CN112358694A - Polyvinyl chloride cable material and preparation method thereof - Google Patents

Polyvinyl chloride cable material and preparation method thereof Download PDF

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CN112358694A
CN112358694A CN202011056726.9A CN202011056726A CN112358694A CN 112358694 A CN112358694 A CN 112358694A CN 202011056726 A CN202011056726 A CN 202011056726A CN 112358694 A CN112358694 A CN 112358694A
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polyvinyl chloride
cable material
mixture
prepared
parts
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黄晓鹏
寿荣
俞晋连
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Hangzhou Futong Electric Wire & Cable Co ltd
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Hangzhou Futong Electric Wire & Cable 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
    • C08F259/02—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine
    • C08F259/04—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine on to polymers of vinyl chloride
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
    • 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
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract

The invention provides a polyvinyl chloride cable material which is prepared from the following raw materials: modified polyvinyl chloride, composite anti-aging agent, modifier, plasticizer and flame retardant. According to the preparation method of the polyvinyl chloride cable material, the components in the formula are mixed, so that the components can be mixed uniformly, and the additives generate a synergistic effect to modify the material in the process of melting, extruding and plasticating the mixed material, so that the polyvinyl chloride cable material has excellent high temperature resistance, low temperature resistance, high insulating property, high impact resistance, high toughness, oil resistance, environmental friendliness and no toxicity. In addition, the preparation method has easily controlled process, so that the produced polyvinyl chloride cable material has stable performance and low cost compared with the material with the same temperature-resistant grade.

Description

Polyvinyl chloride cable material and preparation method thereof
Technical Field
The invention relates to the technical field of cable materials, in particular to a polyvinyl chloride cable material and a preparation method thereof.
Background
At present, according to the published technical standards, the highest temperature resistance grade of a polyvinyl chloride cable material is 105 ℃ in the US standards of UL758 and UL1581, the accelerated constant temperature is 136 ℃/168 hours, the highest temperature resistance grade is 90 ℃ in the Chinese standard of GB/T8815-2008, the accelerated aging is 135 ℃/240 hours, and the highest temperature resistance grade is 90 ℃ in the Germany standard of VDE0281, the accelerated aging is 135 ℃/336 hours. However, the temperature-resistant materials with a temperature resistance level of 125 ℃ and above are basically cross-linked polyolefin materials, silicone rubber materials, fluorine materials and the like, but the production process of the materials is relatively complex, the cost is relatively high, and the materials are difficult to recycle.
The polyvinyl chloride is used as a common material in industries such as power cables, building decoration, packaging and transportation, has great consumption and demand, has huge market circulation and has good development prospect. At present, polyvinyl chloride cable materials are widely used in automobiles, such as automobile wire insulation materials and cable insulation sheath materials special for automobile charging piles, but the wire insulation materials generally require high temperature resistance, various oil corrosion resistance, good low temperature resistance, and good wear resistance and mechanical properties. However, the existing polyvinyl chloride cable material cannot simultaneously have the performances of high temperature resistance, low temperature resistance, oil corrosion resistance and the like. Therefore, the use of current polyvinyl chloride cable materials is limited.
Disclosure of Invention
The invention aims to provide a polyvinyl chloride cable material and a preparation method thereof, wherein the components in the formula are mixed, so that the components can be mixed uniformly, and in the process of carrying out melt extrusion plastication treatment on the mixed material, the additives generate a synergistic effect to modify the material, so that the polyvinyl chloride cable material has excellent high temperature resistance, low temperature resistance, high insulativity, high impact resistance, high toughness, oil resistance, environmental protection and no toxicity. In addition, the preparation method has easily controlled process, so that the produced polyvinyl chloride cable material has stable performance and low cost compared with the material with the same temperature-resistant grade.
The technical scheme of the invention is realized as follows:
the invention provides a polyvinyl chloride cable material which is prepared from the following raw materials: modified polyvinyl chloride, a composite anti-aging agent, a modifier, a plasticizer and a flame retardant;
the modified polyvinyl chloride is prepared by the following method:
s1, preparing a seed emulsion: mixing deionized water, emulsifier and styrene, heating to 80-90 deg.C, adding initiator aqueous solution dropwise, stirring, maintaining the temperature for 10-30min, cooling to room temperature, adjusting pH to 7.8-8.2 with ammonia water, and filtering to obtain seed solution;
s2, light crosslinking emulsion: uniformly mixing deionized water and an emulsifier, adding maleic anhydride, styrene and n-butyl acrylate, stirring for 10-30min at the speed of 700r/min, introducing nitrogen, heating to 70-90 ℃, adding the seed emulsion obtained in the step S1, uniformly stirring, and dropwise adding an initiator aqueous solution and NaHSO3After the dropwise addition of the aqueous solution, keeping the temperature for 30-60min, cooling to room temperature, adjusting the pH value to 7.8-8.2 by using ammonia water, and filtering to obtain a slightly crosslinked emulsion;
s3, preparing modified polyvinyl chloride: uniformly mixing polyvinyl alcohol, sodium carboxymethylcellulose and deionized water, introducing nitrogen, adding chloroethylene, heating to 55-60 ℃, adding the lightly crosslinked emulsion prepared in the step S2 while stirring, controlling the polymerization temperature to be not more than 65 ℃, quickly cooling and stopping the reaction when the pressure in the kettle is reduced by 0.2-0.3MPa, discharging unreacted chloroethylene, and filtering, washing and vacuum drying to obtain modified polyvinyl chloride;
the emulsifier is one or a mixture of several of sodium dodecyl benzene sulfonate, allyloxy nonylphenol polyoxyethylene ether ammonium sulfate and nonylphenol polyoxyethylene ether sodium sulfate;
the initiator is selected from one or a mixture of more of ammonium persulfate, potassium persulfate, sodium persulfate, cumyl peroxyneodecanoate and (2-ethylhexyl) peroxydicarbonate.
As a further improvement of the invention, the composite anti-aging agent is prepared by compounding bisphenol A and a synthetic anti-aging agent in a mass ratio of 1: (3-5), the structure of the synthetic anti-aging agent is shown as the formula I:
Figure BDA0002711057020000031
as a further improvement of the invention, the synthetic anti-aging agent is synthesized by the following method: dissolving p-phenylenediamine and sodium hydroxide into methanol, adding 3, 5-di-tert-butyl salicylaldehyde, heating and refluxing for 2-5h to generate a solid, continuing to reflux for 1-2h, cooling to room temperature, filtering, and repeatedly washing the solid with ethanol to obtain the synthetic anti-aging agent.
As a further improvement of the invention, the modifier is a mixture of IM812 and E920, and the mass ratio is 1: (1-5).
As a further improvement of the invention, the plasticizer is selected from at least one of W-797-ZH, C810 and UN 380; the flame retardant is selected from at least one of antimony trioxide and magnesium hydroxide.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 100 portions of modified polyvinyl chloride, 1 to 5 portions of composite anti-aging agent, 5 to 10 portions of modifier, 1 to 3 portions of plasticizer and 0.5 to 1.5 portions of flame retardant.
As a further improvement of the invention, the health-care food is prepared from the following raw materials in parts by weight: 115 parts of modified polyvinyl chloride 105-one, 2-4 parts of composite anti-aging agent, 6-9 parts of modifier, 1.5-2.5 parts of plasticizer and 0.7-1.2 parts of flame retardant.
The invention further provides a preparation method of the polyvinyl chloride cable material, which comprises the following steps:
weighing the components according to the formula of the polyvinyl chloride cable material;
mixing the weighed components to obtain a mixed material;
the mixture was melt extruded at a temperature of 170-200 ℃.
As a further improvement of the present invention, the mixing treatment comprises the following steps:
dividing the weighed plasticizer into two parts, and mixing one part with the weighed modified polyvinyl chloride to form a first mixture;
mixing the other part of the plasticizer and the weighed other components to form a second mixture;
and after the temperature of the second mixed material reaches 100-110 ℃, mixing the second mixed material with the first mixture to form the mixed material.
The invention further protects a cable which comprises a conductor and an insulating layer coated on the conductor, wherein the insulating layer is made of the polyvinyl chloride cable material or the polyvinyl chloride cable material prepared by the preparation method.
The invention has the following beneficial effects: in the invention, the pure rubber phase lightly crosslinked emulsion with narrow particle size distribution, no shell and slight crosslinking is prepared by a seed emulsion polymerization process, so that the vinyl chloride can be uniformly granulated in suspension polymerization, but also facilitates the diffusion of vinyl chloride monomer into rubber phase, the generation of graft copolymerization reaction, the improvement of toughening effect, the reactive emulsifier is introduced in the emulsion polymerization to reduce the amount of free emulsifier when the mild crosslinking emulsion is added into a vinyl chloride suspension polymerization system, avoid the generation of coarse particles, shaft sticking and kettle sticking, meanwhile, the difficulty of wastewater treatment after polymerization is reduced, the slightly crosslinked emulsion is added into a suspension polymerization system after the vinyl chloride monomer is well dispersed, the distribution of the slightly crosslinked emulsion to the dispersing agent can be controlled, the suspension polymerization stability is improved, but also can improve the distribution of maleic anhydride, styrene and n-butyl acrylate in the resin and improve the toughening effect. The invention adopts the cross-linking method to modify the polyvinyl chloride, can obviously improve the thermal stability, the shock resistance and the toughness of the polyvinyl chloride, improve the use temperature, the stress fracture, the solvent resistance and the permanent deformability of the material, not only keep the inherent characteristics of the polyvinyl chloride material, but also endow the polyvinyl chloride material with the characteristics of a rubber elastomer.
The novel age resister synthesized by the invention is prepared by organically combining hindered phenol and hindered amine age resisters, has simple preparation method and temperature conditions, and can effectively improve the aging resistance, mechanical property and high and low temperature resistance of materials. In addition, the system adopts bisphenol A as an antioxidant aid of a formula system, and the Schiff base type synthetic anti-aging agent as a synthetic anti-aging agent, and the bisphenol A and the Schiff base type synthetic anti-aging agent are mixed according to a certain proportion to form a composite anti-aging agent, so that the tensile strength change rate and the elongation at break change rate of the polyvinyl chloride material are obviously improved, and the anti-aging performance is better.
The compound modifier is a mixture of IM812 and E920, and the mass ratio of the modifier to the modifier is 1: (1-5), in a specific example, the IM812 is Korean LG chemical IM 812; the E920 is E920 produced by Achima, France. The two modifiers have good impact strength at low temperature, can improve the overall processability of the material, solve the problem that the polyvinyl chloride resin powder with polymerization degree is difficult to process and form in the embodiment of the invention, and can improve the appearance of the material, so that the material is smoother, finer and more exquisite and has the synergistic effect.
According to the preparation method of the polyvinyl chloride cable material, the components in the formula are mixed, so that the components can be mixed uniformly, and the additives generate a synergistic effect to modify the material in the process of melting, extruding and plasticating the mixed material, so that the polyvinyl chloride cable material has excellent high temperature resistance, low temperature resistance, high insulating property, high impact resistance, high toughness, oil resistance, environmental friendliness and no toxicity. In addition, the preparation method has easily controlled process, so that the produced polyvinyl chloride cable material has stable performance and low cost compared with the material with the same temperature-resistant grade.
Description of the drawings:
in order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art 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 for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a scheme showing the synthesis of an antiaging agent according to preparation example 3 of the present invention.
The specific implementation mode is as follows:
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.
Preparation example 1 modified polyvinyl chloride
S1, preparing a seed emulsion: mixing 100g of deionized water, 1g of sodium dodecyl benzene sulfonate and 5g of styrene, heating to 80 ℃, dropwise adding 10g of aqueous solution containing 1.5 wt% of peroxydicarbonate (2-ethylhexyl) ester, stirring, keeping the temperature for 10min, cooling to room temperature, adjusting the pH value to 7.8 by using ammonia water, and filtering to obtain a seed solution;
s2, light crosslinking emulsion: 100g of deionized water and 1.5g of allyloxy nonyl phenol polyoxyethylene ether sulfurAfter ammonium acid is mixed evenly, 7g of maleic anhydride, 4g of styrene and 10g of n-butyl acrylate are added, stirring is carried out for 10min at the speed of 500r/min, nitrogen is introduced, the temperature is heated to 70 ℃, 20g of seed emulsion obtained in the step S1 is added, after even stirring, 10g of aqueous solution containing 1.5 wt% of peroxydicarbonate (2-ethylhexyl) ester and 10g of aqueous solution containing 2.5 wt% of NaHSO are added dropwise3After the dropwise addition, the temperature is kept for 30min, the temperature is reduced to room temperature, the pH value is adjusted to 7.8 by ammonia water, and the mixture is filtered to obtain a mild crosslinking emulsion;
s3, preparing modified polyvinyl chloride: uniformly mixing 1.5g of polyvinyl alcohol, 2g of sodium carboxymethylcellulose and 50g of deionized water, introducing nitrogen, adding 55g of chloroethylene, heating to 55 ℃, adding 20g of the lightly crosslinked emulsion prepared in the step S2 while stirring, controlling the polymerization temperature to be not more than 65 ℃, quickly cooling and stopping the reaction when the pressure in the kettle is reduced by 0.2MPa, discharging unreacted chloroethylene, and filtering, washing and vacuum drying to obtain the modified polyvinyl chloride.
Preparation example 2 modified polyvinyl chloride
S1, preparing a seed emulsion: mixing 100g of deionized water, 1g of sodium nonylphenol polyoxyethylene ether sulfate and 5g of styrene, heating to 90 ℃, dropwise adding 10g of aqueous solution containing 1.5 wt% of peroxydicarbonate (2-ethylhexyl) ester, stirring, keeping the temperature for 30min, cooling to room temperature, adjusting the pH value to 8.2 by using ammonia water, and filtering to obtain a seed solution;
s2, light crosslinking emulsion: 100g of deionized water and 1.5g of ammonium allyloxy nonylphenol polyoxyethylene ether sulfate are uniformly mixed, then 7g of maleic anhydride, 4g of styrene and 10g of n-butyl acrylate are added, the mixture is stirred for 30min at 700r/min, nitrogen is introduced, the mixture is heated to 90 ℃, 20g of the seed emulsion obtained in the step S1 is added, after uniform stirring, 10g of aqueous solution containing 1.5 wt% of peroxydicarbonate (2-ethylhexyl) and 10g of aqueous solution containing 2.5 wt% of NaHSO are added3After the dropwise addition, the temperature is kept for 60min, the temperature is reduced to room temperature, the pH value is adjusted to 8.2 by ammonia water, and the mixture is filtered to obtain a mild crosslinking emulsion;
s3, preparing modified polyvinyl chloride: uniformly mixing 1.5g of polyvinyl alcohol, 2g of sodium carboxymethylcellulose and 50g of deionized water, introducing nitrogen, adding 55g of chloroethylene, heating to 60 ℃, adding 20g of the lightly crosslinked emulsion prepared in the step S2 while stirring, controlling the polymerization temperature to be not more than 65 ℃, quickly cooling and stopping the reaction when the pressure in the kettle is reduced by 0.3MPa, discharging unreacted chloroethylene, and filtering, washing and vacuum drying to obtain the modified polyvinyl chloride.
Comparative example 1 modified polyvinyl chloride
In step S1 and step S2, ammonia was used to adjust the pH to 9, as compared to example 2, and the other conditions were not changed.
S1, preparing a seed emulsion: mixing 100g of deionized water, 1g of sodium nonylphenol polyoxyethylene ether sulfate and 5g of styrene, heating to 90 ℃, dropwise adding 10g of aqueous solution containing 1.5 wt% of peroxydicarbonate (2-ethylhexyl) ester, stirring, keeping the temperature for 30min, cooling to room temperature, adjusting the pH value to 9 by using ammonia water, and filtering to obtain a seed solution;
s2, light crosslinking emulsion: 100g of deionized water and 1.5g of ammonium allyloxy nonylphenol polyoxyethylene ether sulfate are uniformly mixed, then 7g of maleic anhydride, 4g of styrene and 10g of n-butyl acrylate are added, the mixture is stirred for 30min at 700r/min, nitrogen is introduced, the mixture is heated to 90 ℃, 20g of the seed emulsion obtained in the step S1 is added, after uniform stirring, 10g of aqueous solution containing 1.5 wt% of peroxydicarbonate (2-ethylhexyl) and 10g of aqueous solution containing 2.5 wt% of NaHSO are added3After the dropwise addition, the temperature is kept for 60min, the temperature is reduced to room temperature, the pH value is adjusted to 9 by ammonia water, and the mixture is filtered to obtain a mild crosslinking emulsion;
s3, preparing modified polyvinyl chloride: uniformly mixing 1.5g of polyvinyl alcohol, 2g of sodium carboxymethylcellulose and 50g of deionized water, introducing nitrogen, adding 55g of chloroethylene, heating to 60 ℃, adding 20g of the lightly crosslinked emulsion prepared in the step S2 while stirring, controlling the polymerization temperature to be not more than 65 ℃, quickly cooling and stopping the reaction when the pressure in the kettle is reduced by 0.3MPa, discharging unreacted chloroethylene, and filtering, washing and vacuum drying to obtain the modified polyvinyl chloride.
Preparation example 3 Synthesis of antiaging agent
Dissolving 1mol of p-phenylenediamine and 4mol of sodium hydroxide in 200mL of methanol, adding 2mol of 3, 5-di-tert-butyl salicylaldehyde, heating for reflux reaction for 3.5h to generate a solid, continuing reflux reaction for 1.5h, cooling to room temperature, filtering, and repeatedly washing the solid with ethanol to obtain the synthetic anti-aging agent, wherein the yield is 90%, the synthetic route is shown in figure 1, and the structural formula is as follows:
Figure BDA0002711057020000081
from the infrared spectrum, 3450--1The peak is assigned as a hydroxyl absorption peak; 2965. 2901, 2870cm-1Respectively ascribed to CH3、CH2Symmetric and asymmetric stretching vibration; 1605cm-1The peak is the characteristic absorption peak of the CN double bond.
In a specific example, the IM812 is Korean LG chemical IM 812; the E920 is E920 produced by Achima, France. The W-797-ZH is W-797-ZH produced by DIC, C810 is C810 produced by ADK, and UN380 is UN380 produced by Taiwan Union
Example 1
The raw materials comprise the following components in parts by weight: 100 parts of modified polyvinyl chloride prepared in preparation example 1, 1 part of composite anti-aging agent, 5 parts of modifier, 8101 parts of plasticizer and 0.5 part of flame retardant antimony trioxide. The composite anti-aging agent is prepared by compounding bisphenol A and the synthetic anti-aging agent prepared in the preparation example 3, wherein the mass ratio of the bisphenol A to the synthetic anti-aging agent is 1: 3. the modifier is a mixture of IM812 and E920, and the mass ratio is 1: 1.
the preparation method comprises the following steps:
weighing the components according to the formula;
mixing the weighed components to obtain a mixed material, wherein the mixed material specifically comprises the following components:
dividing the weighed plasticizer C810 into two parts, and mixing one part with the weighed modified polyvinyl chloride to form a first mixture;
mixing the other part of the plasticizer C810 and the weighed other components to form a second mixture;
after the temperature of the second mixed material reaches 100 ℃, mixing the second mixed material with the first mixture to form the mixed material;
the mixture was melt extruded at a temperature of 170 ℃.
Example 2
The raw materials comprise the following components in parts by weight: 120 parts of modified polyvinyl chloride prepared in preparation example 1, 5 parts of composite anti-aging agent, 10 parts of modifier, 8103 parts of plasticizer and 1.5 parts of flame retardant antimony trioxide. The composite anti-aging agent is prepared by compounding bisphenol A and the synthetic anti-aging agent prepared in the preparation example 3, wherein the mass ratio of the bisphenol A to the synthetic anti-aging agent is 1: 5. the modifier is a mixture of IM812 and E920, and the mass ratio is 1: 5.
the preparation method comprises the following steps:
weighing the components according to the formula;
mixing the weighed components to obtain a mixed material, wherein the mixed material specifically comprises the following components:
dividing the weighed plasticizer C810 into two parts, and mixing one part with the weighed modified polyvinyl chloride to form a first mixture;
mixing the other part of the plasticizer C810 and the weighed other components to form a second mixture;
after the temperature of the second mixed material reaches 110 ℃, mixing the second mixed material with the first mixture to form the mixed material;
the mixture was melt extruded at a temperature of 200 ℃.
Example 3
The raw materials comprise the following components in parts by weight: 105 parts of modified polyvinyl chloride prepared in preparation example 2, 2 parts of composite anti-aging agent, 6 parts of modifier, 3801.5 parts of plasticizer UN and 0.7 part of flame retardant magnesium hydroxide. The composite anti-aging agent is prepared by compounding bisphenol A and the synthetic anti-aging agent prepared in the preparation example 3, wherein the mass ratio of the bisphenol A to the synthetic anti-aging agent is 1: 4. the modifier is a mixture of IM812 and E920, and the mass ratio is 1: 2.
the preparation method comprises the following steps:
weighing the components according to the formula;
mixing the weighed components to obtain a mixed material, wherein the mixed material specifically comprises the following components:
dividing the weighed plasticizer UN380 into two parts, and mixing one part with the weighed modified polyvinyl chloride to form a first mixture;
mixing another part of the plasticizer UN380 and other weighed components to form a second mixture;
after the temperature of the second mixed material reaches 102 ℃, mixing the second mixed material with the first mixture to form the mixed material;
the mixture was melt extruded at a temperature of 175 ℃.
Example 4
The raw materials comprise the following components in parts by weight: 115 parts of modified polyvinyl chloride prepared in preparation example 2, 4 parts of composite anti-aging agent, 9 parts of modifier, 2.5 parts of plasticizer W-797-ZH and 1.2 parts of flame retardant magnesium hydroxide. The composite anti-aging agent is prepared by compounding bisphenol A and the synthetic anti-aging agent prepared in the preparation example 3, wherein the mass ratio of the bisphenol A to the synthetic anti-aging agent is 1: 4. the modifier is a mixture of IM812 and E920, and the mass ratio is 1: 4.
the preparation method comprises the following steps:
weighing the components according to the formula;
mixing the weighed components to obtain a mixed material, wherein the mixed material specifically comprises the following components:
dividing the weighed plasticizer W-797-ZH into two parts, and mixing one part with the weighed modified polyvinyl chloride to form a first mixture;
mixing the other part of the plasticizer W-797-ZH and the weighed other components to form a second mixture;
after the temperature of the second mixed material reaches 108 ℃, mixing the second mixed material with the first mixture to form the mixed material;
the mixture was melt extruded at a temperature of 195 ℃.
Example 5
The raw materials comprise the following components in parts by weight: 110 parts of modified polyvinyl chloride prepared in preparation example 2, 3 parts of composite anti-aging agent, 7 parts of modifier, 2 parts of plasticizer W-797-ZH and 1 part of flame retardant magnesium hydroxide. The composite anti-aging agent is prepared by compounding bisphenol A and the synthetic anti-aging agent prepared in the preparation example 3, wherein the mass ratio of the bisphenol A to the synthetic anti-aging agent is 1: 4. the modifier is a mixture of IM812 and E920, and the mass ratio is 1: 3.
the preparation method comprises the following steps:
weighing the components according to the formula;
mixing the weighed components to obtain a mixed material, wherein the mixed material specifically comprises the following components:
dividing the weighed plasticizer W-797-ZH into two parts, and mixing one part with the weighed modified polyvinyl chloride to form a first mixture;
mixing the other part of the plasticizer W-797-ZH and the weighed other components to form a second mixture;
after the temperature of the second mixed material reaches 105 ℃, mixing the second mixed material with the first mixture to form the mixed material;
the mixture was melt extruded at a temperature of 185 ℃.
Example 6
Compared with example 5, the modified polyvinyl chloride prepared in comparative example 1 was used without changing other conditions.
Example 7
Compared with example 5, the composite aging inhibitor is only bisphenol A, and other conditions are not changed.
Example 8
Compared with example 5, the composite antioxidant is only the synthetic antioxidant prepared in preparation example 3, and other conditions are not changed.
Example 9
Compared with example 5, the modifier is only IM812, and other conditions are not changed.
Example 10
Compared with example 5, the modifier is only E920, and other conditions are not changed.
Test example 1
The polyvinyl chloride cable materials prepared in the embodiments 1-5 of the invention are subjected to an anti-aging test, and the hot air aging test is tested according to GB/T3515-2001, and the specific data are shown in the following table 1.
TABLE 1
Performance of Before aging After aging I After aging II After aging III
Heat stability, min (200 ℃ C.) >270 - - -
Heat distortion,% (150 ℃ C.) <20 - - -
Low temperature resistance, DEG C -55 - - -
Dielectric Strength, MV/m >32 - - -
Tensile strength, Mpa >30 >28 >27 >26
Elongation at break,% >320 >310 >305 >315
Residual rate of tensile strength,% - >90 >92 >94
Residual rate of elongation at break,% - >90 >92 >95
Rate of change of tensile strength% - <±10 - <±6
Rate of change of elongation at break,% - <±15 - <±10
Note: aging conditions I: keeping the temperature at 150 ℃ for 240h, and aging under the condition II: standard 902# Experimental oil, 60 ℃, 168h, aging conditions III: keeping the temperature at 125 ℃ for 3000 h.
As can be seen from the data in Table 1, the polyvinyl chloride cable material provided by the embodiment of the invention has excellent high temperature resistance, low temperature resistance (-55 ℃), high insulation, oil resistance, weather resistance, environmental friendliness, no toxicity and stable mechanical properties.
Test example 2
The polyvinyl chloride cable materials prepared in the embodiments 1 to 10 of the present invention and the commercially available polyvinyl chloride cable materials were subjected to performance tests, and specific data are shown in table 2 below.
TABLE 2
Figure BDA0002711057020000131
As can be seen from the above table, the polyvinyl chloride cable materials prepared in examples 1 to 5 of the present invention have good performance, which is significantly better than those of examples 6 to 10 and commercially available products.
Example 6 in comparison with example 5, the modified polyvinyl chloride prepared in comparative example 1 was used. The mechanical property, the aging resistance and the shock resistance of the polyvinyl chloride are obviously reduced, the polyvinyl chloride is modified by a crosslinking method, the pH value of the prepared system is controlled by ammonia water to be not too high, and the crosslinking of the polyvinyl chloride is influenced.
In examples 7 and 8, compared with example 5, the composite aging inhibitor is only bisphenol a or the synthetic aging inhibitor prepared in preparation example 3, and the aging resistance is remarkably reduced. The novel age resister synthesized by the invention is prepared by organically combining hindered phenol and hindered amine age resisters, has simple preparation method and temperature conditions, and can effectively improve the aging resistance, mechanical property and high and low temperature resistance of materials. In addition, bisphenol A is adopted as an antioxidant aid of a formula system, and a Schiff base type synthetic anti-aging agent is adopted as a synthetic anti-aging agent, and the bisphenol A and the Schiff base type synthetic anti-aging agent are mixed according to a certain proportion to form a composite anti-aging agent, so that the tensile strength change rate and the elongation at break change rate of the polyvinyl chloride material are obviously improved, and the anti-aging performance is better.
In examples 9 and 10, compared with example 5, the modifier is only IM812 or E920, and all performances are reduced. The two modifiers have good impact strength at low temperature, can improve the overall processability of the material, solve the problem that the polyvinyl chloride resin powder with polymerization degree is difficult to process and form in the embodiment of the invention, and can improve the appearance of the material, so that the material is smoother, finer and more exquisite and has the synergistic effect.
Compared with the prior art, the invention prepares the pure rubber phase lightly crosslinked emulsion with narrow particle size distribution, no shell and slight crosslinking through a seed emulsion polymerization process, not only can ensure that vinyl chloride suspension polymerization has uniform particles, but also is beneficial to the vinyl chloride monomer to diffuse into the rubber phase, is beneficial to the occurrence of graft copolymerization reaction and improves toughening effect, introduces a reaction type emulsifier in emulsion polymerization to reduce the amount of free emulsifier when the lightly crosslinked emulsion is added into a vinyl chloride suspension polymerization system, avoids the phenomena of coarse particles, shaft sticking and kettle sticking, simultaneously reduces the difficulty of wastewater treatment after polymerization, adds the lightly crosslinked emulsion into the suspension polymerization system after the vinyl chloride monomer is well dispersed, can control the distribution of the slightly crosslinked emulsion to a dispersing agent, improves the suspension polymerization stability, and can also improve the distribution of grafting modifiers maleic anhydride, styrene and n-butyl acrylate in resin, improving the toughening effect. The invention adopts the cross-linking method to modify the polyvinyl chloride, can obviously improve the thermal stability, the shock resistance and the toughness of the polyvinyl chloride, improve the use temperature, the stress fracture, the solvent resistance and the permanent deformability of the material, not only keep the inherent characteristics of the polyvinyl chloride material, but also endow the polyvinyl chloride material with the characteristics of a rubber elastomer.
The novel age resister synthesized by the invention is prepared by organically combining hindered phenol and hindered amine age resisters, has simple preparation method and temperature conditions, and can effectively improve the aging resistance, mechanical property and high and low temperature resistance of materials. In addition, the system adopts bisphenol A as an antioxidant aid of a formula system, and the Schiff base type synthetic anti-aging agent as a synthetic anti-aging agent, and the bisphenol A and the Schiff base type synthetic anti-aging agent are mixed according to a certain proportion to form a composite anti-aging agent, so that the tensile strength change rate and the elongation at break change rate of the polyvinyl chloride material are obviously improved, and the anti-aging performance is better.
The compound modifier is a mixture of IM812 and E920, and the mass ratio of the modifier to the modifier is 1: (1-5), in a specific example, the IM812 is Korean LG chemical IM 812; the E920 is E920 produced by Achima, France. The two modifiers have good impact strength at low temperature, can improve the overall processability of the material, solve the problem that the polyvinyl chloride resin powder with polymerization degree is difficult to process and form in the embodiment of the invention, and can improve the appearance of the material, so that the material is smoother, finer and more exquisite and has the synergistic effect.
According to the preparation method of the polyvinyl chloride cable material, the components in the formula are mixed, so that the components can be mixed uniformly, and the additives generate a synergistic effect to modify the material in the process of melting, extruding and plasticating the mixed material, so that the polyvinyl chloride cable material has excellent high temperature resistance, low temperature resistance, high insulating property, high impact resistance, high toughness, oil resistance, environmental friendliness and no toxicity. In addition, the preparation method has easily controlled process, so that the produced polyvinyl chloride cable material has stable performance and low cost compared with the material with the same temperature-resistant grade.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. The polyvinyl chloride cable material is characterized by being prepared from the following raw materials: modified polyvinyl chloride, a composite anti-aging agent, a modifier, a plasticizer and a flame retardant;
the modified polyvinyl chloride is prepared by the following method:
s1, preparing a seed emulsion: mixing deionized water, emulsifier and styrene, heating to 80-90 deg.C, adding initiator aqueous solution dropwise, stirring, maintaining the temperature for 10-30min, cooling to room temperature, adjusting pH to 7.8-8.2 with ammonia water, and filtering to obtain seed solution;
s2, light crosslinking emulsion: uniformly mixing deionized water and an emulsifier, adding maleic anhydride, styrene and n-butyl acrylate, stirring for 10-30min at the speed of 700r/min, introducing nitrogen, heating to 70-90 ℃, adding the seed emulsion obtained in the step S1, uniformly stirring, and dropwise adding an initiator aqueous solution and NaHSO3After the dropwise addition of the aqueous solution, keeping the temperature for 30-60min, cooling to room temperature, adjusting the pH value to 7.8-8.2 by using ammonia water, and filtering to obtain a slightly crosslinked emulsion;
s3, preparing modified polyvinyl chloride: uniformly mixing polyvinyl alcohol, sodium carboxymethylcellulose and deionized water, introducing nitrogen, adding chloroethylene, heating to 55-60 ℃, adding the lightly crosslinked emulsion prepared in the step S2 while stirring, controlling the polymerization temperature to be not more than 65 ℃, quickly cooling and stopping the reaction when the pressure in the kettle is reduced by 0.2-0.3MPa, discharging unreacted chloroethylene, and filtering, washing and vacuum drying to obtain modified polyvinyl chloride;
the emulsifier is one or a mixture of several of sodium dodecyl benzene sulfonate, allyloxy nonylphenol polyoxyethylene ether ammonium sulfate and nonylphenol polyoxyethylene ether sodium sulfate;
the initiator is selected from one or a mixture of more of ammonium persulfate, potassium persulfate, sodium persulfate, cumyl peroxyneodecanoate and (2-ethylhexyl) peroxydicarbonate.
2. The polyvinyl chloride cable material of claim 1, wherein the composite anti-aging agent is prepared by compounding bisphenol A and a synthetic anti-aging agent in a mass ratio of 1: (3-5), the structure of the synthetic anti-aging agent is shown as the formula I:
Figure FDA0002711057010000021
3. the polyvinyl chloride cable material according to claim 2, wherein the synthetic aging inhibitor is synthesized by the following method: dissolving p-phenylenediamine and sodium hydroxide into methanol, adding 3, 5-di-tert-butyl salicylaldehyde, heating and refluxing for 2-5h to generate a solid, continuing to reflux for 1-2h, cooling to room temperature, filtering, and repeatedly washing the solid with ethanol to obtain the synthetic anti-aging agent.
4. The polyvinyl chloride cable material as claimed in claim 1, wherein the modifier is a mixture of IM812 and E920, and the mass ratio is 1: (1-5).
5. The polyvinyl chloride cable material according to claim 1, wherein the plasticizer is selected from at least one of W-797-ZH, C810, UN 380; the flame retardant is selected from at least one of antimony trioxide and magnesium hydroxide.
6. The polyvinyl chloride cable material as claimed in claim 1, which is prepared from the following raw materials in parts by weight: 100 portions of modified polyvinyl chloride, 1 to 5 portions of composite anti-aging agent, 5 to 10 portions of modifier, 1 to 3 portions of plasticizer and 0.5 to 1.5 portions of flame retardant.
7. The polyvinyl chloride cable material as claimed in claim 6, which is prepared from the following raw materials in parts by weight: 115 parts of modified polyvinyl chloride 105-one, 2-4 parts of composite anti-aging agent, 6-9 parts of modifier, 1.5-2.5 parts of plasticizer and 0.7-1.2 parts of flame retardant.
8. A method for preparing a polyvinyl chloride cable material as claimed in any one of claims 1 to 7, comprising the steps of:
weighing the components according to the formula of the polyvinyl chloride cable material as defined in any one of claims 1 to 7;
mixing the weighed components to obtain a mixed material;
the mixture was melt extruded at a temperature of 170-200 ℃.
9. The method for preparing as claimed in claim 8, wherein the compounding treatment comprises the steps of:
dividing the weighed plasticizer into two parts, and mixing one part with the weighed modified polyvinyl chloride to form a first mixture;
mixing the other part of the plasticizer and the weighed other components to form a second mixture;
and after the temperature of the second mixed material reaches 100-110 ℃, mixing the second mixed material with the first mixture to form the mixed material.
10. A cable, comprising a conductor and an insulating layer coated on the conductor, characterized in that: the insulating layer material is the polyvinyl chloride cable material as defined in any one of claims 1 to 7 or the polyvinyl chloride cable material prepared by the preparation method as defined in any one of claims 8 to 9.
CN202011056726.9A 2020-09-30 2020-09-30 Polyvinyl chloride cable material and preparation method thereof Withdrawn CN112358694A (en)

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CN114933764A (en) * 2022-05-31 2022-08-23 宁波格亿达光缆科技有限公司 Luminous high-performance PVC optical cable material and preparation method thereof
CN117089105A (en) * 2023-07-25 2023-11-21 江苏隆科明泰新材料科技有限公司 Manufacturing process and application of polyvinyl chloride coiled material floor based on closed cell foaming technology

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CN101397356A (en) * 2008-11-19 2009-04-01 河北工业大学 Method for preparing butadiene-styrene latex particle grafted polychloroethylene compound resin
CN107226968A (en) * 2016-03-24 2017-10-03 新疆兵团现代绿色氯碱化工工程研究中心(有限公司) A kind of preparation method of transparent impact-resistant polyvinyl chloride granules composition

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Application publication date: 20210212