CN111621105A - Heat-resistant flame-retardant polyvinyl chloride cable material - Google Patents

Heat-resistant flame-retardant polyvinyl chloride cable material Download PDF

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CN111621105A
CN111621105A CN202010577483.7A CN202010577483A CN111621105A CN 111621105 A CN111621105 A CN 111621105A CN 202010577483 A CN202010577483 A CN 202010577483A CN 111621105 A CN111621105 A CN 111621105A
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chlorinated paraffin
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isocyanurate
flame retardant
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徐松波
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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
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
    • C10G73/38—Chemical modification of petroleum
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating

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  • General Chemical & Material Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a heat-resistant flame-retardant polyvinyl chloride cable material, which comprises a novel flame retardant, and the preparation method of the flame retardant comprises the steps of firstly preparing chlorinated paraffin containing carboxyl by the reaction of chlorinated paraffin and p-hydroxybenzoic acid, then acylating the chlorinated paraffin containing carboxyl to obtain chlorinated paraffin containing acyl chloride, then carrying out esterification reaction with tris (2-hydroxyethyl) isocyanurate to obtain chlorinated paraffin containing hydroxyl isocyanurate modification, then carrying out reaction with tetrabromophthalic anhydride to obtain chlorinated paraffin containing carboxyl isocyanurate modification, and finally carrying out reaction with 2- (bromomethyl) -2- (hydroxymethyl) -1, 3-propylene glycol to obtain the novel flame retardant, wherein the flame retardant is used for preparing the heat-resistant flame-retardant polyvinyl chloride cable material and can ensure that the material has good mechanical property, processing property and high temperature resistance, it also has very good flame retardant property and low cost.

Description

Heat-resistant flame-retardant polyvinyl chloride cable material
Technical Field
The invention relates to a heat-resistant flame-retardant polyvinyl chloride cable material, and belongs to the technical field of heat-resistant flame-retardant high polymer materials.
Background
The PVC cable material is a plastic particle which is prepared by taking polyvinyl chloride resin as a main body, adding various auxiliaries, fillers and the like, mixing and granulating, is mainly used for outer layer sheaths of wires and cables, and has better mechanical property and electrical insulation property. At present, a plurality of PVC cable materials are available on the market, but most of the existing cable materials have poor mechanical properties or flame resistance, can be used only in some common occasions, and cannot be used in some occasions with higher requirements.
The chlorinated paraffin is a traditional polyvinyl chloride auxiliary additive and has the characteristics of low volatility, flame retardance, good electrical insulation, low price and the like. But the flame retardant effect is general, and the flame retardant effect needs to be improved by compounding other flame retardants when in use, so that the wide application of the flame retardant is hindered.
Disclosure of Invention
Aiming at the defects of chlorinated paraffin in the prior art, the invention aims to provide a brominated isocyanurate-containing modified chlorinated paraffin flame retardant which has high flame retardant efficiency and is applied to PVC cable materials. The physical and chemical properties are stable, the heat resistance is good, the compatibility with high polymer materials is good, the functions of plasticization and carbon formation and dripping prevention are achieved, and the defects in the prior art can be overcome.
The invention also aims to provide a method for preparing the bromine-containing isocyanurate modified chlorinated paraffin flame retardant, which is applied to PVC cable materials and has the advantages of wide raw material source, simple operation and mild reaction conditions.
A heat-resistant flame-retardant polyvinyl chloride cable material is characterized in that the heat-resistant flame-retardant polyvinyl chloride cable material is prepared by processing PVC resin, a calcium-zinc stabilizer, magnesium hydroxide, antimony trioxide, calcium stearate and a flame retardant; the flame retardant has a structure represented by formula (I):
Figure BDA0002551462360000021
wherein, in the formula (I), R1、R2、R3、R4、R5And R6 is a chlorinated paraffin segment.
The invention also provides a preparation method of the flame retardant, which comprises the following steps:
step (1): preparation of chlorinated paraffins containing carboxyl groups
Dissolving chlorinated paraffin in butanone, adding a certain amount of p-hydroxybenzoic acid and potassium carbonate, and heating to react under the protection of nitrogen to obtain chlorinated paraffin containing carboxyl;
step (2): preparation of chlorinated paraffins containing acid chlorides
Adding the chlorinated paraffin containing carboxyl obtained in the step (1) into a reaction kettle, and dropwise adding excessive phosphorus trichloride into the reaction kettle to react to obtain chlorinated paraffin containing acyl chloride;
and (3): preparation of hydroxyl-containing isocyanurate modified chlorinated Paraffin
Slowly dripping the chlorinated paraffin containing acyl chloride prepared in the step (2) into a mixed system of tris (2-hydroxyethyl) isocyanurate and triethylamine serving as an acid-binding agent for esterification reaction, wherein the molar ratio of the chlorinated paraffin containing acyl chloride to the tris (2-hydroxyethyl) isocyanurate is 2-2.2: 1, and reacting to obtain chlorinated paraffin containing hydroxyl isocyanurate modification;
and (4): preparation of carboxyl-containing isocyanurate-modified chlorinated Paraffin
Reacting the hydroxyl-containing chlorinated paraffin obtained in the step (3) with tetrabromophthalic anhydride to obtain carboxyl-containing isocyanurate modified chlorinated paraffin;
and (5): preparation of flame retardant
And (3) adding the chlorinated paraffin modified by the isocyanuric ester containing carboxyl prepared in the step (4), 2- (bromomethyl) -2- (hydroxymethyl) -1, 3-propylene glycol and a proper amount of toluene or cyclohexane as a water-carrying agent into a reaction kettle, adding p-toluenesulfonic acid with the mass fraction of 1-5% of the total mass of reactants, heating to 150-220 ℃ under stirring, reacting for 3-6 h, and drying the product to obtain the flame retardant.
The preparation method of the flame retardant further comprises the following preferred scheme:
in the preferable scheme, the chlorinated paraffin and the p-hydroxybenzoic acid in the step (1) react at the temperature of 55-80 ℃ for 10-30 h to prepare the chlorinated paraffin containing carboxyl.
In the preferable scheme, the chlorinated paraffin containing carboxyl in the step (2) reacts with excessive phosphorus trichloride at the temperature of 50-70 ℃ for 4-6 h to prepare chlorinated paraffin containing acyl chloride.
In a preferable scheme, the esterification reaction in the step (3) is carried out under the reaction condition that chlorinated paraffin containing acyl chloride is slowly dripped into the mixed solution of the tris (2-hydroxyethyl) isocyanurate and the acid-binding agent in an ice-water bath for reaction, and the reaction is continued in the ice-water bath for 2-4 hours after the dripping is finished.
In the preferable scheme, the reaction condition in the step (4) is that the reaction is carried out for 3-7 hours at the temperature of 60-80 ℃.
In a preferred scheme, the reaction molar ratio of the isocyanuric ester modified chlorinated paraffin containing carboxyl to the 2- (bromomethyl) -2- (hydroxymethyl) -1, 3-propanediol in the step (5) is 3: 1.
The invention has the beneficial effects that: the branched chlorinated paraffin is embedded with three excellent flame-retardant elements of nitrogen, bromine and chlorine simultaneously, and the three elements generate synergistic interaction from different flame-retardant mechanisms, so that higher flame-retardant efficiency can be shown.
Drawings
FIG. 1 is an infrared image of a flame retardant prepared in example 2.
FIG. 1: 2920cm-1And 2850cm-1Respectively represents the stretching vibration absorption peak of methylene and methyl, 1470cm-1And 1370cm-1Bending vibration absorption peak of methyl group, 1745cm-1Is the absorption peak of stretching vibration of C ═ O in the ester group, 1690cm-1And 1420cm-1Is the expansion vibration absorption peak of C ═ O in isocyanurate, 1150cm-1At the stretching vibration peak of the C-N single bond, 1230cm-1And 1050cm-1Is a characteristic absorption peak of the C-O-C ether bond of 710cm-1Is the stretching vibration peak of C-Cl bond, 550cm-1And (b) is a stretching vibration peak of the C-Br bond.
Detailed Description
The following examples are intended to further illustrate the content of the invention, but not to limit the scope of the invention.
Example 1
(1) Preparation of chlorinated paraffin 42 containing carboxyl group: dissolving 20g of chlorinated paraffin 42 in 200mL of acetone, stirring to dissolve, adding 20g of p-hydroxybenzoic acid and 30g of potassium carbonate, and reacting at 55 ℃ for 30h under the protection of nitrogen. After the reaction is finished, hydrochloric acid is used for adjusting the pH value to 3.0, then ethanol is used for extraction, and the product is dried in vacuum at 100 ℃ for 5 hours to obtain chlorinated paraffin 42 containing carboxyl.
(2) Preparation of acid chloride-containing chlorinated paraffin 42: adding 70mol of chlorinated paraffin 42 containing carboxyl into a reaction kettle, dropwise adding 85mol of phosphorus trichloride, stirring, heating to 50 ℃, reacting for 6 hours, cooling to room temperature, standing and layering to obtain chlorinated paraffin 42 containing acyl chloride.
(3) Preparation of hydroxyl-containing isocyanurate-modified chlorinated paraffin 42: adding 100mol of tris (2-hydroxyethyl) isocyanurate and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding dichloromethane solution containing 203mol of chlorinated paraffin 42 containing acyl chloride at 0 ℃, reacting the reactants at 0 ℃ for 2h, washing the reaction product with 4% sodium bicarbonate solution until the pH value is 7, transferring the reaction product to ethyl acetate for extraction and separation, washing the organic phase with distilled water, drying with anhydrous calcium chloride, drying for 8h, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the hydroxyl-containing isocyanurate modified chlorinated paraffin 42.
(4) Preparation of chlorinated paraffin modified by isocyanuric ester containing carboxyl: adding 100mol of carbon tetrachloride, 100mol of hydroxyl-containing isocyanurate modified chlorinated paraffin 42 and 100mol of tetrabromophthalic anhydride into a reaction kettle, introducing nitrogen into the reaction kettle, stirring and heating to 60 ℃, reacting for 7h, cooling, extracting and separating by using ethyl acetate, drying an organic phase by using anhydrous calcium chloride, filtering under reduced pressure after drying for 8h, and distilling the filtrate to remove the solvent to obtain the carboxyl-containing isocyanurate modified chlorinated paraffin 42.
(5) Preparation of the flame retardant: and (3) adding 90mol of the carboxyl-containing isocyanurate modified chlorinated paraffin 42 prepared in the step (4), 30mol of 2- (bromomethyl) -2- (hydroxymethyl) -1, 3-propylene glycol, a proper amount of water-carrying agent toluene or cyclohexane and p-toluenesulfonic acid with the mass fraction of 1-5% of the total mass of reactants into a reaction kettle, heating to 150 ℃ under stirring, reacting for 6h, and drying the product to obtain the flame retardant F1.
(6) Preparing a heat-resistant flame-retardant polyvinyl chloride cable material: 100 parts of PVC resin, 2 parts of calcium-zinc stabilizer, 8 parts of magnesium hydroxide, 5 parts of antimony trioxide, 2 parts of calcium stearate and 35 parts of flame retardant F1 are put into a mixer, and are uniformly mixed and stirred at 110 ℃ to obtain a mixture, and then the mixture is sent into a double-screw extruder and is extruded and granulated at 150 ℃ to obtain the PVC cable material.
Example 2
(1) Preparation of chlorinated paraffin 52 containing carboxyl group: dissolving 20g of chlorinated paraffin 52 in 200mL of acetone, stirring to dissolve, adding 20g of p-hydroxybenzoic acid and 30g of potassium carbonate, and reacting at 80 ℃ for 10 hours under the protection of nitrogen. After the reaction is finished, hydrochloric acid is used for adjusting the pH value to 3.0, then ethanol is used for extraction, and the product is dried in vacuum at 100 ℃ for 5 hours to obtain chlorinated paraffin 52 containing carboxyl.
(2) Preparation of chlorinated paraffin 52 containing acid chloride: adding 70mol of carboxyl-containing chlorinated paraffin 52 into a reaction kettle, dropwise adding 85mol of phosphorus trichloride, stirring, heating to 70 ℃, reacting for 4 hours, cooling to room temperature, standing and layering to obtain the chlorinated paraffin 52 containing acyl chloride.
(3) Preparation of hydroxyl-containing isocyanurate-modified chlorinated paraffin 52: adding 100mol of tris (2-hydroxyethyl) isocyanurate and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding a dichloromethane solution containing 202mol of chlorinated paraffin 52 containing acyl chloride at 0 ℃, reacting the reactants at 0 ℃ for 4 hours, washing the reaction product with 4% sodium bicarbonate solution until the pH value is 7, transferring the reaction product to ethyl acetate for extraction and separation, washing the organic phase with distilled water, drying the organic phase with anhydrous calcium chloride, drying the organic phase for 8 hours, filtering the organic phase under reduced pressure, and distilling the filtrate to remove the solvent to obtain the hydroxyl-containing isocyanurate modified chlorinated paraffin 52.
(4) Preparation of chlorinated paraffin modified by isocyanuric ester containing carboxyl: adding 100mol of carbon tetrachloride, 100mol of hydroxyl-containing isocyanurate modified chlorinated paraffin 52 and 100mol of tetrabromophthalic anhydride into a reaction kettle, introducing nitrogen into the reaction kettle, stirring and heating to 80 ℃, reacting for 3h, cooling, extracting and separating by using ethyl acetate, drying an organic phase by using anhydrous calcium chloride, filtering under reduced pressure after drying for 8h, and distilling the filtrate to remove the solvent to obtain the carboxyl-containing isocyanurate modified chlorinated paraffin 52.
(5) Preparation of the flame retardant: and (3) adding 90mol of the carboxyl-containing isocyanurate modified chlorinated paraffin 52 prepared in the step (4), 30mol of 2- (bromomethyl) -2- (hydroxymethyl) -1, 3-propylene glycol, a proper amount of water-carrying agent toluene or cyclohexane and p-toluenesulfonic acid with the mass fraction of 1-5% of the total mass of reactants into a reaction kettle, heating to 220 ℃ under stirring, reacting for 3h, and drying the product to obtain the flame retardant F2.
(6) Preparing a heat-resistant flame-retardant polyvinyl chloride cable material: 100 parts of PVC resin, 2 parts of calcium-zinc stabilizer, 8 parts of magnesium hydroxide, 5 parts of antimony trioxide, 2 parts of calcium stearate and 35 parts of flame retardant F2 are put into a mixer, and are uniformly mixed and stirred at 110 ℃ to obtain a mixture, and then the mixture is sent into a double-screw extruder and is extruded and granulated at 150 ℃ to obtain the PVC cable material.
Example 3
(1) Preparation of carboxyl group-containing chlorinated paraffin 70: dissolving 20g of chlorinated paraffin 52 in 200mL of acetone, stirring to dissolve, adding 20g of p-hydroxybenzoic acid and 30g of potassium carbonate, and reacting at 65 ℃ for 24h under the protection of nitrogen. After the reaction is finished, hydrochloric acid is used for adjusting the pH value to 3.0, then ethanol is used for extraction, and the product is dried in vacuum at 100 ℃ for 5 hours to obtain chlorinated paraffin 70 containing carboxyl.
(2) Preparation of acid chloride-containing chlorinated paraffin 70: adding 70mol of carboxyl-containing chlorinated paraffin 70 into a reaction kettle, dropwise adding 85mol of phosphorus trichloride, stirring, heating to 60 ℃, reacting for 5 hours, cooling to room temperature, standing and layering to obtain the chlorinated paraffin 70 containing acyl chloride.
(3) Preparation of hydroxyl-containing isocyanurate-modified chlorinated paraffin 70: adding 100mol of tris (2-hydroxyethyl) isocyanurate and a proper amount of acid-binding agent anhydrous triethylamine into a reaction kettle, introducing nitrogen into the reaction kettle, dropwise adding dichloromethane solution containing 205mol of chlorinated paraffin 70 containing acyl chloride at 0 ℃, reacting the reactants at 0 ℃ for 3h, washing the reaction product with 4% sodium bicarbonate solution until the pH value is 7, transferring the reaction product to ethyl acetate for extraction and separation, washing the organic phase with distilled water, drying with anhydrous calcium chloride, drying for 8h, filtering under reduced pressure, and distilling the filtrate to remove the solvent to obtain the hydroxyl-containing isocyanurate modified chlorinated paraffin 70.
(4) Preparation of chlorinated paraffin modified by isocyanuric ester containing carboxyl: adding 100mol of carbon tetrachloride, 100mol of hydroxyl-containing isocyanurate modified chlorinated paraffin 70 and 100mol of tetrabromophthalic anhydride into a reaction kettle, introducing nitrogen into the reaction kettle, stirring and heating to 70 ℃, reacting for 5h, cooling, extracting and separating by using ethyl acetate, drying an organic phase by using anhydrous calcium chloride, filtering under reduced pressure after drying for 8h, and distilling the filtrate to remove the solvent to obtain the carboxyl-containing isocyanurate modified chlorinated paraffin 70.
(5) Preparation of the flame retardant: and (3) adding 90mol of the carboxyl-containing isocyanurate modified chlorinated paraffin 70 prepared in the step (4), 30mol of 2- (bromomethyl) -2- (hydroxymethyl) -1, 3-propylene glycol, a proper amount of water-carrying agent toluene or cyclohexane and p-toluenesulfonic acid with the mass fraction of 1-5% of the total mass of reactants into a reaction kettle, heating to 200 ℃ under stirring, reacting for 4h, and drying the product to obtain the flame retardant F3.
(6) Preparing a heat-resistant flame-retardant polyvinyl chloride cable material: 100 parts of PVC resin, 2 parts of calcium-zinc stabilizer, 8 parts of magnesium hydroxide, 5 parts of antimony trioxide, 2 parts of calcium stearate and 35 parts of flame retardant F3 are put into a mixer, and are uniformly mixed and stirred at 110 ℃ to obtain a mixture, and then the mixture is sent into a double-screw extruder and is extruded and granulated at 150 ℃ to obtain the PVC cable material.
Comparative example 1
100 parts of PVC resin, 2 parts of calcium-zinc stabilizer, 8 parts of magnesium hydroxide, 5 parts of antimony trioxide, 2 parts of calcium stearate and 35 parts of flame retardant chlorinated paraffin 42 are put into a mixer, mixed and stirred uniformly at 110 ℃ to obtain a mixture, and then the mixture is sent into a double-screw extruder and extruded and granulated at 150 ℃ to obtain the PVC cable material.
Comparative example 2
100 parts of PVC resin, 2 parts of calcium-zinc stabilizer, 8 parts of magnesium hydroxide, 5 parts of antimony trioxide, 2 parts of calcium stearate and 35 parts of flame retardant chlorinated paraffin 52 are put into a mixer, mixed and stirred uniformly at 110 ℃ to obtain a mixture, and then the mixture is sent into a double-screw extruder and extruded and granulated at 150 ℃ to obtain the PVC cable material.
Comparative example 3
100 parts of PVC resin, 2 parts of calcium-zinc stabilizer, 8 parts of magnesium hydroxide, 5 parts of antimony trioxide, 2 parts of calcium stearate and 35 parts of flame retardant chlorinated paraffin 70 are put into a mixer, mixed and stirred uniformly at 110 ℃ to obtain a mixture, and then the mixture is sent into a double-screw extruder and extruded and granulated at 150 ℃ to obtain the PVC cable material.
The performance of the PVC cable materials of examples 1-3 and comparative examples 1-3 was tested according to the experimental methods specified in the GB/T8815-2002 and GB/T5470-2008 standards, and the test results are shown in Table 1.
Table 1 performance data of the PVC cable materials of examples 1-3 and comparative examples 1-3:
Figure BDA0002551462360000071
in conclusion, the branched chlorinated paraffin is embedded with three excellent flame retardant elements, namely nitrogen, bromine and chlorine, and the three elements generate synergistic interaction from different flame retardant mechanisms, so that higher flame retardant efficiency can be shown.

Claims (7)

1. A heat-resistant flame-retardant polyvinyl chloride cable material is characterized in that the heat-resistant flame-retardant polyvinyl chloride cable material is prepared by processing PVC resin, a calcium-zinc stabilizer, magnesium hydroxide, antimony trioxide, calcium stearate and a flame retardant; the flame retardant has a structure represented by formula (I):
Figure FDA0002551462350000011
wherein, in the formula (I), R1、R2、R3、R4、R5And R6 is a chlorinated paraffin segment.
2. The preparation method of the flame retardant is characterized by comprising the following steps:
step (1): preparation of chlorinated paraffins containing carboxyl groups
Dissolving chlorinated paraffin in butanone, adding a certain amount of p-hydroxybenzoic acid and potassium carbonate, and heating to react under the protection of nitrogen to obtain chlorinated paraffin containing carboxyl;
step (2): preparation of chlorinated paraffins containing acid chlorides
Adding the chlorinated paraffin containing carboxyl obtained in the step (1) into a reaction kettle, and dropwise adding excessive phosphorus trichloride into the reaction kettle to react to obtain chlorinated paraffin containing acyl chloride;
and (3): preparation of hydroxyl-containing isocyanurate modified chlorinated Paraffin
Slowly dripping the chlorinated paraffin containing acyl chloride prepared in the step (2) into a mixed system of tris (2-hydroxyethyl) isocyanurate and triethylamine serving as an acid-binding agent for esterification reaction, wherein the molar ratio of the chlorinated paraffin containing acyl chloride to the tris (2-hydroxyethyl) isocyanurate is 2-2.2: 1, and reacting to obtain chlorinated paraffin containing hydroxyl isocyanurate modification;
and (4): preparation of carboxyl-containing isocyanurate-modified chlorinated Paraffin
Reacting the hydroxyl-containing chlorinated paraffin obtained in the step (3) with tetrabromophthalic anhydride to obtain carboxyl-containing isocyanurate modified chlorinated paraffin;
and (5): preparation of flame retardant
And (3) adding the chlorinated paraffin modified by the isocyanuric ester containing carboxyl prepared in the step (4), 2- (bromomethyl) -2- (hydroxymethyl) -1, 3-propylene glycol and a proper amount of toluene or cyclohexane as a water-carrying agent into a reaction kettle, adding p-toluenesulfonic acid with the mass fraction of 1-5% of the total mass of reactants, heating to 150-220 ℃ under stirring, reacting for 3-6 h, and drying the product to obtain the flame retardant.
3. The method according to claim 2, wherein the chlorinated paraffin containing carboxyl group is prepared by reacting the chlorinated paraffin with p-hydroxybenzoic acid in the step (1) at a temperature of 55-80 ℃ for 10-30 hours.
4. The preparation method of claim 2, wherein the chlorinated paraffin containing carboxyl in the step (2) reacts with excess phosphorus trichloride at a temperature of 50-70 ℃ for 4-6 h to obtain chlorinated paraffin containing acyl chloride.
5. The preparation method of claim 2, wherein the esterification reaction in the step (3) is carried out under the reaction conditions that chlorinated paraffin containing acyl chloride is slowly added dropwise into the mixed solution of tris (2-hydroxyethyl) isocyanurate and the acid-binding agent in an ice-water bath for reaction, and after the dropwise addition is completed, the reaction is continued in the ice-water bath for 2-4 hours.
6. The preparation method according to claim 2, wherein the reaction conditions in the step (4) are reaction at a temperature of 60-80 ℃ for 3-7 h.
7. The method according to claim 2, wherein the reaction molar ratio of the carboxyl group-containing isocyanurate-modified chlorinated paraffin and 2- (bromomethyl) -2- (hydroxymethyl) -1, 3-propanediol in the step (5) is 3: 1.
CN202010577483.7A 2020-06-22 2020-06-22 Heat-resistant flame-retardant polyvinyl chloride cable material Withdrawn CN111621105A (en)

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