CN117089153A - Environment-friendly modified PVC material - Google Patents

Environment-friendly modified PVC material Download PDF

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Publication number
CN117089153A
CN117089153A CN202311138182.4A CN202311138182A CN117089153A CN 117089153 A CN117089153 A CN 117089153A CN 202311138182 A CN202311138182 A CN 202311138182A CN 117089153 A CN117089153 A CN 117089153A
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environment
pvc material
polyvinyl chloride
friendly
parts
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CN117089153B (en
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黄浩聪
黄淇
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Jieyang Youshi Science And Technology Industry Co ltd
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Jieyang Youshi Science And Technology Industry Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to the technical field of high polymer materials, and discloses an environment-friendly modified PVC material, which is prepared by taking polyvinyl chloride resin as a base material, taking an environment-friendly plasticizer, a rubber reinforcing agent, an antioxidant, a lubricant and a filler as auxiliary agents through a premixing-melt extrusion granulation process, wherein the environment-friendly plasticizer is epoxidized soybean oil containing triazole heterocycle and phosphorus-containing compound in a structure, and the rubber reinforcing agent is nitrile rubber containing imide heterocycle in the structure, and the invention has the advantages that: through the improvement to the material composition, the polyvinyl chloride can be quickly carbonized to form a carbon layer when being burnt, the flame-retardant capability of the polyvinyl chloride material is improved, and simultaneously, the silicon oxide generated after the combustion of the silicon element is combined with the expanded carbon layer, so that the flame-retardant capability of the polyvinyl chloride material is further improved, the generation of harmful substances is reduced, and the environmental protection degree of the polyvinyl chloride material is also improved.

Description

Environment-friendly modified PVC material
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an environment-friendly modified PVC material.
Background
Polyvinyl chloride (PVC) has low price, strong corrosion resistance and good insulativity, is one of the most widely applied plastics, and particularly occupies a large number of markets in the fields of power cables, shoes, pipes, daily necessities, packaging materials and the like. In order to optimize the performance of the polyvinyl chloride product, a plasticizer is often required to be added for blending modification in the process of preparing the polyvinyl chloride material, however, the common phthalic acid plasticizer is used as a starting raw material and has certain toxicity, and does not meet the requirement of green sustainable development, so that the polyvinyl chloride product is gradually forbidden to be used, and the environment-friendly plasticizer is used for blending modification of the polyvinyl chloride, so that the polyvinyl chloride product has important significance.
The invention patent application with the application number of CN201911422606.3 discloses an environment-friendly and nontoxic polymer clay material and a preparation method thereof, and the mixture of vegetable oil-based hydrogenated castor oil and epoxidized soybean oil is used as a plasticizer of polyvinyl chloride resin, so that the environment-friendly and nontoxic polymer clay material is environment-friendly, has no pollution, can meet the molding requirement of the polymer clay, and can be used as the plasticizer of polyvinyl chloride. However, the polyvinyl chloride material prepared by adding a large amount of vegetable oil-based plasticizer and other auxiliary agents not only maintains the defect of poor toughness and heat resistance of the polyvinyl chloride, but also reduces the flame retardant property of the polyvinyl chloride, and the defects have serious impeding effect on the development of the polyvinyl chloride material in the field of power cables,
the invention patent with the application number of CN201910040668.1 discloses a high-temperature-resistant and high-flame-retardant polyvinyl chloride insulating cable material and a preparation method thereof, wherein carbon nano tubes, molybdenum trioxide, aluminum hydroxide and silicon dioxide are used as main raw materials, the main raw materials are mixed and ground to prepare flame-retardant filler, and a polyvinyl chloride base material is subjected to physical filling modification to enhance the flame retardant property of the polyvinyl chloride material, but the modification mode tends to cause a large addition amount of flame retardant, so that interface problems are easily generated between the polyvinyl chloride base material and the flame retardant, and the flame retardant are mutually separated, so that the mechanical property of the polyvinyl chloride material is greatly reduced.
Disclosure of Invention
The invention aims to provide a green and environment-friendly modified PVC material, which solves the problems of poor toughness and heat resistance and poor flame retardant property of a polyvinyl chloride material.
The aim of the invention can be achieved by the following technical scheme:
the environment-friendly modified PVC material comprises the following raw materials in parts by weight: 85-100 parts of polyvinyl chloride resin, 15-24 parts of environment-friendly plasticizer, 5-12 parts of rubber reinforcing agent, 0.2-0.5 part of lubricant and 2-5 parts of filler;
the environment-friendly plasticizer is epoxidized soybean oil containing triazole heterocycle and phosphorus-containing flame retardant in the structure;
the rubber reinforcing agent is nitrile rubber containing imide heterocycle in the structure.
Further, the antioxidant is any one of hindered phenol antioxidants; the lubricant is any one of calcium stearate or zinc stearate; the filler is any one of titanium dioxide or calcium carbonate.
Further, the specific preparation method of the environment-friendly plasticizer comprises the following steps:
step S1: mixing the epoxidized soybean oil and the triazole compound, uniformly stirring, introducing nitrogen for protection, preserving heat for 1-3 hours at the temperature of 100-110 ℃, and cooling and discharging to obtain an epoxidized soybean oil intermediate;
step S2: uniformly stirring and mixing the epoxidized soybean oil intermediate and the phosphorus compound, adding the accelerator, introducing nitrogen to remove oxygen, raising the temperature to 70-75 ℃, stirring for 4-8 hours at constant temperature, and cooling and discharging to obtain the environment-friendly plasticizer.
Further, in step S1, the triazole compound is any one of 1,2, 4-triazole or benzotriazole.
Further, in step S2, the phosphorus compound is any one of dimethyl chlorophosphate or 2-chloro-2-oxo-1, 3, 2-dioxaphospholane.
Further, in step S2, the promoter is triethylamine.
In the technical scheme, the epoxy soybean oil structure contains epoxy groups, the epoxy soybean oil structure can be subjected to ring opening reaction with secondary amine groups in the triazole compound structure at high temperature to prepare an epoxy soybean oil intermediate containing the triazole groups, and under the action of an accelerator, hydroxyl generated by the ring opening reaction in the epoxy soybean oil intermediate structure can be subjected to reaction with P-C l bonds in the phosphorus compound structure, so that triazole heterocycle and phosphorus-containing compounds are introduced into the epoxy soybean oil structure to form the nitrogen-phosphorus synergistic flame retardant, and the environment-friendly plasticizer is prepared.
Further, the specific preparation method of the rubber reinforcing agent comprises the following steps:
step S10: mixing hydroxyl-terminated nitrile rubber with tetrahydrofuran, continuously adding dimethyl chlorosilane for mixing, raising the temperature to 50-60 ℃, stirring for 4-6 hours at constant temperature under the protection of nitrogen, distilling under reduced pressure to remove low-boiling substances and unreacted substances, cooling and discharging to obtain modified nitrile rubber;
step S20: mixing the modified nitrile rubber and 1, 4-dioxane uniformly, adding maleimide, raising the system temperature to 70-80 ℃, continuously adding a catalyst, introducing nitrogen for protection after the addition, preserving heat for 6-9h, decompressing and distilling to remove low-boiling substances and unreacted substances, cooling and discharging to obtain the rubber reinforcing agent.
Further, in step S10, the average molecular weight of the hydroxyl-terminated nitrile rubber is 6000.
Further, in the step S20, the catalyst is chloroplatinic acid, and the added mass of the chloroplatinic acid is 0.1-0.15% of the total mass of the modified nitrile rubber and the maleimide.
In the technical scheme, the hydroxyl-terminated group at the tail end of the molecular chain of the hydroxyl-terminated nitrile rubber can react with Si-C l bond in the dimethylchlorosilane structure, so that Si-H bond is introduced at the tail end of the molecular chain of the nitrile rubber, and further the hydroxyl-terminated group further reacts with unsaturated alkenyl in the maleimide structure in a hydrosilylation manner under the action of a chloroplatinic acid catalyst, so that Si-O and rigid imide heterocycle are introduced at the tail end of the nitrile rubber structure, and the rubber reinforcing agent is prepared.
Further, the preparation method of the modified PVC material comprises the following steps:
step one: weighing polyvinyl chloride resin and rubber reinforcing agent in parts by weight, placing in a high-speed mixer, stirring and mixing for 30-60min at 80-100 ℃, reducing the temperature to 40-50 ℃, continuously adding environment-friendly plasticizer, antioxidant, lubricant and filler in parts by weight, and continuously stirring for 20-40min to obtain a prefabricated material;
step two: transferring the prefabricated material into an extruder, setting the screw speed of the extruder to be 50-80rpm and the extrusion temperature to be 120-180 ℃, and carrying out melt extrusion and granulation on the prefabricated material to obtain the modified PVC material.
In the technical scheme, halogen groups in the polyvinyl chloride resin structure can interact with secondary amine in the imide heterocyclic structure in the rubber reinforcing agent structure in the high-temperature mixing process, so that the interface performance of the rubber reinforcing agent and the polyvinyl chloride resin is effectively improved, a rubber-polyvinyl chloride interpenetrating network is formed, the crosslinking density of the polyvinyl chloride resin is effectively improved, and then the polyvinyl chloride resin is mixed with auxiliary agents such as environment-friendly plasticizer and the like to form a prefabricated material, and the modified PVC material is prepared through an extrusion granulation process.
The invention has the beneficial effects that:
a) According to the invention, the epoxidized soybean oil is used as a matrix to prepare the environment-friendly plasticizer, and because the epoxidized soybean oil contains flexible long-chain alkyl branched chains, the epoxidized soybean oil has good compatibility with polyvinyl chloride resin and is not easy to migrate, and the triazole grafted in the structure and the phosphorus-containing compound can form the nitrogen-phosphorus synergistic flame retardant, when the material burns, phosphorus element can generate oxyacid with strong dehydration effect, polyvinyl chloride is used as a carbonizing agent, so that the polyvinyl chloride material system is quickly carbonized, a stable compact carbon layer is formed on the surface, incombustible gas formed after the nitrogen element burns can be matched with the carbon layer to form an expanded carbon layer, and the heat and substance exchange between gas phase and condensed phase of the polyvinyl chloride material system is slowed down, so that the continuous burning is prevented, and the problem that the flame retardant performance of the polyvinyl chloride material system is poor due to the mass addition of the plasticizer is avoided. In addition, the flame retardant is connected in the epoxidized soybean oil structure by chemical bonds, so that the flame retardant and the polyvinyl chloride resin have good compatibility by utilizing good compatibility between the epoxidized soybean oil and the polyvinyl chloride, and the precipitation phenomenon of the flame retardant is avoided.
b) According to the invention, the rubber reinforcing agent with the structure containing Si-O bond and rigid imide heterocycle is prepared, and an interpenetrating network structure is formed between a rubber molecular chain and a polyvinyl chloride molecular chain by utilizing the high temperature condition in the blending process, so that the polyvinyl chloride material system has higher structural compactness, and the prepared modified polyvinyl chloride material can show more excellent mechanical properties by matching with the unique toughening effect of rubber. In addition, the Si-O bond and the rigid imide heterocycle introduced in the rubber molecular chain structure can enhance the heat resistance of the modified polyvinyl chloride material, and the silicon oxide generated after the combustion of the silicon element can be combined with the expansion carbon layer, so that the compactness and the isolation of the carbon layer are better, and the carbon layer can be mutually cooperated with an environment-friendly plasticizer, thereby further enhancing the flame retardant property of the modified polyvinyl chloride material, reducing the generation of harmful substances and improving the environment-friendly degree of the polyvinyl chloride material.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared spectrum of an environmentally friendly plasticizer prepared in example 1 of the present invention;
FIG. 2 is an infrared spectrum of the rubber reinforcing agent prepared in example 2 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Preparation of environment-friendly plasticizer
Step S1: mixing 5g of epoxidized soybean oil and 1.22g of benzotriazole, stirring uniformly, introducing nitrogen for protection, preserving heat for 2 hours at 110 ℃, and cooling and discharging to obtain an epoxidized soybean oil intermediate;
step S2: 3.5g of epoxidized soybean oil intermediate and 0.83g of dimethyl chlorophosphate are stirred and mixed uniformly, 1.2g of triethylamine is added, nitrogen is introduced for deoxidization, the temperature is increased to 70 ℃, stirring is carried out for 6 hours at constant temperature, and then the environment-friendly plasticizer is obtained after cooling and discharging.
The infrared spectrum of the environment-friendly plasticizer is shown in figure 1, wherein 3026cm -1 Is characterized by the characteristic absorption peak of C-H bond on benzene ring, 1741cm -1 The characteristic absorption peak of ester carbonyl C=O on the fatty chain of the epoxidized soybean oil is 1602cm -1 Is characterized by an absorption peak of N=N in benzotriazole, 1381cm -1 At P=O absorption peak, 1213cm -1 The characteristic absorption peak of C-N bond generated by ring-opening reaction of benzotriazole and epoxidized soybean oil is 1022cm -1 The absorption peak of P-O-C is 831cm -1 The absorption peak of the epoxy group in the epoxidized soybean oil.
Example 2
Preparation of rubber reinforcing agent
Step S10: mixing 2.4g of hydroxyl-terminated nitrile rubber with the average molecular weight of 6000 with tetrahydrofuran, continuously adding 0.08g of dimethylchlorosilane for mixing, raising the temperature to 50 ℃, stirring for 5 hours under the protection of nitrogen at constant temperature, performing reduced pressure distillation to remove low-boiling substances and unreacted substances, cooling and discharging to obtain modified nitrile rubber;
step S20: uniformly mixing 2g of modified nitrile rubber and 1, 4-dioxane, adding 0.07g of maleimide, increasing the system temperature to 75 ℃, continuously adding 0.003g of chloroplatinic acid, introducing nitrogen for protection after the addition is finished, preserving heat for 8 hours, decompressing and distilling to remove low-boiling substances and unreacted substances, cooling and discharging to obtain the rubber reinforcing agent.
The rubber reinforcing agent has infrared spectrogram such asFIG. 2 shows a 2229cm section -1 The peak is 1639cm of-CN cyano characteristic absorption peak in nitrile rubber -1 And 1563cm -1 The characteristic absorption peak of amide in imide is 1013-1085 cm -1 The reaction of hydroxyl-terminated nitrile rubber and dimethylchlorosilane produces Si-O-C characteristic absorption peak, and the reaction of modified nitrile rubber and maleimide produces Si-C characteristic absorption peak.
Example 3
The environment-friendly modified PVC material comprises the following raw materials in parts by weight: 95 parts of polyvinyl chloride resin, 20 parts of environment-friendly plasticizer, 6 parts of rubber reinforcing agent, 10100.6 parts of antioxidant, 0.3 part of lubricant calcium stearate and 4 parts of filler titanium dioxide;
the preparation method of the modified PVC material comprises the following steps:
step one: weighing polyvinyl chloride resin and rubber reinforcing agent in parts by weight, placing in a high-speed mixer, stirring and mixing for 40min at 90 ℃, reducing the temperature to 40 ℃, continuously adding environment-friendly plasticizer, antioxidant 1010, lubricant calcium stearate and filler titanium dioxide in parts by weight, and continuously stirring for 30min to obtain a prefabricated material;
step two: transferring the prefabricated material into an extruder, setting the screw speed of the extruder to be 60rpm and the extrusion temperature to be 160 ℃, and carrying out melt extrusion and granulation on the prefabricated material to obtain the modified PVC material.
The preparation method of the environment-friendly plasticizer is shown in example 1, and the preparation method of the rubber reinforcing agent is shown in example 2.
Comparative example 1
The PVC material comprises the following raw materials in parts by weight: 95 parts of polyvinyl chloride resin, 20 parts of epoxidized soybean oil, 6 parts of rubber reinforcing agent, 0.6 part of antioxidant 1010, 0.3 part of lubricant calcium stearate and 4 parts of filler titanium dioxide;
the preparation method of the PVC material comprises the following steps:
step one: weighing polyvinyl chloride resin and rubber reinforcing agent in parts by weight, placing in a high-speed mixer, stirring and mixing for 40min at 90 ℃, reducing the temperature to 40 ℃, continuously adding epoxidized soybean oil, antioxidant 1010, lubricant calcium stearate and filler titanium dioxide in parts by weight, and continuously stirring for 30min to obtain a prefabricated material;
step two: transferring the prefabricated material into an extruder, setting the screw speed of the extruder to be 60rpm and the extrusion temperature to be 160 ℃, and carrying out melt extrusion and granulation on the prefabricated material to obtain the PVC material.
The preparation method of the rubber reinforcing agent is shown in example 2.
Comparative example 2
The PVC material comprises the following raw materials in parts by weight: 95 parts of polyvinyl chloride resin, 20 parts of environment-friendly plasticizer, 6 parts of hydroxyl-terminated nitrile rubber, 0.6 part of antioxidant 1010, 0.3 part of lubricant calcium stearate and 4 parts of filler titanium dioxide;
the preparation method of the PVC material comprises the following steps:
step one: weighing polyvinyl chloride resin and hydroxyl-terminated nitrile rubber in parts by weight, placing the polyvinyl chloride resin and the hydroxyl-terminated nitrile rubber in a high-speed mixer, stirring and mixing for 40min at 90 ℃, reducing the temperature to 40 ℃, continuously adding environment-friendly plasticizer, antioxidant 1010, lubricant calcium stearate and filler titanium dioxide in parts by weight, and continuously stirring for 30min to obtain a prefabricated material;
step two: transferring the prefabricated material into an extruder, setting the screw speed of the extruder to be 60rpm and the extrusion temperature to be 160 ℃, and carrying out melt extrusion and granulation on the prefabricated material to obtain the PVC material.
The preparation method of the environment-friendly plasticizer is shown in the example 1.
Comparative example 3
The PVC material comprises the following raw materials in parts by weight: 95 parts of polyvinyl chloride resin, 20 parts of environment-friendly plasticizer, 0.6 part of antioxidant 1010, 0.3 part of lubricant calcium stearate and 4 parts of filler titanium dioxide;
the preparation method of the PVC material comprises the following steps:
step one: weighing polyvinyl chloride resin and rubber reinforcing agent in parts by weight, placing in a high-speed mixer, stirring and mixing for 40min at 90 ℃, reducing the temperature to 40 ℃, continuously adding environment-friendly plasticizer, antioxidant 1010, lubricant calcium stearate and filler titanium dioxide in parts by weight, and continuously stirring for 30min to obtain a prefabricated material;
step two: transferring the prefabricated material into an extruder, setting the screw speed of the extruder to be 60rpm and the extrusion temperature to be 160 ℃, and carrying out melt extrusion and granulation on the prefabricated material to obtain the PVC material.
The preparation method of the environment-friendly plasticizer is shown in the example 1.
Comparative example 4
The PVC material comprises the following raw materials in parts by weight: 95 parts of polyvinyl chloride resin, 20 parts of epoxidized soybean oil, 0.6 part of antioxidant 1010, 0.3 part of lubricant calcium stearate and 4 parts of filler titanium dioxide;
the preparation method of the PVC material comprises the following steps:
step one: weighing polyvinyl chloride resin, epoxidized soybean oil, antioxidant 1010, lubricant calcium stearate and filler titanium dioxide, and stirring at 40 ℃ for 30min to obtain a prefabricated material;
step two: transferring the prefabricated material into an extruder, setting the screw speed of the extruder to be 60rpm and the extrusion temperature to be 160 ℃, and carrying out melt extrusion and granulation on the prefabricated material to obtain the PVC material.
Comparative example 5
The PVC material comprises the following raw materials in parts by weight: 95 parts of polyvinyl chloride resin, 0.6 part of antioxidant 1010, 0.3 part of lubricant calcium stearate and 4 parts of filler titanium dioxide;
the preparation method of the PVC material comprises the following steps:
step one: weighing polyvinyl chloride resin, antioxidant 1010, lubricant calcium stearate and filler titanium dioxide, and stirring at 40 ℃ for 30min to obtain a prefabricated material;
step two: transferring the prefabricated material into an extruder, setting the screw speed of the extruder to be 60rpm and the extrusion temperature to be 160 ℃, and carrying out melt extrusion and granulation on the prefabricated material to obtain the PVC material.
The following performance tests were carried out on the PVC materials prepared in example 3 and comparative examples 1 to 5 according to the invention:
testing the tensile property of the PVC material by referring to a standard GB/T1040-2006, wherein the tensile rate is set to be 50mm/min; testing the limiting oxygen index of the PVC material by referring to a standard GB/T2406-2008; referring to GB/T1843-2008, the impact strength of the PVC material is tested; the PVC material was tested for Vicat softening temperature with reference to standard GB/T1633-2000, and the test results are recorded in the following table.
The data presented in the above table can be summarized, and the PVC material prepared in the embodiment 3 of the invention has good mechanical properties, higher limiting oxygen index value and Vicat softening temperature value, thus showing good toughness, flame retardant property and heat resistance.
In comparative example 1, unmodified epoxidized soybean oil was used as a plasticizer, and thus the prepared PVC material contained no nitrogen-phosphorus flame retardant, and thus the limiting oxygen index value was low, the flame retardant performance was poor, but other properties were excellent.
In comparative example 2, unmodified hydroxyl-terminated nitrile rubber is used as a reinforcing agent, so that the prepared PVC material does not contain Si-O bond and imide heterocycle, and cannot form an interpenetrating network structure with a polyvinyl chloride resin molecular chain, and the prepared PVC material has lower structural compactness, so that the mechanical property and heat resistance performance of the PVC material are generally represented, and the flame retardant performance is also reduced to a certain extent.
The PVC material prepared in comparative example 3 does not contain a rubber reinforcing agent, so that further deterioration of various performance performances occurs, but the deterioration of flame retardant performance is not obvious.
The PVC material prepared in comparative example 4 uses only epoxidized soybean oil as a plasticizer and no reinforcing agent is added, so that only a slight reinforcing effect is exerted on polyvinyl chloride by using the plasticizing effect of epoxidized soybean oil.
The PVC material prepared in comparative example 5 was not added with plasticizer and reinforcing agent, so that each performance was the worst.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
The foregoing is merely illustrative and explanatory of the principles of the invention, as various modifications and additions may be made to the specific embodiments described, or similar thereto, by those skilled in the art, without departing from the principles of the invention or beyond the scope of the appended claims.

Claims (10)

1. The environment-friendly modified PVC material is characterized by comprising the following raw materials in parts by weight: 85-100 parts of polyvinyl chloride resin, 15-24 parts of environment-friendly plasticizer, 5-12 parts of rubber reinforcing agent, 0.5-0.8 part of antioxidant, 0.2-0.5 part of lubricant and 2-5 parts of filler;
the environment-friendly plasticizer is epoxidized soybean oil containing triazole heterocycle and phosphorus-containing compound in the structure;
the rubber reinforcing agent is nitrile rubber containing imide heterocycle in the structure.
2. The environment-friendly modified PVC material according to claim 1, wherein the antioxidant is any one of hindered phenol antioxidants; the lubricant is any one of calcium stearate or zinc stearate; the filler is any one of titanium dioxide or calcium carbonate.
3. The environment-friendly modified PVC material as claimed in claim 1, wherein the specific preparation method of the environment-friendly plasticizer comprises the following steps:
step S1: mixing the epoxidized soybean oil and the triazole compound, uniformly stirring, introducing nitrogen for protection, preserving heat for 1-3 hours at the temperature of 100-110 ℃, and cooling and discharging to obtain an epoxidized soybean oil intermediate;
step S2: uniformly stirring and mixing the epoxidized soybean oil intermediate and the phosphorus compound, adding the accelerator, introducing nitrogen to remove oxygen, raising the temperature to 70-75 ℃, stirring for 4-8 hours at constant temperature, and cooling and discharging to obtain the environment-friendly plasticizer.
4. The modified PVC material according to claim 3, wherein in the step S1, the triazole compound is any one of 1,2, 4-triazole or benzotriazole.
5. A modified PVC material according to claim 3, wherein in step S2, the phosphorus compound is any one of dimethyl chlorophosphate or 2-chloro-2-oxo-1, 3, 2-dioxaphospholane.
6. A modified PVC material according to claim 3, wherein in step S2, the accelerator is triethylamine.
7. The environment-friendly modified PVC material as claimed in claim 1, wherein the specific preparation method of the rubber reinforcing agent comprises the following steps:
step S10: mixing hydroxyl-terminated nitrile rubber with tetrahydrofuran, continuously adding dimethyl chlorosilane for mixing, raising the temperature to 50-60 ℃, stirring for 4-6 hours at constant temperature under the protection of nitrogen, distilling under reduced pressure to remove low-boiling substances and unreacted substances, cooling and discharging to obtain modified nitrile rubber;
step S20: mixing the modified nitrile rubber and 1, 4-dioxane uniformly, adding maleimide, raising the system temperature to 70-80 ℃, continuously adding a catalyst, introducing nitrogen for protection after the addition, preserving heat for 6-9h, decompressing and distilling to remove low-boiling substances and unreacted substances, cooling and discharging to obtain the rubber reinforcing agent.
8. The environmentally friendly modified PVC material according to claim 7, wherein in the step S10, the average molecular weight of the hydroxyl-terminated nitrile rubber is 6000.
9. The environment-friendly modified PVC material according to claim 7, wherein in the step S20, the catalyst is chloroplatinic acid, and the addition mass of the chloroplatinic acid is 0.1-0.15% of the total mass of the modified nitrile rubber and the maleimide.
10. The environment-friendly modified PVC material as claimed in claim 1, wherein the preparation method of the modified PVC material comprises the following steps:
step one: weighing polyvinyl chloride resin and rubber reinforcing agent in parts by weight, placing in a high-speed mixer, stirring and mixing for 30-60min at 80-100 ℃, reducing the temperature to 40-50 ℃, continuously adding environment-friendly plasticizer, antioxidant, lubricant and filler in parts by weight, and continuously stirring for 20-40min to obtain a prefabricated material;
step two: transferring the prefabricated material into an extruder, setting the screw speed of the extruder to be 50-80rpm and the extrusion temperature to be 120-180 ℃, and carrying out melt extrusion and granulation on the prefabricated material to obtain the modified PVC material.
CN202311138182.4A 2023-09-05 Environment-friendly modified PVC material Active CN117089153B (en)

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