PVC cable material special resin and its preparation method

Abstract

The application relates to a PVC cable material special resin and a preparation method thereof, and belongs to the technical field of cable sheath materials. The compression permanent deformation resistance of a PVC cable is poor, and the sheath produced by using the PVC resin is often concave when being extruded in the use process, which not only affects the appearance, but also reduces the protection performance. The raw materials of the PVC cable material special resin include, by weight, 0.1-10 parts of polyethylene glycol diacrylate, 0.1-10 parts of trimethylsilyl acrylate and 1300 parts of chloroethylene monomer. The polyethylene glycol diacrylate, the trimethylsilyl acrylate and the chloroethylene monomer are used to form a ternary monomer copolymer. The PVC cable material special resin has more excellent compression permanent deformation resistance, better cable protection effect and shorter plasticizing time.

Description

Technical Field

[0001] A special resin for PVC cable materials and its preparation method are disclosed, belonging to the technical field of cable sheath materials. 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, PVC cables have poor resistance to compression set. When the sheath made of PVC resin is subjected to compression during use, it often becomes dented, affecting both aesthetics and protective performance.

[0003] In existing technologies, to improve the compressive strength of cables, aggregates, inorganic materials, and other materials are generally added to PVC resin. On the one hand, this affects the plasticizing properties of the material itself, and on the other hand, most of the final resistance to permanent compression deformation is achieved by increasing the hardness of the PVC resin through the addition of the above materials. This does not meet the usage specifications of cable materials and results in poor deformation and expansion capabilities of the cable material.

[0004] Patent CN201510099100.9 discloses a PVC granule composition with low compression set, its preparation method and uses, but the process involves a large amount of fully cross-linked NBR, resulting in poor processing performance and poor ozone oxidation resistance of the NBR. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the shortcomings of the prior art and provide a special resin for PVC cable material with low compression set and short plasticizing time, and a method for preparing the same.

[0006] The technical solution adopted by the present invention to solve its technical problem is: a special resin for PVC cable material, characterized in that: the raw materials include 0.1 to 10 parts of polyethylene glycol diacrylate, 0.1 to 10 parts of trimethylsilyl acrylate and 1300 parts of vinyl chloride monomer by weight.

[0007] A ternary monomer copolymer was constructed using polyethylene glycol diacrylate, trimethylsilyl acrylate, and vinyl chloride monomer. The copolymers formed by polyethylene glycol diacrylate or trimethylsilyl acrylate alone with vinyl chloride monomer have a low internal 3D network density, resulting in little improvement in compression set resistance. The addition of trimethylsilyl acrylate not only enriches the internal network structure of the polyethylene glycol diacrylate / trimethylsilyl acrylate / vinyl chloride copolymer, improving compression set performance, but also, due to its high steric hindrance, imparts superior compression set resistance at high temperatures. Furthermore, the use of trimethylsilyl acrylate with vinyl chloride is difficult, as trimethylsilyl acrylate readily self-polymerizes; therefore, it must be used in combination with polyethylene glycol diacrylate to effectively form a ternary monomer copolymer and fully utilize its excellent compression set resistance.

[0008] Preferably, the raw materials include, by weight, 1.95 to 3.9 parts of polyethylene glycol diacrylate, 1.95 to 3.9 parts of trimethylsilyl acrylate, and 1300 parts of vinyl chloride monomer.

[0009] With the optimal weight distribution, it exhibits lower compression set and shorter plasticizing time.

[0010] Preferably, it also includes initiators diisobutyryl peroxide (IPO), cumyl peroxyneodecanate (CNP), and bis(2-ethylhexyl) peroxydicarbonate (EHP).

[0011] The preferred use of three initiators leverages their different half-lives: high-efficiency, medium-efficiency, and long-lasting initiators. IPO is a high-efficiency initiator, CNP is medium-efficiency, and EHP is long-lasting. The high-efficiency initiator rapidly initiates the polymerization reaction in the early stages but has almost no effect on later stages. The medium-efficiency initiator plays a major role in the middle stages of polymerization, while also contributing to later stages. The long-lasting initiator primarily ensures the reaction rate in the later stages of polymerization. The synergistic use of these three initiators ensures a stable and efficient polymerization reaction.

[0012] Further preferred, by weight, it comprises 0.26-0.39 parts of initiator diisobutyryl peroxide (IPO), 0.52-0.65 parts of initiator cumyl peroxyneodecanate (CNP), and 0.13-0.26 parts of initiator bis(2-ethylhexyl) peroxydicarbonate (EHP).

[0013] The preferred amount of initiator is slightly less in the early stage to quickly initiate the reaction; slightly more in the middle stage, because most of the reaction is completed in the middle period; and then a little long-acting initiator is added to avoid the problem of slow reaction or even stagnation in the later stage.

[0014] Preferably, it also includes 1900-2700 parts of water and 0.91-1.30 parts of dispersant.

[0015] More preferably, the dispersant comprises, by weight, 0.39 to 0.52 parts of dispersant KH-20, 0.26 to 0.39 parts of dispersant L-9, and 0.26 to 0.39 parts of dispersant E50.

[0016] The combination of three dispersants is mainly used to improve the morphology of resin particles, increase the porosity of resin particles, facilitate the absorption of additives by the resin, and improve the processing performance of the resin.

[0017] A method for preparing the above-mentioned PVC cable material resin, characterized in that: polyethylene glycol diacrylate and trimethylsilyl acrylate are each divided into 2-3 parts, and in each part of the above-mentioned PVC cable material resin, polyethylene glycol diacrylate and trimethylsilyl acrylate each account for 1 / 5 to 1 / 2 of their respective weights, and each part is added to the polymerization system at the following 2-3 times: 1) It is added to the reaction system together with the vinyl chloride monomer before the reaction begins; 2) When the initiator is added to the reaction system and the reaction is allowed to proceed for 0.5~1.5 hours; 3) When the initiator is added to the reaction system and the reaction is carried out for 1.5~2.5 hours.

[0018] When polyethylene glycol diacrylate and trimethylsilyl acrylate are added to the vinyl chloride polymerization system in 2-3 stages, the self-polymerization of polyethylene glycol diacrylate and trimethylsilyl acrylate can be effectively avoided. This allows for the successful copolymerization of polyethylene glycol diacrylate, trimethylsilyl acrylate, and vinyl chloride monomers, significantly improving the low compression set and plasticizing properties of the resin used in PVC cable materials. Preferably, the polyethylene glycol diacrylate and trimethylsilyl acrylate are each divided into 3 parts, and the weight of each part is 1 / 3 of the total weight of polyethylene glycol diacrylate and trimethylsilyl acrylate.

[0019] Adding the components evenly in three stages ensures a stable reaction state, forms a robust internal network structure, and improves resistance to permanent compression deformation.

[0020] Preferably, the three portions are added to the polymerization system at the following times: 1) It is added to the reaction system together with the vinyl chloride monomer before the reaction begins; 2) When the initiator is added to the reaction system and the reaction lasts for 1 hour; 3) When the initiator is added to the reaction system and the reaction is carried out for 2 hours.

[0021] Preferably, the process includes the following steps: polyethylene chloride monomer, water, dispersant, polyethylene glycol diacrylate and trimethylsilyl acrylate are mixed evenly; an initiator is added; the temperature is raised to 38-43°C; after reacting for 0.5-1.5 hours, polyethylene glycol diacrylate and trimethylsilyl acrylate are added with nitrogen gas; after reacting for 1.5-2.5 hours, polyethylene glycol diacrylate and trimethylsilyl acrylate are added with nitrogen gas; when the pressure inside the reactor drops to 0.08 MPa, a terminator is added to terminate the reaction; the mixture is then dried to obtain a special resin for PVC cable materials.

[0022] Compared with the prior art, the beneficial effects of the present invention are as follows: by combining polyethylene glycol diacrylate and trimethylsilyl acrylate with vinyl chloride monomer to form a ternary copolymer system, the final PVC cable material resin has better resistance to compression set and better cable protection effect, while not affecting the processing performance during copolymerization preparation or processing, and has a shorter plasticizing time. Detailed Implementation

[0023] 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.

[0024] In the following examples and comparative examples, PEGDA is polyethylene glycol diacrylate, and T3633 is trimethylsilyl acrylate.

[0025] In the following examples and comparative examples, the vinyl chloride monomer was a liquid monomer, which was added to the polymerization reactor by nitrogen pressure injection or vacuum suction. Example

[0026] A special resin for PVC cable materials, the raw materials and weight formulas used in each embodiment are shown in Table 1 below.

[0027] Table 1 Examples of resins for PVC cable materials with low compression set (parts by weight) .

[0028] A method for preparing a special resin for PVC cable materials is as follows: Accurately weigh the materials listed in Table 1 according to the formula. First, add vinyl chloride monomer, deionized water, 1 / 3 to 1 / 2 mass of polyethylene glycol diacrylate and trimethylsilyl acrylate, and three dispersants to a 5-liter polymerization reactor and stir at room temperature for 15 to 30 minutes. Then, add three initiators and heat to 38 to 43°C to begin the polymerization reaction. After one hour of reaction, pressurize 1 / 3 to 1 / 2 mass of polyethylene glycol diacrylate and trimethylsilyl acrylate into the reactor using nitrogen gas. After two hours of reaction, pressurize the remaining mass of polyethylene glycol diacrylate and trimethylsilyl acrylate into the reactor using nitrogen gas. Record the highest pressure inside the reactor thereafter. Continue the reaction until the pressure inside the reactor drops to 0.08 MPa, then add a terminator to terminate the reaction. Discharge the material into a centrifuge for centrifugal dehydration. Dry the dehydrated wet material in a 60°C oven. After drying, sieve the resin to obtain a special resin for low compression set PVC cable materials.

[0029] The polyethylene glycol diacrylate and trimethylsilyl acrylate are added as follows: according to the above-mentioned addition timing, polyethylene glycol diacrylate and trimethylsilyl acrylate are divided into three parts, each part being one-third the weight of polyethylene glycol diacrylate and trimethylsilyl acrylate in the formula, and added in batches according to the above-mentioned addition timing.

[0030] In Example 6, polyethylene glycol diacrylate and trimethylsilyl acrylate were each divided into two portions, each weighing half the total weight of the formulation, and added at the following times: 1) Add it to the polymerization reactor simultaneously with vinyl chloride monomer, deionized water and dispersant; 2) After adding the initiator, nitrogen gas is introduced during the reaction after 2 hours.

[0031] Comparative Example A special resin for PVC cable materials, the raw materials and weight formulas used in each comparative proportion are shown in Table 2 below.

[0032] Table 2 Comparative examples (parts by mass) of resins for PVC cable materials with low compression set. .

[0033] A method for preparing a special resin for PVC cable materials, according to the formulation in Table 2, adopts the same preparation method as in the examples. In Comparative Example 5, polyethylene glycol diacrylate and trimethylsilyl acrylate are added to the polymerization reactor simultaneously with vinyl chloride monomer, water, etc. before the reaction begins. In Comparative Example 6, after adding the initiator and heating to the target temperature, the polyethylene glycol diacrylate and trimethylsilyl acrylate are reacted for 1.5 hours, and then nitrogen gas is completely injected into the reaction system.

[0034] Performance testing The performance of the PVC cable material resins obtained in the above embodiments and comparative examples was tested: The obtained resin was mixed according to the cable material formula. The basic formula of the cable material is 100 parts PVC resin, 8.0 parts calcium-zinc stabilizer, 55 parts plasticizer DOP, 10 parts fine calcium carbonate, 10 parts calcined clay, and 0.5 parts lubricant. The mixed cable material 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 10mm thick flexible sheets on a press. Samples were prepared on the flexible sheets, and the compression set was tested according to GB / T 1683-2018 at a test temperature of 23±2℃. The test results of plasticizing time and compression set are shown in Table 3.

[0035] Table 3. Performance of PVC cable material resins with low compression set: Examples and comparative examples. .

[0036] As can be seen from the performance test results in the examples and Comparative Example Table 3, polyethylene glycol diacrylate and trimethylsilyl acrylate have a synergistic effect in improving the compression set resistance and plasticizing properties of the special resin. When polyethylene glycol diacrylate and trimethylsilyl acrylate are added to the vinyl chloride polymerization system in 2-3 stages, the self-polymerization of polyethylene glycol diacrylate and trimethylsilyl acrylate can be effectively avoided, thereby achieving good copolymerization of polyethylene glycol diacrylate, trimethylsilyl acrylate and vinyl chloride monomer, significantly improving the low compression set resistance and plasticizing properties of the special resin for PVC cable materials. In Comparative Example 3, when the dispersion performance of the polymerization dispersion system is weak, it will affect the dispersion effect of the comonomer, thus affecting the compression set resistance and plasticizing properties of the special resin. In Comparative Example 4, improper use of the initiator system will also affect the copolymerization effect of polyethylene glycol diacrylate, trimethylsilyl acrylate and vinyl chloride monomer, thereby affecting the compression set resistance and plasticizing properties of the special resin.

[0037] 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 resin specifically for PVC cable materials, characterized in that: The raw materials, by weight, include 0.1-10 parts of polyethylene glycol diacrylate, 0.1-10 parts of trimethylsilyl acrylate, and 1300 parts of vinyl chloride monomer; It also includes initiators and dispersants; The initiator comprises, by weight, 0.26-0.39 parts of initiator diisobutyryl peroxide, 0.52-0.65 parts of initiator cumyl peroxyneodecanate, and 0.13-0.26 parts of initiator bis(2-ethylhexyl) percarbonate. The dispersant comprises, by weight, 0.39–0.52 parts of dispersant KH-20, 0.26–0.39 parts of dispersant L-9, and 0.26–0.39 parts of dispersant E50; The method for preparing the PVC cable material resin involves dividing polyethylene glycol diacrylate and trimethylsilyl acrylate into 2-3 parts each, with each part weighing 1 / 5 to 1 / 2 of the respective weights of polyethylene glycol diacrylate and trimethylsilyl acrylate in the PVC cable material resin. Each part is added to the polymerization system at the following 2-3 specific times: 1) It is added to the reaction system together with the vinyl chloride monomer before the reaction begins; 2) When the initiator is added to the reaction system and the reaction is allowed to proceed for 0.5~1.5 hours; 3) When the initiator is added to the reaction system and the reaction is carried out for 1.5~2.5 hours.

2. The PVC cable material resin according to claim 1, characterized in that: The raw materials, by weight, include 1.95 to 3.9 parts of polyethylene glycol diacrylate, 1.95 to 3.9 parts of trimethylsilyl acrylate, and 1300 parts of vinyl chloride monomer.

3. The PVC cable material resin according to claim 1, characterized in that: It also includes initiators diisobutyryl peroxide, cumyl peroxyneodecanate, and bis(2-ethylhexyl) peroxydicarbonate.

4. The PVC cable material resin according to claim 1, characterized in that: It also includes 1900-2700 parts of water and 0.91-1.30 parts of dispersant.

5. The method for preparing the PVC cable material resin according to claim 1, characterized in that: The polyethylene glycol diacrylate and trimethylsilyl acrylate are each divided into 3 parts, and the weight of each part is 1 / 3 of the total weight of polyethylene glycol diacrylate and trimethylsilyl acrylate.

6. The method for preparing the PVC cable material resin according to claim 5, characterized in that: The three components were added to the polymerization system at the following times: 1) It is added to the reaction system together with the vinyl chloride monomer before the reaction begins; 2) When the initiator is added to the reaction system and the reaction lasts for 1 hour; 3) When the initiator is added to the reaction system and the reaction is carried out for 2 hours.

7. The method for preparing the PVC cable material resin according to claim 1, characterized in that: Includes the following steps: Vinyl chloride monomer, water, dispersant, polyethylene glycol diacrylate and trimethylsilyl acrylate are mixed evenly, an initiator is added, the temperature is raised to 38~43℃, and polyethylene glycol diacrylate and trimethylsilyl acrylate are added with nitrogen gas after 0.5~1.5h of reaction; polyethylene glycol diacrylate and trimethylsilyl acrylate are added with nitrogen gas after 1.5~2.5h of reaction; when the pressure in the reactor drops to 0.08MPa, a terminator is added to terminate the reaction, and the mixture is dried to obtain a special resin for PVC cable materials.