High-temperature-resistant polyvinyl chloride insulation material and application thereof in cable

Abstract

The invention relates to the technical field of insulating materials, and discloses a high-temperature-resistant polyvinyl chloride insulating material and application thereof in a cable, parachloroaniline, formaldehyde, bisphenol S, diethanol amine, phthalic anhydride and the like are used as raw materials, a Mannich reaction, a substitution reaction and a ring-opening polymerization reaction are performed to obtain phthalic anhydride polyester polyol, and the phthalic anhydride polyester polyol, 4, 4 '-diphenyl-1, 3-pentanediol, 4, 4'-diphenyl-1, 3-pentanediol and 4, 4 '-diphenyl-1, 3-pentanediol are used as raw materials to prepare the high-temperature-resistant polyvinyl chloride insulating material. The high-temperature-resistant polyvinyl chloride insulation material is prepared by taking 1, 4-diphenylmethane diisocyanate and 1, 4-butanediol as raw materials to obtain modified thermoplastic polyurethane, initiating crosslinking of the modified thermoplastic polyurethane, polyvinyl chloride resin and the like, and uniformly mixing the modified thermoplastic polyurethane, the polyvinyl chloride resin and the like to obtain the high-temperature-resistant polyvinyl chloride insulation material, and the prepared polyvinyl chloride insulation material has relatively good high-temperature resistance and wear resistance.

Description

Technical Field

[0001] The invention relates to the technical field of insulating materials, in particular to a high-temperature resistant polyvinyl chloride insulating material and application thereof in cables. Background Art

[0002] Polyvinyl chloride has excellent properties such as flame retardancy and insulation, and is widely used in chemical, construction, agriculture and other fields. Polyvinyl chloride insulation materials prepared from polyvinyl chloride have excellent physical and mechanical properties, chemical properties, etc., but their high temperature resistance and wear resistance are poor. With the rapid development of science and technology, traditional polyvinyl chloride insulation materials can no longer meet actual needs. Therefore, how to improve the wear resistance and high temperature resistance of polyvinyl chloride insulation materials to meet the growing actual needs has become a hot topic in current research.

[0003] Thermoplastic polyurethane is an elastomer with excellent performance, excellent acid and alkali resistance, mechanical properties, etc., and is widely used in the fields of chemical industry, agriculture, machinery, etc. For example, the patent application publication number is CN116178933A, which discloses a highly flame-retardant and highly wear-resistant cable material and cable. The invention uses thermoplastic polyurethane elastomer, polyvinyl chloride, etc. as raw materials, and the prepared cable material has good flame retardancy and mechanical properties, but does not improve the high temperature resistance of the material. Summary of the invention

[0004] 1. Technical issues to be resolved

[0005] In view of the deficiencies in the prior art, the present invention provides a high-temperature resistant polyvinyl chloride insulating material and application thereof in cables. The prepared insulating material has good high-temperature resistance and wear resistance.

[0006] (II) Technical solution

[0007] A high temperature resistant polyvinyl chloride insulating material, the high temperature resistant polyvinyl chloride insulating material is composed of the following components by weight:

[0008] 100 parts by weight of polyvinyl chloride resin, 30-50 parts by weight of plasticizer, 0.1-0.5 parts by weight of initiator, 0.5-1 parts by weight of antioxidant, 6-10 parts by weight of stabilizer, 2-5 parts by weight of co-crosslinking agent, and 10-30 parts by weight of modified thermoplastic polyurethane;

[0009] The high temperature resistant polyvinyl chloride insulating material is prepared by the following method:

[0010] Add polyvinyl chloride resin, plasticizer trioctyl trimellitate (TOTM), initiator diisopropyl peroxide (DCP), antioxidant, stabilizer, and cross-linking agent triallyl isocyanurate (TAIC) into a high-speed mixer, stir and mix for 10-30 minutes, then add modified thermoplastic polyurethane, continue mixing for 5-10 minutes, and discharge to obtain high-temperature resistant polyvinyl chloride insulation material.

[0011] According to the above technical solution, preferably, the modified thermoplastic polyurethane is prepared by the following method:

[0012] Step (1) adding p-chloroaniline and 35-40% formaldehyde aqueous solution into a flask containing dioxane solvent, stirring and mixing at 5-10° C. for 12-20 min, then adding bisphenol S thereto, reacting at 90-100° C. for 5-10 h, and after the reaction is completed, distilling under reduced pressure, washing with deionized water, and drying to obtain intermediate 1;

[0013] Step (2) adding the intermediate 1 to a flask containing an ethanol solvent, stirring and dispersing, and then adding diethanolamine thereto, reacting at 95-110° C. for 10-18 hours. After the reaction is completed, vacuum rotary evaporation is performed to remove the solvent to obtain a benzoxazinyl polyol;

[0014] Step (3) under nitrogen conditions, benzoxazine-based polyol and phthalic anhydride are added to a flask, stirred and dispersed, and then 3% by mass of tetrabutyl titanate is added thereto, and the reaction is carried out at 140-160° C. for 20-36 hours. After the reaction is completed, the temperature is lowered to room temperature to obtain phthalic anhydride polyester polyol;

[0015] Step (4) adding the vacuum dehydrated phthalic anhydride polyester polyol into a beaker, controlling the temperature to 50-60°C, stirring for 20-30min, then adding 4,4-diphenylmethane diisocyanate thereto, reacting at 60-70°C for 30-50min, then adding 1,4-butanediol thereto, stirring at 70-80°C for 1-2min, placing in a nitrogen-protected 120°C oven, maturing for 3-5h, and then cooling to room temperature to obtain a modified thermoplastic polyurethane.

[0016] According to the above technical solution, preferably, in the step (1), the mass ratio of p-chloroaniline to bisphenol S is 1-1.5:1.

[0017] According to the above technical solution, preferably, in the step (2), the mass ratio of the intermediate 1 to diethanolamine is 1:0.35-0.5.

[0018] According to the above technical solution, preferably, in the step (3), the mass ratio of benzoxazine-based polyol to phthalic anhydride is 2-5:1.

[0019] According to the above technical solution, preferably, in the step (4), the mass ratio of phthalic anhydride polyester polyol, 4,4-diphenylmethane diisocyanate, and 1,4-butanediol is 1:0.55-0.9:0.2-0.35.

[0020] According to the above technical solution, preferably, the high temperature resistant polyvinyl chloride insulation material is used in the preparation of cables.

[0021] (III) Beneficial technical effects

[0022] The invention uses p-chloroaniline, formaldehyde and bisphenol S as raw materials, performs a Mannich reaction to obtain an intermediate 1, uses the intermediate 1 and diethanolamine to undergo a substitution reaction to obtain a benzoxazine-based polyol, uses the benzoxazine-based polyol and phthalic anhydride to undergo a ring-opening polymerization reaction under the catalysis of tetra-n-butyl titanate to obtain a phthalic anhydride polyester polyol, uses the phthalic anhydride polyester polyol, 4,4-diphenylmethane diisocyanate and 1,4-butanediol as raw materials to obtain a modified thermoplastic polyurethane, and mixes and cross-links the modified thermoplastic polyurethane with a polyvinyl chloride resin and the like to obtain a high-temperature resistant polyvinyl chloride insulating material.

[0023] The intermediate 1 prepared by the Mannich reaction of the present invention contains a benzene ring structure and a six-membered ring structure, which are heat-resistant rigid groups. When added to the insulating material, the heat resistance of polyvinyl chloride can be increased. Moreover, when the six-membered ring structure is heated, it can absorb heat to open the ring and crosslink, further improving the heat resistance and wear resistance of the insulating material. In the presence of a co-crosslinking agent, the modified thermoplastic polyurethane prepared by the present invention can be induced by the initiator to induce a crosslinking reaction between polyvinyl chloride and the modified thermoplastic polyurethane, thereby increasing the degree of crosslinking and increasing the wear resistance and high temperature resistance of the insulating material. Moreover, the insulating material prepared by the present invention has good wear resistance and high temperature resistance after experimental verification. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is a preparation route for benzoxazinyl polyols. DETAILED DESCRIPTION

[0025] The following examples are merely listed as examples of embodiments of the present invention and do not constitute any limitation to the present invention. Those skilled in the art will appreciate that modifications within the scope of the spirit and concept of the present invention fall within the protection scope of the present invention.

[0026] Example 1

[0027] Step (1) Add 13 g of p-chloroaniline and 40% formaldehyde aqueous solution into a flask containing dioxane solvent, stir and mix at 10° C. for 15 min, then add 13 g of bisphenol S, react at 100° C. for 6 h, and after the reaction is completed, distill under reduced pressure, wash with deionized water, and dry to obtain intermediate 1.

[0028] Step (2) Add 20 g of intermediate 1 to a flask filled with ethanol solvent, stir and disperse, then add 8 g of diethanolamine, react at 100° C. for 16 h, and after the reaction is completed, remove the solvent by rotary evaporation under reduced pressure to obtain benzoxazine-based polyol.

[0029] Step (3) Under nitrogen conditions, 30 g of benzoxazine polyol and 10 g of phthalic anhydride are added to a flask, stirred and dispersed, and then 3% by mass of tetrabutyl titanate is added thereto, and the reaction is carried out at 150° C. for 28 hours. After the reaction is completed, the temperature is cooled to room temperature to obtain phthalic anhydride polyester polyol.

[0030] Step (4) Add 50g of vacuum dehydrated phthalic anhydride polyester polyol into a beaker, control the temperature to 55°C, stir for 30min, then add 45g of 4,4-diphenylmethane diisocyanate thereto, react at 65°C for 40min, then add 12g of 1,4-butanediol thereto, stir at 80°C for 2min, put into a nitrogen-protected 120°C oven, mature for 4h, and after completion, cool to room temperature to obtain a modified thermoplastic polyurethane.

[0031] Step (5) 100 g of polyvinyl chloride resin, 50 g of plasticizer TOTM, 0.4 g of initiator DCP, 1 g of antioxidant bisphenol A, 8 g of calcium zinc stabilizer, and 5 g of auxiliary crosslinking agent TAIC are added to a high-speed mixer, stirred and mixed for 20 minutes, and then 10 g of modified thermoplastic polyurethane is added thereto, and mixing is continued for 10 minutes, and the material is discharged to obtain a high temperature resistant polyvinyl chloride insulation material.

[0032] Example 2

[0033] Step (1) Add 15 g of p-chloroaniline and 40% formaldehyde aqueous solution into a flask containing dioxane solvent, stir and mix at 5° C. for 20 min, then add 13 g of bisphenol S, react at 90° C. for 10 h, and after the reaction is completed, distill under reduced pressure, wash with deionized water, and dry to obtain intermediate 1.

[0034] Step (2) Add 20 g of intermediate 1 to a flask filled with ethanol solvent, stir and disperse, then add 8 g of diethanolamine, react at 100° C. for 12 h, and after the reaction is completed, remove the solvent by rotary evaporation under reduced pressure to obtain benzoxazine-based polyol.

[0035] Step (3) Under nitrogen conditions, 50 g of benzoxazine polyol and 10 g of phthalic anhydride are added to a flask, stirred and dispersed, and then 3% by mass of tetrabutyl titanate is added thereto, and the reaction is carried out at 150° C. for 24 hours. After the reaction is completed, the temperature is cooled to room temperature to obtain phthalic anhydride polyester polyol.

[0036] Step (4) Add 50g of vacuum dehydrated phthalic anhydride polyester polyol into a beaker, control the temperature to 50°C, stir for 25min, then add 27.5g of 4,4-diphenylmethane diisocyanate thereto, react at 60°C for 50min, then add 10g of 1,4-butanediol thereto, stir at 75°C for 1min, put into a nitrogen-protected 120°C oven, mature for 5h, and after completion, cool to room temperature to obtain a modified thermoplastic polyurethane.

[0037] Step (5) 100 g of polyvinyl chloride resin, 40 g of plasticizer TOTM, 0.4 g of initiator DCP, 0.6 g of antioxidant bisphenol A, 9 g of calcium zinc stabilizer, and 5 g of auxiliary crosslinking agent TAIC are added to a high-speed mixer, stirred and mixed for 20 minutes, and then 15 g of modified thermoplastic polyurethane is added thereto, and mixing is continued for 6 minutes, and the material is discharged to obtain a high temperature resistant polyvinyl chloride insulation material.

[0038] Example 3

[0039] Step (1) Add 19.5 g of p-chloroaniline and 35% formaldehyde aqueous solution into a flask containing dioxane solvent, stir and mix at 10° C. for 12 min, then add 13 g of bisphenol S, react at 95° C. for 5 h. After the reaction is completed, distill under reduced pressure, wash with deionized water, and dry to obtain intermediate 1.

[0040] Step (2) Add 20 g of intermediate 1 to a flask filled with ethanol solvent, stir and disperse, then add 8 g of diethanolamine, react at 110° C. for 12 h, and after the reaction is completed, remove the solvent by rotary evaporation under reduced pressure to obtain benzoxazine-based polyol.

[0041] Step (3) Under nitrogen conditions, 20 g of benzoxazine polyol and 10 g of phthalic anhydride are added to a flask, stirred and dispersed, and then 3% by mass of tetrabutyl titanate is added thereto, and the reaction is carried out at 140° C. for 20 hours. After the reaction is completed, the temperature is cooled to room temperature to obtain phthalic anhydride polyester polyol.

[0042] Step (4) Add 50 g of vacuum dehydrated phthalic anhydride polyester polyol into a beaker, control the temperature to 60° C., stir for 20 min, then add 35 g of 4,4-diphenylmethane diisocyanate thereto, react at 70° C. for 30 min, then add 17.5 g of 1,4-butanediol thereto, stir at 70° C. for 2 min, put into a nitrogen-protected 120° C. oven, mature for 3 h, and after completion, cool to room temperature to obtain a modified thermoplastic polyurethane.

[0043] Step (5) 100 g of polyvinyl chloride resin, 30 g of plasticizer TOTM, 0.5 g of initiator DCP, 0.5 g of antioxidant bisphenol A, 10 g of calcium zinc stabilizer, and 4 g of co-crosslinking agent TAIC are added to a high-speed mixer, stirred and mixed for 20 minutes, and then 20 g of modified thermoplastic polyurethane is added thereto, and mixing is continued for 5 minutes, and the material is discharged to obtain a high temperature resistant polyvinyl chloride insulation material.

[0044] Example 4

[0045] Step (1) Add 18 g of p-chloroaniline and 40% formaldehyde aqueous solution into a flask containing dioxane solvent, stir and mix at 5° C. for 20 min, then add 13 g of bisphenol S, react at 95° C. for 6 h. After the reaction is completed, distill under reduced pressure, wash with deionized water, and dry to obtain intermediate 1.

[0046] Step (2) Add 20 g of intermediate 1 to a flask filled with ethanol solvent, stir and disperse, then add 10 g of diethanolamine, react at 95° C. for 18 h, and after the reaction is completed, remove the solvent by rotary evaporation under reduced pressure to obtain benzoxazine-based polyol.

[0047] Step (3) Under nitrogen conditions, 30 g of benzoxazine polyol and 10 g of phthalic anhydride are added to a flask, stirred and dispersed, and then 3% by mass of tetrabutyl titanate is added thereto, and the reaction is carried out at 150° C. for 36 hours. After the reaction is completed, the temperature is cooled to room temperature to obtain phthalic anhydride polyester polyol.

[0048] Step (4) Add 50 g of vacuum dehydrated phthalic anhydride polyester polyol into a beaker, control the temperature to 55 ° C, stir for 30 minutes, then add 40 g of 4,4-diphenylmethane diisocyanate thereto, react at 65 ° C for 40 minutes, then add 16 g of 1,4-butanediol thereto, stir at 80 ° C for 1 minute, put into a nitrogen-protected 120 ° C oven, mature for 4 hours, and after completion, cool to room temperature to obtain a modified thermoplastic polyurethane.

[0049] Step (5) 100 g of polyvinyl chloride resin, 40 g of plasticizer TOTM, 0.3 g of initiator DCP, 1 g of antioxidant bisphenol A, 6 g of calcium zinc stabilizer, and 5 g of auxiliary crosslinking agent TAIC are added to a high-speed mixer, stirred and mixed for 30 minutes, and then 25 g of modified thermoplastic polyurethane is added thereto, and mixing is continued for 5 minutes, and the material is discharged to obtain a high temperature resistant polyvinyl chloride insulation material.

[0050] Example 5

[0051] Step (1) Add 16 g of p-chloroaniline and 38% formaldehyde aqueous solution into a flask containing dioxane solvent, stir and mix at 10° C. for 15 min, then add 13 g of bisphenol S, react at 95° C. for 6 h. After the reaction is completed, distill under reduced pressure, wash with deionized water, and dry to obtain intermediate 1.

[0052] Step (2) Add 20 g of the intermediate 1 into a flask filled with an ethanol solvent, stir and disperse, then add 7 g of diethanolamine, react at 100° C. for 10 h, and after the reaction is completed, remove the solvent by rotary evaporation under reduced pressure to obtain a benzoxazine-based polyol.

[0053] Step (3) Under nitrogen conditions, 50 g of benzoxazine polyol and 10 g of phthalic anhydride are added to a flask, stirred and dispersed, and then 3% by mass of tetrabutyl titanate is added thereto, and the reaction is carried out at 140° C. for 24 hours. After the reaction is completed, the temperature is cooled to room temperature to obtain phthalic anhydride polyester polyol.

[0054] Step (4) Add 50g of vacuum dehydrated phthalic anhydride polyester polyol into a beaker, control the temperature to 55°C, stir for 25min, then add 40g of 4,4-diphenylmethane diisocyanate thereto, react at 65°C for 40min, then add 15g of 1,4-butanediol thereto, stir at 75°C for 2min, put into a nitrogen-protected 120°C oven, mature for 4h, and after completion, cool to room temperature to obtain a modified thermoplastic polyurethane.

[0055] Step (5) 100 g of polyvinyl chloride resin, 50 g of plasticizer TOTM, 0.1 g of initiator DCP, 0.8 g of antioxidant bisphenol A, 6 g of calcium zinc stabilizer, and 2 g of auxiliary crosslinking agent TAIC are added to a high-speed mixer, stirred and mixed for 10 minutes, and then 30 g of modified thermoplastic polyurethane is added thereto, and mixing is continued for 10 minutes, and the material is discharged to obtain a high temperature resistant polyvinyl chloride insulation material.

[0056] Comparative Example 1

[0057] The difference between this comparative example and Example 1 is that poly(hexamethylene adipate) is used in step (4) instead of phthalic anhydride polyester polyol.

[0058] Comparative Example 2

[0059] The difference between this comparative example and Example 1 is that step (5) does not contain modified thermoplastic polyurethane.

[0060] High temperature resistance test: Place the insulating material in a 150°C high temperature oven for 10 days, take it out, and test its tensile properties according to GB / T1040.1-2018. The change rate of tensile strength (%) = tensile strength after aging (MPa) / tensile strength before aging (MPa).

[0061] Table 1 Change rate of tensile strength of Examples 1-5 and Comparative Examples 1-2

[0062] Tensile strength change rate (%) Example 1 +17.2 Example 2 +19.1 Example 3 +20.5 Example 4 +22.4 Example 5 +22.0 Comparative Example 1 +15.4 Comparative Example 2 -12.45

[0063] As can be seen from Table 1, the change rate of tensile strength of Examples 1-5 and Comparative Example 1 is greater than that of Comparative Example 2. This is because, in Examples 1-5 and Comparative Example 1, more crosslinking density is generated during the thermal aging process, which increases the mechanical properties of the material, while Comparative Example 2 does not contain polyurethane, so its mechanical properties decrease with the progress of thermal aging, and the change rate of tensile strength of Examples 1-5 is greater than that of Comparative Example 1. This is because, in Examples 1-5, there are more rigid structures, which are better heat-resistant structures, and the benzoxazine structures therein can be open-loop crosslinked when heated, further improving the mechanical properties and high temperature resistance of the insulating material. Therefore, the change rate of tensile strength of Examples 1-5 is greater than that of Comparative Example 1. Therefore, the insulating material prepared by the present invention has better high temperature resistance.

[0064] The material is pressed into a 3mm thin sheet, and the mass is weighed to an accuracy of 0.001g. The thin sheet is placed on an abrasion tester and subjected to the same conditions and number of scraping. After the test, the sheet is removed and weighed. The difference in mass of the thin sheet before and after scraping is calculated as the amount of wear. The smaller the amount of wear, the better the wear resistance of the material.

[0065] Table 2 Wear amount of Examples 1-5 and Comparative Examples 1-2

[0066] Wear amount (g) Example 1 1.0019 Example 2 0.9891 Example 3 0.9804 Example 4 0.9724 Example 5 0.9753 Comparative Example 1 1.0595 Comparative Example 2 1.4824

[0067] It can be seen from Table 2 that the insulating material prepared by the present invention has good wear resistance.

[0068] For any technician familiar with the art, without departing from the scope of the technical solution of the present invention, the technical content disclosed above can be used to make many possible changes and modifications to the technical solution of the present invention, or modified into equivalent embodiments with equivalent changes. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention without departing from the content of the technical solution of the present invention should still fall within the scope of protection of the technical solution of the present invention.

Claims

1. A high temperature resistant polyvinyl chloride insulation material, characterized in that: The high temperature resistant polyvinyl chloride insulation material is composed of the following components by weight: 100 parts by weight of polyvinyl chloride resin, 30-50 parts by weight of plasticizer, 0.1-0.5 parts by weight of initiator, 0.5-1 parts by weight of antioxidant, 6-10 parts by weight of stabilizer, 2-5 parts by weight of co-crosslinking agent, and 10-30 parts by weight of modified thermoplastic polyurethane; The high temperature resistant polyvinyl chloride insulating material is prepared by the following method: Add polyvinyl chloride resin, plasticizer, initiator, antioxidant, stabilizer and cross-linking agent into a high-speed mixer, stir and mix for 10-30 minutes, then add modified thermoplastic polyurethane, continue mixing for 5-10 minutes, discharge and obtain high temperature resistant polyvinyl chloride insulation material.

2. The high temperature resistant polyvinyl chloride insulation material according to claim 1, characterized in that: The modified thermoplastic polyurethane is prepared by the following method: Step (1) adding p-chloroaniline and 35-40% formaldehyde aqueous solution into a flask containing dioxane solvent, stirring and mixing at 5-10° C. for 12-20 min, then adding bisphenol S thereto, reacting at 90-100° C. for 5-10 h, and after the reaction is completed, distilling under reduced pressure, washing with deionized water, and drying to obtain intermediate 1; Step (2) adding the intermediate 1 to a flask containing an ethanol solvent, stirring and dispersing, and then adding diethanolamine thereto, reacting at 95-110° C. for 10-18 hours. After the reaction is completed, vacuum rotary evaporation is performed to remove the solvent to obtain a benzoxazinyl polyol; Step (3) under nitrogen conditions, benzoxazine-based polyol and phthalic anhydride are added to a flask, stirred and dispersed, and then 3% by mass of tetrabutyl titanate is added thereto, and the reaction is carried out at 140-160° C. for 20-36 hours. After the reaction is completed, the temperature is lowered to room temperature to obtain phthalic anhydride polyester polyol; Step (4) adding the vacuum dehydrated phthalic anhydride polyester polyol into a beaker, controlling the temperature to 50-60°C, stirring for 20-30min, then adding 4,4-diphenylmethane diisocyanate thereto, reacting at 60-70°C for 30-50min, then adding 1,4-butanediol thereto, stirring at 70-80°C for 1-2min, placing in a nitrogen-protected 120°C oven, maturing for 3-5h, and then cooling to room temperature to obtain a modified thermoplastic polyurethane.

3. The high temperature resistant polyvinyl chloride insulation material according to claim 2, characterized in that: In the step (1), the mass ratio of p-chloroaniline to bisphenol S is 1-1.5:

1.

4. The high temperature resistant polyvinyl chloride insulation material according to claim 2, characterized in that: In the step (2), the mass ratio of the intermediate 1 to diethanolamine is 1:0.35-0.

5.

5. The high temperature resistant polyvinyl chloride insulation material according to claim 2, characterized in that: In the step (3), the mass ratio of benzoxazine-based polyol to phthalic anhydride is 2-5:

1.

6. The high temperature resistant polyvinyl chloride insulation material according to claim 2, characterized in that: In the step (4), the mass ratio of phthalic anhydride polyester polyol, 4,4-diphenylmethane diisocyanate, and 1,4-butanediol is 1:0.55-0.9:0.2-0.

35.

7. Use of the high temperature resistant polyvinyl chloride insulation material as claimed in claim 1 in the preparation of cables.

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