PVC cable material resin and preparation method thereof

Abstract

The application relates to a PVC cable material resin and a preparation method thereof, and belongs to the technical field of PVC cable material resin compositions. In the prior art, a large amount of antioxidants needs to be added to improve the aging resistance of the PVC cable material resin, and on the other hand, more other additives need to be added to consider other performances of the PVC cable material resin, which influences other performances of the PVC cable material. The raw materials of the application include vinyl chloride monomers, water, a dispersing agent, an initiator and a terminator, and the application is characterized in that the raw materials further include 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butyl phenyl acrylate and trimethylolpropane triacrylate. The PVC resin produced by using the trimethylolpropane triacrylate, 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butyl phenyl acrylate and vinyl chloride monomers for copolymerization has excellent wear resistance and aging resistance.

Description

Technical Field

[0001] A PVC cable material resin and its preparation method are disclosed, belonging to the technical field of PVC cable material resin compositions. Background Technology

[0002] PVC cables are widely used in automotive, marine, computer, office, and home applications due to their advantages such as flexibility, abrasion resistance, high mechanical properties, ease of processing, and cost-effectiveness. However, soft PVC cables generally suffer from poor abrasion resistance and low aging resistance, requiring enhancement of these two properties for practical outdoor applications.

[0003] In the existing technology, in order to solve the problem of poor aging resistance of PVC cable materials, there is a technical solution of adding antioxidants. However, on the one hand, the amount of antioxidant added is not directly proportional to the final aging resistance performance, and a large amount needs to be added. On the other hand, it is also necessary to take into account other properties of PVC cable material resin, which requires the addition of more other additives. Excessive additives may affect other properties of PVC cable materials. At present, there is no effective method to significantly improve the aging resistance and wear resistance of PVC cable materials. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide a PVC cable material resin with high wear resistance and aging resistance, and a method for preparing the same.

[0005] The technical solution adopted by the present invention to solve its technical problem is: a PVC cable material resin, the raw materials of which include vinyl chloride monomer, water, dispersant, initiator and terminator, characterized in that: the raw materials also include 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate and trimethylolpropane triacrylate.

[0006] Cable materials made from PVC resin copolymerized with trimethylolpropane triacrylate, 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate and vinyl chloride monomer have excellent wear resistance and aging resistance.

[0007] Since the organic solid phase 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate is difficult to disperse in an aqueous suspension system, the introduction of trimethylolpropane triacrylate into the raw material can effectively improve the solubility and dispersion performance of 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate, making it easier to form a good mixed system. The two are added to the polymerization system simultaneously, which solves the problem of the difficulty in dispersing the solid phase 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate without introducing other solvents.

[0008] The functional monomer trimethylolpropane triacrylate exhibits a high reactivity ratio and is prone to self-polymerization, making it difficult to form copolymers with vinyl chloride monomers. 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate shows good compatibility with trimethylolpropane triacrylate, both preventing its self-polymerization and forming a uniform dispersion. This significantly improves the copolymerization efficiency of trimethylolpropane triacrylate, 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate with vinyl chloride monomers, achieving the overall effect of forming copolymers with vinyl chloride monomers. This fully utilizes the excellent aging resistance and wear resistance modification capabilities of 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate.

[0009] The preferred amount of water used is 1 to 2 times the amount of vinyl chloride monomer used.

[0010] Preferably, the amount of 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate is 0.1~0.5 wt% of the amount of vinyl chloride monomer.

[0011] Preferably, the amount of trimethylolpropane triacrylate used is 0.5 to 1 wt% of the amount of vinyl chloride monomer used.

[0012] Preferably, the weight ratio of 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate to trimethylolpropane triacrylate is 1:2~5.

[0013] Increasing the amount of these two functional monomers not only increases costs but also causes cross-linking, leading to processing difficulties and performance degradation. Excessive amounts of 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate will hinder the reaction. However, the 2-5 ratio of trimethylolpropane acrylate to 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate ensures the full utilization of the 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate.

[0014] Preferably, the dispersant is a composition of dispersant KH-20, dispersant L-9 and dispersant E50.

[0015] More preferably, the amounts of dispersant KH-20, dispersant L-9 and dispersant E50 are 0.03~0.04wt%, 0.03~0.04wt% and 0.02~0.03wt% of the amount of vinyl chloride monomer, respectively.

[0016] Preferably, the initiator is a combination of cumene peroxyneodecanate and bis(2-ethylhexyl) peroxydicarbonate.

[0017] More preferably, the amounts of cumyl peroxyneodecanate and bis(2-ethylhexyl) peroxydicarbonate are 0.005~0.025wt% and 0.04~0.05wt% of the amount of vinyl chloride monomer, respectively.

[0018] The preferred initiator system and initiator dosage are more suitable for the preparation of the above-mentioned PVC cable material resin, which helps to ensure the stability of the reaction process.

[0019] A method for preparing the above-mentioned PVC cable material resin is characterized by: mixing vinyl chloride monomer, water, dispersant, 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate and trimethylolpropane triacrylate, adding an initiator, heating to the reaction temperature in a sealed environment, and adding a terminator to terminate the reaction after the pressure drop reaches 0.07~0.13 MPa at the maximum pressure. The obtained material is then dehydrated and dried to obtain the PVC cable material resin.

[0020] The terminator can be diethylhydroxylamine or acetone thiourea.

[0021] Preferably, the reaction temperature is 42~48℃.

[0022] The optimal temperature ensures a mild reaction process, which is conducive to the formation of easily plasticized copolymers, resulting in copolymers with more uniform properties in all aspects.

[0023] The 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate and trimethylolpropane triacrylate are mixed and dissolved in water, and then mixed with vinyl chloride monomer and dispersant.

[0024] By shortening the possibility and time of individual contact between 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate and vinyl chloride monomer, the self-polymerization of 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate is further prevented, while improving the dispersion effect of 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate, thus fully utilizing the modifying effect of 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate.

[0025] Preferably, the raw materials are mixed and stirred for 15-30 minutes before the initiator is added.

[0026] Compared with existing technologies, the beneficial effects of this invention are as follows: the copolymerization of trimethylolpropane triacrylate, 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate with vinyl chloride monomer solves the problem of poor dispersion of solid-phase 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate without introducing other solvents. It can prevent the self-polymerization of trimethylolpropane triacrylate and form a uniform dispersion with it, significantly improving the copolymerization efficiency of trimethylolpropane triacrylate, 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate with vinyl chloride monomer, ultimately achieving the effect of forming a copolymer with vinyl chloride monomer. By fully utilizing the excellent aging and wear resistance modification capabilities of 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate, a PVC cable material resin with excellent wear and aging resistance is finally obtained. Detailed Implementation

[0027] The present invention will be further described below with reference to the embodiments, of which Embodiment 3 is the preferred embodiment of the present invention.

[0028] The following examples and comparative examples use the following methods for preparing PVC cable material resin:

[0029] 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate and trimethylolpropane triacrylate were dissolved in deionized water and mixed evenly. Then, together with vinyl chloride monomer and dispersant, they were added to a 5-liter polymerization reactor and stirred at room temperature for 15-30 minutes until evenly mixed. An initiator was added, and the reactor was sealed and heated to 42-48°C. After the reaction reached the maximum pressure, the pressure drop inside the reactor was recorded. When the pressure drop reached 0.1 MPa, a terminator was added to terminate the reaction. The obtained material was centrifuged and dehydrated to obtain a wet material. The wet material was dried in a 60°C oven to obtain PVC cable resin.

[0030] In the following examples and comparative examples, the dispersants included: KH-20 dispersant (polyvinyl alcohol with a degree of hydrolysis of 80%), L-9 dispersant (polyvinyl alcohol with a degree of hydrolysis of 70%), and E50 dispersant (hydroxypropyl methylcellulose ether).

[0031] Initiators include: EHP initiator (di(2-ethylhexyl) peroxide dicarbonate) and CNP initiator (isopropylphenyl peroxide neodecanoate).

[0032] Antioxidant 3052 is 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate.

[0033] Diethylhydroxylamine was chosen as the terminator. Example

[0034] A PVC cable material resin, wherein the raw materials of the PVC cable material resin in each embodiment are weighed according to the formulation in Table 1 below.

[0035] Table 1 Formulation of Examples

[0036] .

[0037] Comparative Example

[0038] A PVC cable material resin was prepared, and the raw materials for each comparative example of the PVC cable material resin were weighed according to the formulations in Table 2 below. In comparative examples 5 and 6, the antioxidants were replaced with those listed in Table 2, and in comparative example 6, trimethylolpropane triacrylate was replaced with phthalic acid diacrylate.

[0039] Table 2 Comparative Formulations

[0040] .

[0041] Performance testing

[0042] The performance of the PVC cable material resins obtained in the above embodiments and comparative examples was tested. The PVC cable material resins obtained in the above embodiments and comparative examples, per 100 parts, contained 8.0 parts calcium-zinc stabilizer, 55 parts DOP plasticizer, 10 parts fine calcium carbonate, 10 parts calcined clay, and 0.5 parts lubricant. The mixed cable material compound was milled on a two-roll mill at 162℃. The plasticizing roll wrapping time was tested, and the mixture was milled into sheets. The sheets were then hot-pressed into 2mm and 4mm soft sheets on a press. The 4mm soft sheet was used for abrasion resistance testing at a test temperature of 23±2℃. Test method for abrasion resistance: Weigh a 4mm flexible sheet to an accuracy of 0.0001g. Fix the sheet onto a reciprocating abrasion tester and perform a certain number of abrasion cycles (300 cycles) under the same conditions (no added weights, natural friction). Remove the sheet and weigh it. The weight difference (expressed in grams) is used to evaluate the abrasion resistance of the material; the smaller the difference, the better the abrasion resistance. A 2mm flexible sheet is used to test the aging performance of cable materials. The aging test is conducted according to GB / T 8815-2008 standard, with an aging chamber temperature of 125℃ for 240 hours and an oven air exchange rate of 8-20 times / hour. The test results for aging performance and abrasion resistance are shown in Table 3.

[0043] Table 3 Performance Test Results

[0044] .

[0045] As can be seen from the examples and comparative examples, the copolymer of trimethylolpropane triacrylate, 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate and vinyl chloride has excellent aging resistance and wear resistance; the combination of trimethylolpropane triacrylate and 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate can synergistically improve the aging resistance and wear resistance of the copolymer. The amount of dispersant has a significant impact on the uniformity and stability of the copolymerization reaction of trimethylolpropane triacrylate, 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate with vinyl chloride. In Example 6, the aging resistance and wear resistance of trimethylolpropane triacrylate and 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate at a weight ratio of 1:1 were lower than those of the examples with weight ratios of 1:2 to 5. In Example 7, when the amount of dispersant was low, the dispersibility of trimethylolpropane triacrylate and 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate in the vinyl chloride polymerization system was poor, resulting in poor copolymerization with vinyl chloride and consequently, poor aging resistance and wear resistance of the copolymer. Increasing the amount of these two functional monomers not only increases costs but also causes cross-linking, leading to processing difficulties and performance degradation.

[0046] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention in any other way. Any person skilled in the art may make changes or modifications to the above-disclosed technical content to create equivalent embodiments. However, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A PVC cable material resin, comprising vinyl chloride monomer, water, dispersant, initiator, and terminator as raw materials, characterized in that: The raw materials also include 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate and trimethylolpropane triacrylate; The amount of 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate used is 0.1~0.5 wt% of the amount of vinyl chloride monomer used; The amount of trimethylolpropane triacrylate used is 0.5~1wt% of the amount of vinyl chloride monomer used; The weight ratio of 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate to trimethylolpropane triacrylate is 1:2~5; The method for preparing the PVC cable material resin involves mixing vinyl chloride monomer, water, dispersant, 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate and trimethylolpropane triacrylate, adding an initiator, heating in a sealed environment to 42~48℃, reacting until the pressure drop reaches 0.07~0.13 MPa, adding a terminator to terminate the reaction, and obtaining the material which is then dehydrated and dried to obtain the PVC cable material resin.

2. The PVC cable material resin according to claim 1, characterized in that: The dispersant is a combination of dispersant KH-20, dispersant L-9 and dispersant E50.

3. The PVC cable material resin according to claim 2, characterized in that: The amounts of dispersant KH-20, dispersant L-9 and dispersant E50 are 0.03~0.04wt%, 0.03~0.04wt% and 0.02~0.03wt% of the amount of vinyl chloride monomer, respectively.

4. The PVC cable material resin according to claim 1, characterized in that: The initiator is a combination of cumene peroxyneodecanate and bis(2-ethylhexyl) peroxydicarbonate.

5. The PVC cable material resin according to claim 4, characterized in that: The amounts of cumyl peroxynedecanoate and bis(2-ethylhexyl) peroxydicarbonate are 0.005~0.025wt% and 0.04~0.05wt% of the amount of vinyl chloride monomer, respectively.

6. The PVC cable material resin according to claim 1, characterized in that: The 2-(2-hydroxy-3-tert-butyl-5-methylbenzyl)-4-methyl-6-tert-butylphenyl acrylate and trimethylolpropane triacrylate are mixed and dissolved in water, and then mixed with vinyl chloride monomer and dispersant.