CN115627038A - Super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material and preparation method thereof - Google Patents
Super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material and a preparation method thereof, belonging to the technical field of thermoplastic flame-retardant PVC materials, wherein the flame-retardant PVC cable material comprises the following components in parts by weight: 100-110 parts of polyvinyl chloride, 50-60 parts of a main plasticizer, 5-7 parts of epoxidized soybean oil, 12-14 parts of a calcium-zinc stabilizer, 2-3 parts of an auxiliary heat stabilizer, 3-4 parts of a reinforcing agent, 8-10 parts of a flame retardant, 2-2.5 parts of a lubricant, 0.4-0.6 part of an antioxidant, 8-8.5 parts of CPE and 15-18 parts of nano calcium carbonate; the preparation method of the flame-retardant PVC cable material comprises the following steps: preheating, mixing and molding; the invention can improve the lasting high temperature resistance and the lasting cold resistance of the flame-retardant PVC cable material and simultaneously improve the tensile strength and the elongation at break.
Description
Technical Field
The invention relates to the technical field of thermoplastic flame-retardant PVC materials, and particularly relates to a super-heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material and a preparation method thereof.
Background
The PVC electric wire and cable material is prepared by adding various additives such as a plasticizer, a stabilizer, a lubricant, a filler and the like on the basis of a PVC resin material, and mixing, mixing and thermoforming. At present, the existing PVC cable material has poor high temperature and cold resistance grade, most of the PVC cable materials have 105 ℃ temperature resistance grade, less 125 ℃ temperature resistance grade can be realized, the lasting high temperature resistance at 125 ℃ can be simultaneously maintained, the PVC cable material can also have lasting cold resistance, and the tensile strength and the elongation at break of the PVC cable material are less.
Chinese patent CN104194228A discloses a thermoplastic 125 ℃ temperature-resistant flame-retardant PVC cable material, which is prepared from the following raw materials: 45-55 parts of polyvinyl chloride; 5-8 parts of a stabilizer; 24-28 parts of plasticizer tetraoctyl pyromellitate; 4-6 parts of a filling agent; 2-3 parts of a flame retardant; 0.5-1.5 parts of a lubricant; 0.04-0.12 part of antioxidant N, N' -1,6-hexamethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide ]; 1-3 parts of a processing aid; the thermoplastic 125 ℃ temperature-resistant flame-retardant PVC cable material provided by the invention has the advantages that the changes of the tensile strength and the elongation at break before and after aging are within 10%, the requirements of 125 ℃ temperature-resistant wires and cables can be met, and a low-temperature embrittlement test at-30 ℃ can be passed; however, the PVC cable material has good effect under the test condition of 158 ℃ plus or minus 2 ℃ for 168h, and has extremely poor effect under the test condition of 158 ℃ plus or minus 2 ℃ for 336h, and the tensile strength and the elongation at break are poor.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material and a preparation method thereof, which can improve the lasting high temperature resistance and lasting cold resistance of the flame-retardant PVC cable material and simultaneously improve the tensile strength and the elongation at break.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material comprises the following components in parts by weight: 100-110 parts of polyvinyl chloride, 50-60 parts of a main plasticizer, 5-7 parts of epoxidized soybean oil, 12-14 parts of a calcium-zinc stabilizer, 2-3 parts of an auxiliary heat stabilizer, 3-4 parts of a reinforcing agent, 8-10 parts of a flame retardant, 2-2.5 parts of a lubricant, 0.4-0.6 part of an antioxidant, 8-8.5 parts of CPE and 15-18 parts of nano calcium carbonate.
The main plasticizer is a mixture of tri (n-octyl-n-decyl) trimellitate and tetraoctyl pyromellitate, wherein the weight ratio of the tri (n-octyl-n-decyl) trimellitate to the tetraoctyl pyromellitate is 33-35;
the calcium zinc stabilizer has the following types: MC90566 brand is bear brand;
the flame retardant is antimony trioxide;
the lubricant is OPE wax with the model of A-C316A and the brand of HONEYWELL;
the type of the antioxidant is XH-245, and the brand is Basff;
the particle size of the nano calcium carbonate is 20-30nm;
the preparation method of the auxiliary heat stabilizer comprises the following steps: adding microcrystalline cellulose, carrageenan, sodium carboxymethylcellulose and sodium hexametaphosphate into a ball mill for primary ball milling, controlling the ball-to-material ratio during primary ball milling to be 10-12, the rotating speed to be 300-320rpm, the time to be 35-40min, then adding calcium stearate, nano titanium dioxide and sorbitol, performing secondary ball milling, controlling the ball-to-material ratio during secondary ball milling to be 17-20, the rotating speed to be 300-320rpm, the time to be 40-45min, and obtaining an auxiliary heat stabilizer after the secondary ball milling is finished;
in the preparation of the auxiliary heat stabilizer, the weight ratio of microcrystalline cellulose, carrageenan, sodium carboxymethylcellulose, sodium hexametaphosphate, calcium stearate, nano titanium dioxide and sorbitol is 30-33 to 10-10 to 4-7:6-9;
in the preparation of the auxiliary heat stabilizer, the particle size of the nano titanium dioxide is 30-50nm;
the preparation method of the reinforcing agent comprises the following steps: adding hydroxypropyl cellulose, sodium carboxymethylcellulose and deionized water into a closed reaction container, vacuumizing to the vacuum degree of 0.091-0.093MPa, introducing nitrogen to the gas pressure of 0.18-0.2MPa, controlling the temperature in the closed reaction container to 50-55 ℃, starting stirring, controlling the stirring speed to 100-130rpm, stirring for 15-20min, adding disodium ethylenediamine tetraacetic acid and N-hydroxymethyl acrylamide, continuously stirring for 25-30min, adding pullulan and sodium trimetaphosphate, continuously stirring for 1-1.5h, transferring into a dialysis bag with the molecular weight cutoff of 12000-14000, dialyzing in pure water for 5-7d to obtain a reaction mixture, and freeze-drying the reaction mixture at-40 ℃ to-35 ℃ for 4-4.5h to obtain a reinforcing agent;
in the preparation of the reinforcing agent, the weight ratio of hydroxypropyl cellulose, sodium carboxymethylcellulose, deionized water, ethylene diamine tetraacetic acid, N-hydroxymethyl acrylamide, pullulan and sodium trimetaphosphate is 10-12;
in the preparation of the reinforcing agent, the molecular weight of the hydroxypropyl cellulose is 60000-80000.
A preparation method of a super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material comprises the following steps: preheating, mixing and molding;
preheating, namely preheating the primary plasticizer, controlling the temperature to be 75-85 ℃ during preheating, and the time to be 30-35min, and obtaining the preheated primary plasticizer after preheating is finished;
the mixing step comprises the steps of adding polyvinyl chloride, a calcium-zinc stabilizer, an auxiliary heat stabilizer, a reinforcing agent, a flame retardant, a lubricant, an antioxidant and nano calcium carbonate into a mixer for mixing, controlling the rotating speed of the mixer to be 80-150rpm during mixing, mixing for 10-15min, adding epoxidized soybean oil, mixing for 10-15min, uniformly adding the preheated main plasticizer in three batches, wherein the interval time between each batch is 10-12min, continuing mixing for 30-33min after the preheated main plasticizer in the third batch is added, adding CPE (chlorinated polyethylene), and continuing mixing for 20-22min to obtain a mixture;
and in the molding step, the mixture is extruded, granulated and hot-pressed to obtain the super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material.
Compared with the prior art, the invention has the beneficial effects that:
(1) The density of the super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material prepared by the invention can reach 1.33-1.35g/cm 3 The hardness can reach 91-93A;
(2) According to the preparation method of the super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material, the reinforcing agent is added, so that the lasting cold resistance of the prepared flame-retardant PVC cable material can be improved, and the impact embrittlement performance (-35 ℃) of the prepared flame-retardant PVC cable material is 8-10/30;
(3) According to the preparation method of the super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material, the tensile strength and the elongation at break of the prepared flame-retardant PVC cable material can be improved by adding the reinforcing agent, the tensile strength of the prepared flame-retardant PVC cable material is 28.1-28.9MPa, and the elongation at break is 321-332%;
(4) According to the preparation method of the super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material, the mixture of tri (n-octyl n-decyl) trimellitate and tetraoctyl pyromellitate is used as a main plasticizer, and an auxiliary heat stabilizer and a reinforcing agent are added, so that the lasting high temperature resistance of the prepared flame-retardant PVC cable material can be improved, the tensile strength of the prepared flame-retardant PVC cable material is 27.5-28.9MPa after 158 +/-2 x 168 hours, the elongation at break is 253-265%, and the mass loss is 2.6-3.1%; the tensile strength after 158 +/-2X 336h at the temperature of between 22.7 and 23.8MPa, the elongation at break of between 187 and 194 percent and the mass loss of between 7.5 and 8.2 percent.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described.
Example 1
The super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material comprises the following components in parts by weight: 100 parts of polyvinyl chloride, 50 parts of a primary plasticizer, 5 parts of epoxidized soybean oil, 12 parts of a calcium-zinc stabilizer, 2 parts of an auxiliary heat stabilizer, 3 parts of a reinforcing agent, 8 parts of a flame retardant, 2 parts of a lubricant, 0.4 part of an antioxidant, 8 parts of CPE and 15 parts of nano calcium carbonate.
The main plasticizer is a mixture of tri (n-octyl-n-decyl) trimellitate and tetraoctyl pyromellitate, wherein the weight ratio of the tri (n-octyl-n-decyl) trimellitate to the tetraoctyl pyromellitate is 33;
the calcium zinc stabilizer has the following types: MC90566 brand is bear brand;
the flame retardant is antimony trioxide;
the lubricant is OPE wax with the model of A-C316A and the brand of HONEYWELL;
the type of the antioxidant is XH-245, and the brand is Basff;
the particle size of the nano calcium carbonate is 20nm;
the preparation method of the auxiliary heat stabilizer comprises the following steps: adding microcrystalline cellulose, carrageenan, sodium carboxymethylcellulose and sodium hexametaphosphate into a ball mill for primary ball milling, controlling the ball-to-material ratio of the primary ball milling to be 10;
wherein, the weight ratio of microcrystalline cellulose, carrageenan, sodium carboxymethylcellulose, sodium hexametaphosphate, calcium stearate, nano titanium dioxide and sorbitol is 30;
the particle size of the nano titanium dioxide is 30nm;
the preparation method of the reinforcing agent comprises the following steps: adding hydroxypropyl cellulose, sodium carboxymethylcellulose and deionized water into a closed reaction container, vacuumizing until the vacuum degree is 0.091MPa, then introducing nitrogen until the gas pressure is 0.18MPa, controlling the temperature in the closed reaction container to 50 ℃, starting stirring, controlling the stirring speed to 100rpm, stirring for 15min, adding disodium ethylenediamine tetraacetic acid and N-hydroxymethyl acrylamide, continuously stirring for 25min, then adding pullulan and sodium trimetaphosphate, continuously stirring for 1h, then transferring into a dialysis bag with the molecular weight cutoff of 12000, dialyzing for 5d in pure water to obtain a reaction mixture, placing the reaction mixture at-40 ℃, and freeze-drying for 4h to obtain a reinforcing agent;
wherein, the weight ratio of the hydroxypropyl cellulose to the sodium carboxymethyl cellulose to the deionized water to the ethylene diamine tetraacetic acid to the N-hydroxymethyl acrylamide to the pullulan to the sodium trimetaphosphate is 10;
the molecular weight of the hydroxypropyl cellulose is 60000.
The preparation method of the super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material comprises the following steps:
1. preheating the primary plasticizer, controlling the temperature at 75 ℃ during preheating and the time at 30min, and obtaining the preheated primary plasticizer after preheating;
2. adding polyvinyl chloride, a calcium-zinc stabilizer, an auxiliary heat stabilizer, a reinforcing agent, a flame retardant, a lubricant, an antioxidant and nano calcium carbonate into a mixer for mixing, controlling the rotating speed of the mixer to be 80rpm during mixing, mixing for 10min, adding epoxidized soybean oil, mixing for 10min, uniformly adding the preheated main plasticizer in three batches, wherein the interval time between each batch is 10min, continuing mixing for 30min after the preheated main plasticizer in the third batch is added, adding CPE (chlorinated polyethylene), and continuing mixing for 20min to obtain a mixture;
3. and extruding, granulating and hot-press forming the mixture to obtain the super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material.
Example 2
The super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material comprises the following components in parts by weight: 105 parts of polyvinyl chloride, 55 parts of a main plasticizer, 6 parts of epoxidized soybean oil, 13 parts of a calcium-zinc stabilizer, 2.5 parts of an auxiliary heat stabilizer, 3.5 parts of a reinforcing agent, 9 parts of a flame retardant, 2.2 parts of a lubricant, 0.5 part of an antioxidant, 8.2 parts of CPE and 16 parts of nano calcium carbonate.
The main plasticizer is a mixture of tri (n-octyl-n-decyl) trimellitate and tetraoctyl pyromellitate, wherein the weight ratio of the tri (n-octyl-n-decyl) trimellitate to the tetraoctyl pyromellitate is 34;
the calcium zinc stabilizer is characterized by comprising the following components in percentage by weight: MC90566 brand bear;
the flame retardant is antimony trioxide;
the lubricant is OPE wax with the model of A-C316A and the brand of HONEYWELL;
the type of the antioxidant is XH-245, and the brand is Basff;
the particle size of the nano calcium carbonate is 25nm;
the preparation method of the auxiliary heat stabilizer comprises the following steps: adding microcrystalline cellulose, carrageenan, sodium carboxymethylcellulose and sodium hexametaphosphate into a ball mill for primary ball milling, controlling the ball-to-material ratio of the primary ball milling to be 11, the rotating speed to be 310rpm and the time to be 37min, then adding calcium stearate, nano titanium dioxide and sorbitol, performing secondary ball milling, controlling the ball-to-material ratio of the secondary ball milling to be 18, the rotating speed to be 310rpm and the time to be 42min, and obtaining an auxiliary heat stabilizer after the secondary ball milling is finished;
wherein the weight ratio of microcrystalline cellulose, carrageenan, sodium carboxymethylcellulose, sodium hexametaphosphate, calcium stearate, nano titanium dioxide and sorbitol is (32);
the particle size of the nano titanium dioxide is 40nm;
the preparation method of the reinforcing agent comprises the following steps: adding hydroxypropyl cellulose, sodium carboxymethylcellulose and deionized water into a closed reaction vessel, vacuumizing until the vacuum degree is 0.092MPa, then introducing nitrogen until the gas pressure is 0.19MPa, controlling the temperature in the closed reaction vessel to 52 ℃, starting stirring, controlling the stirring speed to 120rpm, stirring for 17min, adding disodium ethylenediamine tetraacetic acid and N-hydroxymethyl acrylamide, continuing stirring for 27min, then adding pullulan and sodium trimetaphosphate, continuing stirring for 1.2h, then transferring into a dialysis bag with the cut-off molecular weight of 13000, dialyzing for 6d in pure water to obtain a reaction mixture, and freeze-drying the reaction mixture at-37 ℃ for 4.2h to obtain a reinforcing agent;
wherein the weight ratio of the hydroxypropyl cellulose, the sodium carboxymethylcellulose, the deionized water, the ethylene diamine tetraacetic acid disodium, the N-hydroxymethyl acrylamide, the pullulan and the sodium trimetaphosphate is (11);
the hydroxypropyl cellulose has a molecular weight of 70000.
The preparation method of the super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material comprises the following steps:
1. preheating the main plasticizer, controlling the temperature during preheating to be 80 ℃ and the time to be 32min, and obtaining the preheated main plasticizer after preheating;
2. adding polyvinyl chloride, a calcium-zinc stabilizer, an auxiliary heat stabilizer, a reinforcing agent, a flame retardant, a lubricant, an antioxidant and nano calcium carbonate into a mixer for mixing, controlling the rotating speed of the mixer to be 100rpm during mixing, mixing for 12min, adding epoxidized soybean oil, mixing for 12min, uniformly adding the preheated plasticizer into three batches, wherein the interval time between each batch is 11min, continuously mixing for 32min after the third preheated main plasticizer is added, adding CPE, and continuously mixing for 21min to obtain a mixture;
3. and extruding, granulating and hot-press forming the mixture to obtain the super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material.
Example 3
The super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material comprises the following components in parts by weight: 110 parts of polyvinyl chloride, 60 parts of a primary plasticizer, 7 parts of epoxidized soybean oil, 14 parts of a calcium-zinc stabilizer, 3 parts of an auxiliary heat stabilizer, 4 parts of a reinforcing agent, 10 parts of a flame retardant, 2.5 parts of a lubricant, 0.6 part of an antioxidant, 8.5 parts of CPE (chlorinated polyethylene) and 18 parts of nano calcium carbonate.
The main plasticizer is a mixture of tri (n-octyl-n-decyl) trimellitate and tetraoctyl pyromellitate, wherein the weight ratio of the tri (n-octyl-n-decyl) trimellitate to the tetraoctyl pyromellitate is 35;
the calcium zinc stabilizer is characterized by comprising the following components in percentage by weight: MC90566 brand is bear brand;
the flame retardant is antimony trioxide;
the lubricant is OPE wax with the model of A-C316A and the brand of HONEYWELL;
the type of the antioxidant is XH-245, and the brand is Basff;
the particle size of the nano calcium carbonate is 30nm;
the preparation method of the auxiliary heat stabilizer comprises the following steps: adding microcrystalline cellulose, carrageenan, sodium carboxymethylcellulose and sodium hexametaphosphate into a ball mill for primary ball milling, controlling the ball-to-material ratio during primary ball milling to be 12;
wherein, the weight ratio of the microcrystalline cellulose to the carrageenan to the sodium carboxymethylcellulose to the sodium hexametaphosphate to the calcium stearate to the nano titanium dioxide to the sorbitol is 33.5;
the particle size of the nano titanium dioxide is 50nm;
the preparation method of the reinforcing agent comprises the following steps: adding hydroxypropyl cellulose, sodium carboxymethylcellulose and deionized water into a closed reaction container, vacuumizing until the vacuum degree is 0.093MPa, then introducing nitrogen until the gas pressure is 0.2MPa, controlling the temperature in the closed reaction container to 55 ℃, starting stirring, controlling the stirring speed to 130rpm, stirring for 20min, adding disodium ethylene diamine tetraacetate and N-hydroxymethyl acrylamide, continuing stirring for 30min, then adding pullulan and sodium trimetaphosphate, continuing stirring for 1.5h, then transferring into a dialysis bag with the molecular weight cutoff of 14000, dialyzing for 7d in pure water to obtain a reaction mixture, and freeze-drying the reaction mixture at-35 ℃ for 4.5h to obtain a reinforcing agent;
wherein, the weight ratio of the hydroxypropyl cellulose to the sodium carboxymethyl cellulose to the deionized water to the ethylene diamine tetraacetic acid to the N-hydroxymethyl acrylamide to the pullulan to the sodium trimetaphosphate is 12;
the molecular weight of the hydroxypropyl cellulose is 80000.
The preparation method of the super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material comprises the following steps:
1. preheating a main plasticizer, controlling the temperature at 85 ℃ during preheating, and keeping the time at 35min to obtain the preheated main plasticizer after the preheating is finished;
2. adding polyvinyl chloride, a calcium-zinc stabilizer, an auxiliary heat stabilizer, a reinforcing agent, a flame retardant, a lubricant, an antioxidant and nano calcium carbonate into a mixer for mixing, controlling the rotating speed of the mixer to be 150rpm during mixing, mixing for 15min, adding epoxidized soybean oil, mixing for 15min, uniformly adding the preheated main plasticizer in three batches, wherein the interval time between each batch is 12min, continuing mixing for 33min after the preheated main plasticizer in the third batch is added, adding CPE (chlorinated polyethylene), and continuing mixing for 22min to obtain a mixture;
3. and extruding, granulating and hot-press forming the mixture to obtain the super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material.
Comparative example 1
The same super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material composition and preparation method as those in example 3 are adopted, and the difference is that: the tri (n-octyl n-decyl) trimellitate is used for replacing a main plasticizer in equal amount, and the addition of an auxiliary heat stabilizer is omitted; the method specifically comprises the following steps:
the super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material comprises the following components in parts by weight: 110 parts of polyvinyl chloride, 60 parts of tri (n-octyl-n-decyl) trimellitate, 7 parts of epoxidized soybean oil, 14 parts of calcium-zinc stabilizer, 4 parts of reinforcing agent, 10 parts of flame retardant, 2.5 parts of lubricant, 0.6 part of antioxidant, 8.5 parts of CPE (chlorinated polyethylene) and 18 parts of nano calcium carbonate.
The calcium zinc stabilizer has the following types: MC90566 brand is bear brand;
the flame retardant is antimony trioxide;
the lubricant is OPE wax with the model of A-C316A and the brand of HONEYWELL;
the type of the antioxidant is XH-245, and the brand is Basff;
the particle size of the nano calcium carbonate is 30nm;
the preparation method of the reinforcing agent comprises the following steps: adding hydroxypropyl cellulose, sodium carboxymethylcellulose and deionized water into a closed reaction vessel, vacuumizing until the vacuum degree is 0.093MPa, then introducing nitrogen until the gas pressure is 0.2MPa, controlling the temperature in the closed reaction vessel to 55 ℃, starting stirring, controlling the stirring speed to 130rpm, stirring for 20min, adding disodium ethylenediamine tetraacetic acid and N-hydroxymethyl acrylamide, continuously stirring for 30min, then adding pullulan and sodium trimetaphosphate, continuously stirring for 1.5h, then transferring into a dialysis bag with the molecular weight cutoff of 14000, dialyzing for 7d in pure water to obtain a reaction mixture, and freeze-drying the reaction mixture at-35 ℃ for 4.5h to obtain a reinforcing agent;
wherein, the weight ratio of the hydroxypropyl cellulose to the sodium carboxymethyl cellulose to the deionized water to the ethylene diamine tetraacetic acid to the N-hydroxymethyl acrylamide to the pullulan to the sodium trimetaphosphate is 12;
the molecular weight of the hydroxypropyl cellulose is 80000.
A preparation method of a super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material comprises the following steps:
1. preheating tri (n-octyl n-decyl) trimellitate, controlling the temperature at 85 ℃ during preheating and the time at 35min, and obtaining preheated tri (n-octyl n-decyl) trimellitate after preheating is finished;
2. adding polyvinyl chloride, a calcium-zinc stabilizer, a reinforcing agent, a flame retardant, a lubricant, an antioxidant and nano calcium carbonate into a mixer for mixing, controlling the rotating speed of the mixer to be 150rpm during mixing, mixing for 15min, adding epoxidized soybean oil, mixing for 15min, uniformly adding preheated tri (n-octyl-n-decyl) trimellitate into three batches, wherein the interval time between each batch is 12min, continuing mixing for 33min after adding the third batch of preheated tri (n-octyl-n-decyl) trimellitate, adding CPE, and continuing mixing for 22min to obtain a mixture;
3. and extruding, granulating and hot-press forming the mixture to obtain the super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material.
Comparative example 2
The same super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material composition and preparation method as in example 3 are adopted, and the difference is that: omitting the addition of the reinforcing agent; the method comprises the following specific steps:
the super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material comprises the following components in parts by weight: 110 parts of polyvinyl chloride, 60 parts of a primary plasticizer, 7 parts of epoxidized soybean oil, 14 parts of a calcium-zinc stabilizer, 3 parts of an auxiliary heat stabilizer, 10 parts of a flame retardant, 2.5 parts of a lubricant, 0.6 part of an antioxidant, 8.5 parts of CPE and 18 parts of nano calcium carbonate.
The main plasticizer is a mixture of tri (n-octyl-n-decyl) trimellitate and tetraoctyl pyromellitate, wherein the weight ratio of the tri (n-octyl-n-decyl) trimellitate to the tetraoctyl pyromellitate is 35;
the calcium zinc stabilizer is characterized by comprising the following components in percentage by weight: MC90566 brand is bear brand;
the flame retardant is antimony trioxide;
the lubricant is OPE wax with the model of A-C316A and the brand of HONEYWELL;
the type of the antioxidant is XH-245, and the brand is Basff;
the particle size of the nano calcium carbonate is 30nm;
the preparation method of the auxiliary heat stabilizer comprises the following steps: adding microcrystalline cellulose, carrageenan, sodium carboxymethylcellulose and sodium hexametaphosphate into a ball mill for primary ball milling, controlling the ball-to-material ratio during primary ball milling to be 12;
wherein the weight ratio of microcrystalline cellulose, carrageenan, sodium carboxymethylcellulose, sodium hexametaphosphate, calcium stearate, nano titanium dioxide and sorbitol is (33);
the particle size of the nano titanium dioxide is 50nm.
A preparation method of a super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material comprises the following steps:
1. preheating a main plasticizer, controlling the temperature at 85 ℃ during preheating, and keeping the time at 35min to obtain the preheated main plasticizer after the preheating is finished;
2. adding polyvinyl chloride, a calcium-zinc stabilizer, an auxiliary heat stabilizer, a flame retardant, a lubricant, an antioxidant and nano calcium carbonate into a mixer for mixing, controlling the rotating speed of the mixer to be 150rpm during mixing, mixing for 15min, adding epoxidized soybean oil, mixing for 15min, uniformly adding the preheated main plasticizer in three batches, wherein the interval time between each batch is 12min, continuously mixing for 33min after the preheated main plasticizer in the third batch is added, adding CPE, and continuously mixing for 22min to obtain a mixture;
3. and extruding, granulating and hot-press forming the mixture to obtain the super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material.
Test examples
The super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable materials prepared in examples 1-3 and comparative examples 1-2 were subjected to performance tests, and the results of the performance tests of example 1 are shown as follows:
the results of the performance testing of example 2 are shown below:
the results of the performance testing of example 3 are shown below:
the results of the performance test of comparative example 1 are shown below:
the results of the performance test of comparative example 2 are shown below:
according to the performance test results, the mixture of tri (n-octyl n-decyl) trimellitate and tetraoctyl pyromellitate is used as a main plasticizer, and an auxiliary heat stabilizer is added, so that the lasting high temperature resistance of the flame-retardant PVC cable material can be improved; by adding the reinforcing agent, the lasting cold resistance, the tensile strength and the elongation at break of the flame-retardant PVC cable material can be improved, and meanwhile, the lasting high-temperature resistance of the flame-retardant PVC cable material is also improved to a certain extent.
It is noted that the percentages used in the present invention are mass percentages.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material is characterized by comprising the following components in parts by weight: 100-110 parts of polyvinyl chloride, 50-60 parts of a main plasticizer, 5-7 parts of epoxidized soybean oil, 12-14 parts of a calcium-zinc stabilizer, 2-3 parts of an auxiliary heat stabilizer, 3-4 parts of a reinforcing agent, 8-10 parts of a flame retardant, 2-2.5 parts of a lubricant, 0.4-0.6 part of an antioxidant, 8-8.5 parts of CPE and 15-18 parts of nano calcium carbonate;
the main plasticizer is a mixture of tri (n-octyl-n-decyl) trimellitate and tetraoctyl pyromellitate, wherein the weight ratio of the tri (n-octyl-n-decyl) trimellitate to the tetraoctyl pyromellitate is 33-35;
the preparation method of the auxiliary heat stabilizer comprises the following steps: adding microcrystalline cellulose, carrageenan, sodium carboxymethylcellulose and sodium hexametaphosphate into a ball mill for primary ball milling, then adding calcium stearate, nano titanium dioxide and sorbitol, carrying out secondary ball milling, and obtaining an auxiliary heat stabilizer after the secondary ball milling is finished;
the preparation method of the reinforcing agent comprises the following steps: adding hydroxypropyl cellulose, sodium carboxymethylcellulose and deionized water into a closed reaction container, vacuumizing to the vacuum degree of 0.091-0.093MPa, introducing nitrogen to the gas pressure of 0.18-0.2MPa, controlling the temperature in the closed reaction container to 50-55 ℃, stirring, adding disodium ethylenediamine tetraacetic acid and N-hydroxymethyl acrylamide, continuously stirring, adding pullulan and sodium trimetaphosphate, continuously stirring, transferring into a dialysis bag with the molecular weight cutoff of 12000-14000, dialyzing in pure water for 5-7d to obtain a reaction mixture, and freeze-drying the reaction mixture to obtain the reinforcing agent.
2. The super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material as claimed in claim 1, wherein the calcium zinc stabilizer is of the type: MC90566 brand is bear brand;
the flame retardant is antimony trioxide;
the lubricant is OPE wax with the model of A-C316A and the brand of HONEYWELL;
the type of the antioxidant is XH-245, and the brand is Basff;
the particle size of the nano calcium carbonate is 20-30nm.
3. The super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material according to claim 1, wherein in the preparation of the auxiliary heat stabilizer, the weight ratio of microcrystalline cellulose, carrageenan, sodium carboxymethylcellulose, sodium hexametaphosphate, calcium stearate, nano titanium dioxide and sorbitol is 30-33.
4. The super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material as claimed in claim 1, wherein in the preparation of the auxiliary heat stabilizer, the particle size of the nano titanium dioxide is 30-50nm.
5. The super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material according to claim 1, wherein in the preparation of the reinforcing agent, the weight ratio of hydroxypropyl cellulose, sodium carboxymethyl cellulose, deionized water, disodium ethylene diamine tetraacetate, N-hydroxymethyl acrylamide, pullulan and sodium trimetaphosphate is 10-12.
6. The super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material according to claim 1, wherein the molecular weight of the hydroxypropyl cellulose in the preparation of the reinforcing agent is 60000-80000.
7. A preparation method of the super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material as recited in any one of claims 1 to 6, characterized in that the preparation method comprises the following steps: preheating, mixing and molding.
8. The preparation method of the super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material as claimed in claim 7, wherein the primary plasticizer is preheated at 75-85 ℃ for 30-35min, and the preheated primary plasticizer is obtained after preheating.
9. The preparation method of the super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material according to claim 7, wherein the mixing comprises the steps of adding polyvinyl chloride, a calcium-zinc stabilizer, an auxiliary heat stabilizer, a reinforcing agent, a flame retardant, a lubricant, an antioxidant and nano calcium carbonate into a mixer for mixing, controlling the rotation speed of the mixer to be 80-150rpm during mixing, mixing for 10-15min, adding epoxidized soybean oil, mixing for 10-15min, uniformly dividing the preheated main plasticizer into three batches, adding the preheated main plasticizer into the three batches at an interval of 10-12min, continuing to mix for 30-33min after the preheated main plasticizer of the third batch is added, adding CPE, and continuing to mix for 20-22min to obtain a mixed material.
10. The preparation method of the super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material as claimed in claim 7, wherein the molding comprises extruding, granulating and hot-press molding the mixture to obtain the super heat-resistant cold-resistant thermoplastic flame-retardant PVC cable material.
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