CN108659372B - Environment-friendly polyvinyl chloride cable material and preparation method thereof - Google Patents
Environment-friendly polyvinyl chloride cable material and preparation method thereof Download PDFInfo
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Abstract
An environment-friendly polyvinyl chloride cable material and a preparation method thereof, belonging to the technical field of cable materials. The adhesive is characterized by comprising the following components in parts by weight: polyvinyl chloride resin: 100 parts, heat stabilizer: 4-6 parts of a main plasticizer cyclohexane-1, 2 dioctyl phthalate: 18-22 parts of auxiliary plasticizer trioctyl phosphite: 13-17 parts of flame-retardant smoke suppressant: 8-10 parts of calcined montmorillonite: 3-5 parts of tetrakis [ methyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) oleate ] pentaerythritol ester: 0.05-0.1 part of dilauryl thiodipropionate: 0.05-0.1 part of lubricant: 0.1 to 0.2 portion. The preparation steps are as follows: weighing the materials, mixing in a high-speed mixer, and granulating the mixed materials in a double-screw extruder. The invention provides an environment-friendly polyvinyl chloride cable material which is low in flame retardant consumption, good in flame retardance, lead-free, low-smoke, environment-friendly, good in thermal stability and excellent in mechanical property and a preparation method thereof.
Description
Technical Field
An environment-friendly polyvinyl chloride cable material and a preparation method thereof, belonging to the technical field of cable materials.
Background
The polyvinyl chloride cable material is prepared by taking polyvinyl chloride as basic resin, adding a proper amount of auxiliary agents such as a stabilizer, a filler, a lubricant and the like, and mixing, kneading and extruding, and is mainly used for preparing wires, cables and the like. However, the electric wires and cables are easy to generate heat and burn due to short circuit in the using process, and the safety of people's property is seriously threatened.
With the rapid development of global economy and the enhancement of human environmental awareness, the requirements of various fields on the quality and the performance of wires and cables are higher and higher, more and more fires are caused by the aging of the wires and the cables, how to reduce the occurrence rate of the fires and the death rate of the fires, and low smoke, flame retardance and environmental protection also become the development direction of the wire and cable industry. At present, most of the environment-friendly low-smoke flame-retardant cable materials are produced by adding a large amount of aluminum hydroxide or magnesium hydroxide into a base material to achieve a flame-retardant effect, however, the addition of a large amount of inorganic materials influences the physical and mechanical properties and the processing technological properties of the cable materials, and the cable materials are poor in softness, weather resistance, oil resistance and low-temperature resistance at normal temperature.
The existing environment-friendly flame-retardant polyvinyl chloride cable material comprises the following components in percentage by mass: 60-75% of polyvinyl chloride, 10-15% of trioctyl trimellitate, 5-10% of melamine cyanurate, 2-8% of organic montmorillonite, 1-3% of antimony trioxide, 0.5-1.5% of calcium zinc stabilizer, 0.1-0.5% of antioxidant and 1-2% of calcium stearate. The flame-retardant halogen-free flame-retardant low-smoke environment-friendly flame-retardant halogen-free flame-. However, the method adds antimony flame retardant, and because of the good synergistic effect with chlorine atoms in the polyvinyl chloride molecular chain, the method can achieve better flame retardant effect by adding a small amount, and is favored in the industry in recent years. However, the flame-retardant smoke generation amount of the antimony-chlorine flame-retardant system is high, and antimony oxide dust has great harm to a respiratory system, so that the environment-friendly requirement on a flame-retardant product cannot be met.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art, and provides an environment-friendly polyvinyl chloride cable material which has the advantages of small flame retardant consumption, good flame retardance, no lead, low smoke, environmental protection, good thermal stability and excellent mechanical property, and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: the environment-friendly polyvinyl chloride cable material is characterized by comprising the following components in parts by weight: polyvinyl chloride resin: 100 parts, heat stabilizer: 4-6 parts of a main plasticizer cyclohexane-1, 2 dioctyl phthalate: 18-22 parts of auxiliary plasticizer trioctyl phosphite: 13-17 parts of flame-retardant smoke suppressant: 8-10 parts of calcined montmorillonite: 3-5 parts of tetrakis [ methyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) oleate ] pentaerythritol ester: 0.05-0.1 part of dilauryl thiodipropionate: 0.05-0.1 part of lubricant: 0.1-0.2 parts; the polyvinyl chloride resin is PVC resin with the average polymerization degree of 1000-1300.
Preferably, the composition in parts by weight is: polyvinyl chloride resin: 100 parts, heat stabilizer: 4.5-5.0 parts of cyclohexane-1, 2 dioctyl diformate as a main plasticizer: 19-20 parts of an auxiliary plasticizer trioctyl phosphite: 14-16 parts of a flame-retardant smoke suppressant: 9-9.5 parts of calcined montmorillonite: 3.5 to 4 parts of tetrakis [ methyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) oleate ] pentaerythritol ester: 0.07-0.08 parts of dilauryl thiodipropionate: 0.07-0.08 parts of lubricant: 0.13 to 0.15 portion.
Preferably, the preparation method of the flame-retardant smoke inhibitor is as follows:
1) according to the molar ratio of melamine to cyanuric acid of 1.5-3.0: 1 weighing materials, adding the materials into a closed reaction kettle, adding water, and stirring and reacting at 105-110 ℃ for 40-60 minutes;
2) opening the reaction kettle, adding HCl, adding zinc chloride and sodium hydroxystannate into the reaction kettle, wherein the molar ratio of cyanuric acid to HCl, zinc chloride to sodium hydroxystannate is 1: 1-4: 0.5-2: 1-4, uniformly stirring, reacting for 2-3 hours at 90-100 ℃, cooling, washing with water, performing suction filtration, and drying to obtain the flame-retardant smoke suppressant.
Wherein in step 1) the melamine is in excess and the product is melamine cyanurate.
Wherein, the hydrochloric acid in the step 2) reacts with the excessive melamine in the step 1), and then reacts with sodium hydroxystannate and zinc chloride, and the specific reaction equation is as follows:
the preparation method uses cyclohexane-1, 2 dioctyl phthalate as a main plasticizer, and the main components of the flame-retardant smoke suppressant are melamine cyanurate and melamine hydroxyl zinc stannate, wherein the melamine cyanurate can be used as a main flame retardant, the melamine hydroxyl zinc stannate can be used as a smoke suppressant and an auxiliary flame retardant, and calcined clay is used as an auxiliary flame retardant. The nitrogen flame retardants such as melamine cyanurate have the advantages of no halogen, low smoke, stable photo-thermal property, low price, suitability for processing, good compatibility with polymers and the like, are subjected to decomposition reaction when heated, have the functions of absorbing heat, reducing temperature, diluting and the like, and play a role in protecting polymers and preventing combustion; the melamine hydroxyl zinc stannate zinc salt tin-containing flame retardant has the advantages of good thermal stability, no toxicity, high efficiency, no stimulation to human body and good heat resistance, PVC is easily cyclized to generate aromatic hydrocarbon after being heated and decomposed, the substances are also important factors for generating smoke, and Zn of the melamine hydroxyl zinc stannate zinc salt2+And the product ZnCl generated by adsorbing HCl2Step 2) Zn described above2+Plays a catalytic role in the process of generating trans-form multiolefin structure by PVC, and the obtained trans-formThe polyene can not generate aromatic hydrocarbon through cyclization, so that the aim of preventing the PVC main chain from degrading is fulfilled; ZnCl2The high polymer can be helped to carry out crosslinking reaction and carbonization reaction, and a very compact carbonization layer is generated on the surface of the high polymer, so that external oxygen and heat are isolated, the combustion reaction is inhibited, and the smoke release is reduced; the calcined montmorillonite belongs to a silicon flame retardant, the flame retardant mechanism of the silicon flame retardant is that the silicon flame retardant can reinforce a carbon protective layer on the surface of a material and generate a free radical capture active intermediate, so that the flame retardant effect is achieved, the mechanism is mainly expressed as an isolating membrane mechanism, and the flame retardant is a carbon-forming smoke suppressant and has the advantages of excellent flame retardancy, processability, environmental friendliness and the like compared with other flame retardants. The flame retardant and the flame retardant smoke suppressant are effectively combined to prepare the flame retardant smoke suppressant polyvinyl chloride cable material which is good in flame retardance, free of halogen, lead and smoke, low in smoke, environment-friendly, good in thermal stability and excellent in mechanical property.
Preferably, the molar ratio of cyanuric acid to HCl, zinc chloride and sodium hydroxystannate is 1: 2.8-3.4: 0.9-1.3: 2.4 to 3.1.
Preferably, the polyvinyl chloride resin is a PVC resin having an average polymerization degree of 1300.
Preferably, the heat stabilizer is a calcium-zinc heat stabilizer. The calcium-zinc heat stabilizer is preferably German bear calcium-zinc heat stabilizer 9700.
Trioctyl phosphite is selected as a flame-retardant cold-resistant plasticizer.
Preferably, the lubricant is stearic acid.
Tetrakis (methyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) oleate) pentaerythritol ester is preferably the antioxidant 1010, and dilauryl thiodipropionate is preferably the antioxidant DLTP.
The preparation method of the environment-friendly polyvinyl chloride cable material is characterized by comprising the following preparation steps:
1) weighing the materials, mixing the materials in a high-speed mixer with the rotation speed of 1000-1400 revolutions for 10-12 minutes, putting the materials into a low-speed mixer after liquid phase components are completely absorbed by PVC resin and the mixed materials are not bonded and uniformly dispersed, starting stirring and cooling, and discharging the materials after the temperature of the materials is reduced to 55-62 ℃;
2) and (3) granulating the mixed material in a double-screw extruder to obtain the flame-retardant smoke-suppressing polyvinyl chloride cable material.
Preferably, the rotation speed of the high-speed mixer in the step 1) is 1300, and the mixing time is 11 minutes.
The cyclohexane-1, 2 dioctyl phthalate (DECH) is an environment-friendly plasticizer.
The environment-friendly plasticizer cyclohexane-1, 2 dioctyl phthalate is used as a main plasticizer, and has a good synergistic effect with an auxiliary plasticizer TNPP, the prepared flame-retardant smoke suppressant and calcined montmorillonite play a very good synergistic effect, and the prepared cable material has a good flame-retardant smoke suppression effect; the cable material has the advantages of small flame retardant consumption, good flame retardance, no lead, low smoke, environmental protection, good thermal stability, excellent mechanical property and the like.
Compared with the prior art, the environment-friendly polyvinyl chloride cable material and the preparation method thereof have the beneficial effects that: according to the invention, the environment-friendly plasticizer cyclohexane-1, 2 dioctyl phthalate is used as a main plasticizer, and has a good synergistic effect with an auxiliary plasticizer TNPP; the main components of the flame-retardant smoke inhibitor are melamine cyanurate and zinc salt of melamine hydroxyl stannic acid, and the two flame-retardant smoke inhibitors are prepared by reaction; wherein, the melamine cyanurate can be used as a main flame retardant, the melamine hydroxyl zinc stannate can be used as a smoke suppressant and an auxiliary flame retardant, and the calcined montmorillonite can be used as an auxiliary flame-retardant smoke suppressant; the prepared flame-retardant smoke suppressant and the calcined montmorillonite play a very good synergistic role, and the prepared cable material has a good flame-retardant smoke suppression effect.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. Of these, example 1 is the most preferred example.
The formulations of the examples are shown in Table 1.
Table 1 example formulations
In examples 1 to 3, the polymerization degree of the polyvinyl chloride resin was 1300; the polymerization degree of the polyvinyl chloride resin in example 4 was 1200; the polymerization degree of the polyvinyl chloride resin in example 5 was 1100; the polymerization degree of the polyvinyl chloride resin in example 6 was 1000;
the preparation method of the flame-retardant smoke suppressant in the embodiments 1 to 3 is as follows:
1) adding 2.0 mol of melamine and 1 mol of cyanuric acid into a closed reaction kettle, adding 1000 ml of water, and stirring at 110 ℃ for reacting for 50 minutes;
2) opening the reaction kettle, adding 2800ml of 1.0 mol/L hydrochloric acid solution, dissolving 1.3 mol of zinc chloride and 2.4 mol of sodium hydroxystannate in 2000ml of water, adding the obtained solution into the reaction kettle, uniformly stirring, reacting for 2 hours at the temperature of 95 ℃, cooling, washing with water, carrying out suction filtration, and drying to obtain the flame-retardant smoke suppressant.
The preparation method of the flame-retardant smoke suppressant in example 4 is as follows:
1) adding 2.5 mol of melamine and 1 mol of cyanuric acid into a closed reaction kettle, adding 1000 ml of water, and stirring at 108 ℃ for reaction for 55 minutes;
2) opening the reaction kettle, adding 3400ml of 1.0 mol/L hydrochloric acid solution, dissolving 0.9 mol of zinc chloride and 3.1 mol of sodium hydroxystannate in 2000ml of water, adding the solution into the reaction kettle, stirring uniformly, reacting for 2 hours at 95 ℃, cooling, washing with water, carrying out suction filtration, and drying to obtain the flame-retardant smoke suppressant.
The preparation method of the flame-retardant smoke suppressant in example 5 is as follows:
1) adding 3.0 mol of melamine and 1 mol of cyanuric acid into a closed reaction kettle, adding 1000 ml of water, and stirring at 110 ℃ for reacting for 40 minutes;
2) opening the reaction kettle, adding 2000ml of 1.0 mol/L hydrochloric acid solution, dissolving 1.0 mol of zinc chloride and 2.0 mol of sodium hydroxystannate in 2000ml of water, adding the solution into the reaction kettle, stirring uniformly, reacting for 2 hours at 95 ℃, cooling, washing with water, carrying out suction filtration, and drying to obtain the flame-retardant smoke suppressant.
The preparation method of the flame-retardant smoke suppressant in example 6 is as follows:
1) adding 1.5 mol of melamine and 1 mol of cyanuric acid into a closed reaction kettle, adding 1000 ml of water, and stirring at 105 ℃ for reacting for 60 minutes;
2) opening the reaction kettle, adding 2000ml of 1.0 mol/L hydrochloric acid solution, dissolving 1.0 mol of zinc chloride and 2.0 mol of sodium hydroxystannate in 2000ml of water, adding the solution into the reaction kettle, stirring uniformly, reacting for 2 hours at 95 ℃, cooling, washing with water, carrying out suction filtration, and drying to obtain the flame-retardant smoke suppressant.
2) Opening the reaction kettle, adding HCl, adding zinc chloride and sodium hydroxystannate into the reaction kettle, wherein the molar ratio of cyanuric acid to HCl, zinc chloride to sodium hydroxystannate is 1: 1-4: 0.5-2: 1-4, uniformly stirring, reacting for 2-3 hours at 90-100 ℃, cooling, washing with water, performing suction filtration, and drying to obtain the flame-retardant smoke suppressant.
The formula of comparative examples 1 to 5 is as follows:
comparative example 1: the auxiliary TNPP was replaced with cumyl diphenyl phosphate (IPP) on the basis of example 1, and the rest was the same as in example 5.
Comparative example 2: replacing the flame-retardant smoke suppressant on the basis of the embodiment 1, and the rest is the same as the embodiment 1;
the preparation method of the flame-retardant smoke suppressant in comparative example 2 is as follows:
1) adding 2.0 mol of melamine and 1 mol of cyanuric acid into a closed reaction kettle, adding 1000 ml of water, and stirring at 110 ℃ for reacting for 50 minutes;
(2) and opening the reaction kettle, dissolving 2.0 mol of zinc stannate in 2000ml of water, adding the zinc stannate into the reaction kettle, uniformly stirring, cooling, washing with water, performing suction filtration, and drying to obtain the flame-retardant smoke suppressant.
Comparative example 3: the flame retardant smoke suppressant is replaced by melamine cyanurate and zinc stannate based on example 1 at a molar ratio of 1: 2.
Comparative example 4: the flame retardant and smoke suppressant is replaced by melamine cyanurate and zinc hydroxystannate on the basis of example 1 in a molar ratio of 1: 2.
Comparative example 5: the flame retardant smoke suppressant was replaced with melamine cyanurate and melamine hydroxystannate in a 1:1 molar ratio based on example 1.
The preparation method of the melamine hydroxyl stannate comprises the following steps:
adding 1 mol of melamine into a reaction kettle, adding 2000ml of 1.0 mol/L hydrochloric acid solution, dissolving 1.0 mol of zinc chloride and 2.0 mol of sodium hydroxystannate into 2000ml of water, adding the solution into the reaction kettle, uniformly stirring, reacting for 2 hours at the temperature of 95 ℃, cooling, washing with water, carrying out suction filtration, and drying to obtain the melamine hydroxyl stannate.
Comparative example 6: the flame retardant and smoke suppressant was increased to 15 parts based on example 1, and the rest was the same as example 1.
Weighing the PVC resin, the calcium-zinc stabilizer, the antioxidant 1010/DMTP and stearic acid according to the formula, adding the PVC resin, the calcium-zinc stabilizer, the antioxidant 1010/DMTP and the stearic acid into a preheated high-speed mixer, starting stirring (the rotating speed is 1000-1400 revolutions), adding the plasticizer DECH/TNPP into the high-speed mixer to mix for 8-10 minutes when the material temperature reaches 80 ℃, adding the flame-retardant smoke suppressant and the calcined montmorillonite after the plasticizer is fully absorbed by the PVC resin, continuing stirring and mixing for 2-4 minutes, discharging, and cooling. The mixed materials were pelletized in a twin-screw extruder with the pelletizing parameters set forth in table 2. The compound materials are plasticized and split by a heating double roller, and are pressed into two sample slices of 200mm multiplied by 4mm and 200mm multiplied by 2mm by a press. And (3) a mould pressing process: plasticizing for 4min at 180 ℃, wherein the plasticizing process comprises the following steps: keeping the temperature at 180 ℃ and the pressure at 10-15 MPa for 3 min. Preparing a sample strip of 80mm multiplied by 10mm multiplied by 4mm by using a stamping machine for detecting the oxygen index, and preparing a 2mm 5A type tensile sample strip for a tensile test; the smoke density test was performed using twin screw extruded pelletized pellets.
TABLE 2 granulator parameter settings
The performance tests of the above examples and comparative examples are as follows:
TABLE 3 Properties of examples and comparative examples
From the example and comparative example data it can be seen that: the cable materials in the embodiments 1-6 have good mechanical properties and flame retardant and smoke suppression properties, and the smoke density is far lower than the acknowledged low smoke value of 300, wherein the cable material prepared in the embodiment 1 has the best performance. Compared with the embodiment 1, the cable material prepared in the comparative example 1 has lower mechanical property and flame-retardant smoke-suppressing performance, the smoke density is more than 300, the HCl release amount in a combustion test is more than 100mg/g, and a better smoke-suppressing effect is not achieved, which indicates that compared with TNPP, the mutual synergistic effect of IPP, the main plasticizer and the flame-retardant smoke-suppressing agent is poorer; the mechanical properties of the cable materials prepared in comparative examples 2, 3 and 4 are equivalent to those of the material in example 1, but the flame retardant and smoke suppression properties are low; from the performance of comparative example 1, compared with the zinc salt of melamine hydroxystannate, the melamine hydroxy sodium salt has poor synergistic flame-retardant smoke suppression effect with melamine urate and calcined montmorillonite, the oxygen index is obviously low, the smoke density is more than 300, the HCl release amount in a combustion test is more than 100mg/g, and the better smoke suppression effect is not achieved; from the performance of comparative example 6, the flame-retardant smoke-suppressing effect of more flame-retardant smoke-suppressing agent on the cable material is not greatly improved, but the mechanical property of the cable material is reduced.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (8)
1. An environment-friendly polyvinyl chloride cable material is characterized by comprising the following components in parts by weight: polyvinyl chloride resin: 100 parts, heat stabilizer: 4-6 parts of a main plasticizer cyclohexane-1, 2 dioctyl phthalate: 18-22 parts of auxiliary plasticizer trioctyl phosphite: 13-17 parts of flame-retardant smoke suppressant: 8-10 parts of calcined montmorillonite: 3-5 parts of antioxidant 1010: 0.05-0.1 part of dilauryl thiodipropionate: 0.05-0.1 part of lubricant: 0.1-0.2 parts; the polyvinyl chloride resin is PVC resin with the average polymerization degree of 1000-1300;
the preparation method of the flame-retardant smoke suppressant comprises the following steps:
1) according to the molar ratio of melamine to cyanuric acid of 1.5-3.0: 1 weighing materials, adding the materials into a closed reaction kettle, adding water, and stirring and reacting at 105-110 ℃ for 40-60 minutes;
2) opening the reaction kettle, adding HCl, adding zinc chloride and sodium hydroxystannate into the reaction kettle, wherein the molar ratio of cyanuric acid to HCl, zinc chloride to sodium hydroxystannate is 1: 1-4: 0.5-2: 1-4, uniformly stirring, reacting for 2-3 hours at 90-100 ℃, cooling, washing with water, performing suction filtration, and drying to obtain the flame-retardant smoke suppressant.
2. The environment-friendly polyvinyl chloride cable material as claimed in claim 1, wherein: the components by weight portion are as follows: polyvinyl chloride resin: 100 parts, heat stabilizer: 4.5-5.0 parts of cyclohexane-1, 2 dioctyl diformate as a main plasticizer: 19-20 parts of an auxiliary plasticizer trioctyl phosphite: 14-16 parts of a flame-retardant smoke suppressant: 9-9.5 parts of calcined montmorillonite: 3.5-4 parts of antioxidant 1010: 0.07-0.08 parts of dilauryl thiodipropionate: 0.07-0.08 parts of lubricant: 0.13 to 0.15 portion.
3. The environment-friendly polyvinyl chloride cable material as claimed in claim 1, wherein: the molar ratio of cyanuric acid to HCl, zinc chloride and sodium hydroxystannate is 1: 2.8-3.4: 0.9-1.3: 2.4 to 3.1.
4. The environment-friendly polyvinyl chloride cable material as claimed in claim 1 or 2, wherein: the polyvinyl chloride resin is PVC resin with the average polymerization degree of 1300.
5. The environment-friendly polyvinyl chloride cable material as claimed in claim 1 or 2, wherein: the heat stabilizer is a calcium-zinc heat stabilizer.
6. The environment-friendly polyvinyl chloride cable material as claimed in claim 1 or 2, wherein: the lubricant is stearic acid.
7. The preparation method of the environment-friendly polyvinyl chloride cable material as claimed in any one of claims 1 to 6, which is characterized by comprising the following steps:
1) weighing the materials, mixing the materials in a high-speed mixer with the rotation speed of 1000-1400 revolutions for 10-12 minutes, putting the materials into a low-speed mixer after liquid phase components are completely absorbed by PVC resin and the mixed materials are not bonded and uniformly dispersed, starting stirring and cooling, and discharging the materials after the temperature is reduced to 55-62 ℃;
2) and (3) granulating the mixed material in a double-screw extruder to obtain the flame-retardant smoke-suppressing polyvinyl chloride cable material.
8. The preparation method of the environment-friendly polyvinyl chloride cable material as claimed in claim 7, wherein the preparation method comprises the following steps: the rotating speed of the high-speed mixer in the step 1) is 1300, and the mixing is carried out for 11 minutes.
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| CN103450595A (en) * | 2013-08-30 | 2013-12-18 | 江苏达胜高聚物有限公司 | Environment-friendly type PVC (polyvinyl chloride) cable material |
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| CN103450595A (en) * | 2013-08-30 | 2013-12-18 | 江苏达胜高聚物有限公司 | Environment-friendly type PVC (polyvinyl chloride) cable material |
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| 羟基锡酸三聚氰胺盐及羟基锡酸金属盐复合物阻燃PVC的阻燃性能及热性能研究;厉娇蕊等;《塑料科技》;20151210;91-95 * |
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