompanied by fuming and dripping phenomena, and has great potential safety hazard. Therefore, if a safe and reliable polyethylene product meeting special requirements is to be obtained, the polyethylene product needs to be subjected to flame retardant modification treatment.

Polyethylene combustion is a complex thermal oxidation reaction process: after the material is heated, heat can be transmitted into the material to cause the polymer to melt; the polymer is continuously heated, the temperature of the polymer is continuously raised, and a degradation reaction can be carried out to generate various gas-phase combustible materials such as monomer flammable hydrocarbon and the like; enough combustible materials are combusted under the action of oxygen and high temperature; the heat generated by the combustion section is transferred to the adjacent solid section by conduction, radiation, convection, etc., thereby causing sustained combustion. Therefore, the focus of flame retardant modification of polyethylene is on how to effectively interfere with the three elements (oxygen, heat and combustibles) that sustain combustion. Compared with other inorganic flame retardants, the halogen flame retardant has good compatibility with polyethylene and high flame retardant efficiency, can decompose HX for capturing and transferring combustion free radicals in the pyrolysis process, can dilute combustible gas generated in the polyethylene pyrolysis process, has good gas-phase flame retardant effect, and is favored in the early stage. However, the environmental protection problem of countries such as the European Union in 2008 is prohibited from the implementation of halogen flame retardants such as decabromodiphenyl oxide and tetrabromobisphenol A (octabromoether), and decabromodiphenyl ethane, which is an environmental protection substitute for decabromodiphenyl oxide, has a problem of high price although it has a good flame retardant effect.

Polyvinyl chloride (PVC) has the characteristics of excellent mechanical property, good flame retardance, wide application range and the like, and if PVC and PE are blended to prepare the alloy, the PVC and the PE can be complemented in properties, so that the product can obtain good flame retardance. Meanwhile, the PVC is low in price, and if expensive flame retardants such as decabromodiphenylethane can be replaced by the PVC, the cost of the product can be greatly reduced. However, PE and PVC are incompatible polymers, the PVC is easy to agglomerate in the forming process, and a gap is easy to generate at the interface of two phases, so that the mechanical property of the PE/PVC blend is influenced, and defects are easy to exist in the processing process. Therefore, how to improve the compatibility of PE and PVC and prepare the composite material with excellent mechanical property and good flame retardant property is still a big difficulty.

Disclosure of Invention

Aiming at the problems of high addition amount and high price of PE flame retardant materials, poor mechanical property of PE/PVC composite materials, poor PE/PVC compatibility, easy agglomeration of PVC, poor processability and the like in the prior art, the invention provides an environment-friendly flame retardant PVC/PE composite material and a preparation method thereof, so as to solve the problems.

The technical scheme of the invention is as follows:

an environment-friendly flame-retardant PVC/PE composite material comprises the following components in parts by weight: 55-75 parts of polyethylene; 25-45 parts of polyvinyl chloride; 0.2-1 part of a lubricant; 2-5 parts of a compatilizer; 0.6-3 parts of a stabilizer; 2-6 parts of a plasticizer; 10100.1-0.3 part of antioxidant; 1-10 parts of flame-retardant filler; 2-10 parts of chlorinated polyethylene; 0-1 part of ACR resin.

Preferably, the polyethylene is one of High Density Polyethylene (HDPE), Low Density Polyethylene (LDPE), and Linear Low Density Polyethylene (LLDPE).

Preferably, the average polymerization degree of the polyvinyl chloride is 650 to 750. The polymerization degree can influence the plasticizing performance and the fluidity, the polymerization degree is high, the processing temperature is high, the fluidity is poor, the PVC resin produced in China at present is mainly universal in type, the grade of the PVC resin with ultralow polymerization degree is less, and therefore the PVC resin with the polymerization degree of 650-750 is selected.

Preferably, the lubricant is at least one of stearic acid, paraffin wax, polyethylene wax (PE wax), oxidized polyethylene wax (OPE wax), Ethylene Bis Stearamide (EBS), monoglyceride, and polyol fatty acid ester.

Preferably, the compatibilizer is at least one of maleic anhydride grafted polyethylene (PE-g-MAH), maleic anhydride grafted ethylene-vinyl acetate copolymer (EVA-g-MAH), and ethylene-vinyl acetate copolymer (EVA).

Preferably, wherein the plasticizer is: graphene oxide/chloromethoxyfatty acid ester mixtures. And (2) placing the graphene oxide in ethanol for ultrasonic dispersion, adding a certain amount of 3-chloropropyltrimethoxysilane, heating, stirring, refluxing for 10 hours, cleaning, filtering, and drying to obtain the activated graphene oxide. Ball-milling and ultrasonically dispersing the mixture in chloromethoxy fatty acid ester to obtain a graphene oxide/chloromethoxy fatty acid ester mixture. The chloromethoxy fatty acid ester can weaken the acting force between long-chain molecules of PVC resin, improve the plasticity, flexibility and processability of PVC, and contains chlorine elements with a certain flame retardant effect. The graphene oxide generates lamellar obstruction on a PVC molecular chain, so that hydrogen chloride precipitation and PVC degradation can be effectively delayed, in addition, the graphene oxide contains a large amount of oxygen-containing groups and has a certain stabilizing effect on unstable chlorine atoms in the PVC molecular chain, and compared with other environment-friendly plasticizers, the graphene oxide/chloromethoxy fatty acid ester mixture improves the plasticity, flexibility, processability, stability and flame retardance of PVC to a certain extent.

Preferably, the flame-retardant filler is one or more of aluminum hydroxide, antimony trioxide, magnesium hydroxide, kaolin and zinc borate.

Preferably, the stabilizer is one or more of calcium-zinc composite stabilizer, organic tin stabilizer, rare earth stabilizer and epoxidized soybean oil.

The invention also provides a preparation method of the PVC/PE environment-friendly flame-retardant composite material, which comprises the following specific steps:

(1) mixing PVC, a stabilizer, a lubricant, a graphene oxide/chloromethoxy fatty acid ester mixture, CPE and ACR in a high-speed mixer, and extruding and granulating after the materials are cooled to obtain the PVC prefabricated granular material. Wherein the extrusion temperature is: 145-180 ℃;

(2) placing the PE resin, the PVC prefabricated granules, the compatilizer, the antioxidant 1010 and the flame-retardant filler into an internal mixer for internal mixing for 3-5 min, wherein the internal mixing temperature is as follows: 150-180 ℃;

(3) and (3) forming the internally mixed materials at the temperature of 150-180 ℃ and under the pressure of 5-25 MPa for 5-10 min.

The invention has the beneficial effects that:

(1) compared with the traditional flame-retardant method, the flame-retardant PVC PE material has the advantages of low raw material cost, high comprehensive economic performance-price ratio and capability of meeting the market demand on the flame-retardant property.

(2) In order to obtain excellent flame retardant performance, the addition amount of the inorganic flame retardant in the prior art is high, but the addition amount causes serious loss of mechanical properties of the material. According to the invention, PVC flame-retardant PE is used, the PE and the PVC are in a structure of 'sea-island', dispersed phase particles are dispersed in a continuous phase, and graphene oxide/PVC composite effectively blocks flame, so that the flame retardant property of the product is improved.

(3) PE/PVC blends are thermodynamically incompatible and have poor adhesion between two phases, so that direct mixing has the problems of poor compatibility and poor plasticization of PVC phases, resulting in loss of mechanical properties of the product. According to the invention, the graphene oxide/chloromethoxy fatty acid ester mixture is used for treating PVC, PVC is pre-plasticized, the processing temperature of PVC is reduced, the fluidity of PVC is improved, and the pre-plasticization of PVC solves the problems of primary particle agglomeration, difficult plasticization, non-compact product and the like of PVC in a PE system. The relation between the mechanical property and the flame retardant property is balanced.

Detailed Description

In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

A preparation method of a PVC/PE environment-friendly flame-retardant composite material comprises the following specific steps:

(1) 25 parts of polyvinyl chloride (S58), 0.2 part of OPE wax, 0.6 part of polyol fatty acid ester, 0.5 part of organic tin stabilizer, 2 parts of graphene oxide/chloromethoxy fatty acid ester mixture, 3 parts of CPE and 0.5 part of ACR. Mixing PVC, a stabilizer, a lubricant, a graphene oxide/chloromethoxy fatty acid ester mixture, CPE and ACR in a high-speed mixer, and extruding and granulating after the materials are cooled to obtain the PVC prefabricated granular material. Wherein the extrusion temperature is 145-180 ℃.

(2) 75 parts of polyethylene (HDPE), 3 parts of aluminum hydroxide, 2 parts of antimony trioxide, 2 parts of PE-g-MAH, 10100.3 parts of antioxidant and 31.8 parts of PVC prefabricated material are placed in an internal mixer at 170 ℃ for internal mixing for 3-5 min.

(3) And (3) carrying out die pressing on the internally mixed materials at the temperature of 180 ℃ and under the pressure of 20MPa for 7min for forming.

Example 2

(1) 35 parts of polyvinyl chloride (SG-8), 0.1 part of stearic acid, polyol fatty acid ester: 0.5 part, 0.1 part of PE wax, and organotin stabilizer: 0.7 part of epoxidized soybean oil, 0.5 part of graphene oxide/chloromethoxy fatty acid ester mixture, 5 parts of CPE (chlorinated polyethylene) and 0.2 part of ACR (acrylic rubber) are weighed according to the proportion, the materials are placed in a high-speed mixer to be mixed for 5-15 min, and after the materials are cooled, a double-screw extruder is used for extrusion granulation to obtain the PVC prefabricated granule material. Wherein the extrusion temperature is 145-180 ℃.

(2) 65 parts of polyethylene (HDPE), 3 parts of aluminum hydroxide, 1 part of antimony trioxide, 2 parts of zinc borate, 3 parts of PE-g-MAH, 10100.2 parts of antioxidant and 44.1 parts of PVC prefabricated material are placed in an internal mixer at 170 ℃ for internal mixing for 3-5 min.

(3) And (3) carrying out die pressing on the internally mixed materials at the temperature of 180 ℃ and under the pressure of 15MPa for 5min for forming.

Example 3

(1) 30 parts of polyvinyl chloride (S700), 0.1 part of paraffin, polyol fatty acid ester: 0.4 part of PE wax, 0.1 part of organic tin stabilizer, 0.6 part of epoxidized soybean oil, 0.4 part of calcium stearate, 3 parts of graphene oxide/chloro-methoxy fatty acid ester mixture, 4 parts of CPE and 0.4 part of ACR, and placing the materials in a high-speed mixer for mixing for 10-15 min, and after the materials are cooled, extruding and granulating by using a double-screw extruder to obtain the PVC prefabricated granule material. Wherein the extrusion temperature is 145-180 ℃.

(2) 70 parts of polyethylene (LDPE), 1 part of aluminum hydroxide, 3 parts of antimony trioxide, 1 part of zinc borate, 3 parts of EVA-g-MAH, 10100.1 parts of antioxidant and 39.5 parts of PVC prefabricated material are placed in an internal mixer at 175 ℃ for internal mixing for 3-5 min.

(3) And (3) carrying out die pressing on the internally mixed materials at the temperature of 180 ℃ and under the pressure of 20MPa for 8min for forming.

Example 4

(1) weighing materials according to the proportion of 40 parts of polyvinyl chloride (SG-8), 0.2 part of OPE wax, 0.1 part of PE wax, 0.5 part of stearic acid, 1 part of organic tin stabilizer, 1 part of calcium-zinc stabilizer, 6 parts of graphene oxide/chloromethoxy fatty acid ester mixture, 8 parts of CPE and 0.7 part of ACR, placing the materials in a high-speed mixer, mixing for 10-15 min, and extruding and granulating by using a double-screw extruder after the materials are cooled to obtain the PVC prefabricated granular material. Wherein the extrusion temperature is 145-180 ℃.

(2) Placing 60 parts of polyethylene (LDPE), 2 parts of aluminum hydroxide, 2 parts of antimony trioxide, 3 parts of EVA, 10100.3 parts of antioxidant and 57.5 parts of PVC prefabricated material into an internal mixer at 170 ℃ for internal mixing for 3-5 min.

Comparative example 1

A preparation method of a PVC/PE composite material comprises the following specific steps:

(1) 50 parts of polyvinyl chloride (S700), 0.1 part of PE wax, 0.1 part of stearic acid, 0.2 part of paraffin, and calcium-zinc stabilizer: 2 parts of epoxidized soybean oil, 0.5 part of chloromethoxy fatty acid ester, 3 parts of CPE (chlorinated polyethylene), 0.7 part of ACR (acrylic rubber), 50 parts of polyethylene (LLDPE), 1 part of aluminum hydroxide, 3 parts of antimony trioxide, 3 parts of zinc borate, 2 parts of PE-g-MAH (polyethylene-maleic anhydride) and 10100.2 parts of antioxidant, placing the materials into a high-speed mixer, mixing for 10-15 min, and then pouring the materials into an internal mixer at 175 ℃ for internal mixing for 3-5 min.

(2) And (3) carrying out die pressing on the internally mixed materials at the temperature of 180 ℃ and under the pressure of 20MPa for 5min for forming.

Comparative example 2

(1) 15 parts of polyvinyl chloride (SG-8), 0.1 part of PE wax, 0.2 part of polyol fatty acid ester, 0.1 part of paraffin, 2 parts of calcium-zinc stabilizer, 0.5 part of epoxidized soybean oil, 0.5 part of chloromethoxy fatty acid ester, 3 parts of CPE and 0.2 part of ACR, wherein the materials are weighed and placed in a high-speed mixer to be mixed for 10-15 min, and the temperature of a double-screw extruder is set as follows: 145-180 ℃, and after the material is cooled, extruding and granulating by using a double-screw extruder to obtain the PVC prefabricated granular material.

(2) Weighing 85 parts of polyethylene (HDPE), 4 parts of aluminum hydroxide, 1 part of antimony trioxide, 3 parts of zinc borate, 0.5 part of PE-g-MAH, 10100.3 parts of antioxidant and 21.6 parts of PVC prefabricated particles, and then pouring the materials into an internal mixer at 170 ℃ for internal mixing for 3-5 min.

Test example

For the above examples 1 to 3 and comparative examples 1 to 2, the performance test of the material was performed according to the following criteria, and the results are shown in table 1:

(1) flame retardancy performance criteria: UL-94.

(2) Tensile strength performance criteria: GB/T1040.3-2006;

(3) impact strength performance criteria: ASTMD 6110-10;

TABLE 1 results of the measurements

As can be seen from the test results in Table 1, the flame retardancy of the composite material prepared by the preparation method disclosed by the invention reaches V0 (after the sample is subjected to two 10-second combustion tests, the flame is extinguished within 10 seconds, and no combustible substance can fall off), and the composite material is the highest grade of flame retardancy. Compared with comparative examples 1 and 2, the examples 1 to 4 have better flame retardant property and mechanical property.

Although the present invention has been described in detail by way of preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made on the embodiments of the present invention by those skilled in the art without departing from the spirit and scope of the present invention, and these modifications or substitutions are within the scope of the present invention/any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims

1. The environment-friendly flame-retardant PVC/PE composite material is characterized by comprising the following components in parts by weight: 55-75 parts of polyethylene; 25-45 parts of polyvinyl chloride; 0.2-1 part of a lubricant; 2-5 parts of a compatilizer; 0.6-3 parts of a stabilizer; 2-6 parts of a plasticizer; 10100.1-0.3 part of antioxidant; 1-10 parts of flame-retardant filler; 2-10 parts of chlorinated polyethylene; 0-1 part of ACR resin.

2. The environmentally friendly flame retardant PVC/PE composite of claim 1, wherein the polyethylene is one of high density polyethylene, low density polyethylene or linear low density polyethylene.

3. The environment-friendly flame-retardant PVC/PE composite material according to claim 2, wherein the polyvinyl chloride has an average polymerization degree of 650 to 750.

4. The environmentally friendly flame retardant PVC/PE composite of claim 1, wherein the lubricant is at least one of stearic acid, paraffin wax, polyethylene wax, oxidized polyethylene wax, ethylene bis stearamide, monoglycerides or polyol fatty acid esters.

5. The environmentally friendly flame retardant PVC/PE composite of claim 1, wherein the compatibilizer is at least one of maleic anhydride grafted polyethylene, maleic anhydride grafted ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer.

6. The environmentally friendly flame retardant PVC/PE composite of claim 1, wherein the plasticizer is: graphene oxide/chloromethoxyfatty acid ester mixtures.

7. The environment-friendly flame-retardant PVC/PE composite material according to claim 6, wherein the graphene oxide/chloromethoxy fatty acid ester mixture is: placing graphene oxide in ethanol for ultrasonic dispersion, adding a certain amount of 3-chloropropyltrimethoxysilane, heating, stirring, refluxing for 10 hours, cleaning, filtering, and drying to obtain activated graphene oxide; then ball milling and ultrasonic dispersing the mixture in chloromethoxy fatty acid ester to obtain a graphene oxide/chloromethoxy fatty acid ester mixture.

8. The environmentally friendly flame retardant PVC/PE composite of claim 1, wherein the flame retardant filler is one or more of aluminum hydroxide, antimony trioxide, magnesium hydroxide, kaolin, or zinc borate.

9. The environment-friendly flame retardant PVC/PE composite material as claimed in claim 1, wherein the stabilizer is one or more of calcium zinc composite stabilizer, organic tin stabilizer, rare earth stabilizer or epoxidized soybean oil.

10. The preparation method of the environment-friendly flame-retardant PVC/PE composite material as claimed in claim 1, which is characterized by comprising the following specific steps:

(1) mixing PVC, a stabilizer, a lubricant, a graphene oxide/chloromethoxy fatty acid ester mixture, CPE and ACR in a high-speed mixer, and extruding and granulating after the materials are cooled to obtain a PVC prefabricated granular material; wherein the extrusion temperature is: 145-180 ℃;