CN116041872A - Migration-precipitation-resistant and aging-resistant PVC cable material composition - Google Patents
Migration-precipitation-resistant and aging-resistant PVC cable material composition Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 30
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- 238000006243 chemical reaction Methods 0.000 claims description 12
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
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- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
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- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 claims description 2
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- 239000004800 polyvinyl chloride Substances 0.000 description 46
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- 239000004698 Polyethylene Substances 0.000 description 3
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- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
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- 239000008117 stearic acid Substances 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000005591 trimellitate group Chemical group 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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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
-
- 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
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Insulating Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A precipitation-resistant and aging-resistant PVC composition comprises the following components in parts by mass: 100 parts of medium-high polymerization degree PVC resin; 40-80 parts of high-functional plasticizer. It may further comprise a calcium zinc stabilizer: 6-9 parts; processing aid: 1.0 to 3.0 parts; an antioxidant: 0.5 to 1.0 part; and (3) a lubricant: 1.0 to 2.0 parts; and (3) filling: 10-20 parts, etc. The preparation method comprises the following steps: the materials are accurately weighed according to the formula, added into a high-speed mixer for mixing, and discharged into a cooler for cooling. Granulating the cooled material in a double-screw extruder to finally obtain the PVC composition. The obtained composition has the performances of migration and precipitation resistance, aging resistance, low temperature resistance, oil resistance, flame retardance and the like, and can be widely applied to the fields of automobile cables, charging pile cables and the like.
Description
Technical Field
The invention relates to the application field of PVC (polyvinyl chloride) compositions, in particular to a migration-precipitation-resistant and aging-resistant PVC cable material composition.
Background
In recent years, as cables are being subdivided into products such as safety fire-proof cables, marine cables, communication cables, data cables, servo control cables, encoder cables, charging pile cables, deep well survey cables, deep well submersible pump cables, etc., special requirements are being placed on the cables such as flexibility, high temperature resistance, cold resistance, wear resistance, oil resistance, solvent resistance, water resistance, acid and alkali resistance, etc. The PVC cable has the advantages of softness, wear resistance, high mechanical property, easiness in processing, high cost performance and the like, and is widely applied to places such as vehicles, ships, computers, offices, families and the like. However, the PVC cable has the problems that the added plasticizer is small in molecular weight and often migrates to the surface of the cable, and the wire is hardened and embrittled due to long-term precipitation and migration, so that the use requirement cannot be met, and potential safety hazards are caused. The polyester plasticizer developed in recent years can obviously improve the problem of plasticizer precipitation, the precipitation amount is obviously smaller, but there is still room for improvement in terms of precipitation resistance.
CN109735021a discloses a high-temperature-resistant oil-resistant flame-retardant PVC cable material for welding robots and a preparation method thereof, wherein the cable material comprises the following components in parts by weight: 50-100 parts of PVC resin with the polymerization degree of 1300, 0-50 parts of PVC resin with the polymerization degree of 2500, 20-30 parts of trimellitate, 2050 10-20 parts of polyester plasticizer, 5-10 parts of antimonous oxide, 8-12 parts of zinc borate, 5-10 parts of filler, 10-15 parts of aluminum hydroxide, 10-15 parts of calcium zinc heat stabilizer, 0.2-0.4 part of antioxidant 1076, 0.4-0.6 part of lubricant, 0.8-1.2 part of processing modifier P551J, 5-10 parts of ethylene-vinyl acetate-maleic anhydride copolymer, 20-30 parts of polyester elastomer and 1-3 parts of inorganic silicate clay. The PVC resin used in the invention is two PVC resins with larger polymerization degree difference, which can cause uneven plasticization and reduce the performance of the material. The ethylene-vinyl acetate-maleic anhydride copolymer has poor heat resistance, and is easy to adhere to the inner wall of processing equipment to influence molding processing. CN112552617a discloses a PVC cable material, its preparation method and application, the PVC cable material comprises the following components in parts by weight: 10-30 parts of PVC resin, 40-60 parts of filler, 10-20 parts of ethylene-vinyl acetate-carbon monoxide and micromolecular plasticizer, 2-5 parts of DOS and DOA, 0.1-2 parts of POE-g-MAH and EVA-g-MAH compatilizer, 1-2 parts of silane coupling agent and 1-3 parts of silicone lubricant. The invention can achieve higher performance, but DOS and DOA are small molecular plasticizers, have poor heat resistance and are easy to migrate and separate out.
In order to solve the problems, the invention prepares the migration-resistant precipitation-aging-resistant PVC cable material composition, and solves the problems of precipitation and poor heat resistance of the PVC cable.
Disclosure of Invention
The invention provides a PVC composition, which comprises the following components in parts by mass: 100 parts of medium-high polymerization degree PVC resin; 40-80 parts of high-functional plasticizer. It may further comprise a calcium zinc stabilizer: 6-9 parts; processing aid: 1.0 to 3.0 parts; an antioxidant: 0.5 to 1.0 part; and (3) a lubricant: 1.0 to 2.0 parts; and (3) filling: 10-20 parts, etc. Wherein the high-functional plasticizer is a random copolymer of methyl methacrylate, long-chain acrylic ester, acrylonitrile and styrene, and the mass ratio of methyl methacrylate/long-chain acrylic ester/acrylonitrile/styrene is 0.5-1.0/5.0-7.0/0.5-1.0/1.0-2.0; the long-chain acrylic ester is one or more of butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate and tetradecyl acrylate.
The preparation method of the high-function plasticizer comprises the following steps: at normal temperature, adding 5-8 parts of emulsifier potassium oleate, 50-70 parts of long-chain acrylic ester and 0.5-1.0 part of initiator into 100 parts of water in a reaction kettle, vacuumizing, filling nitrogen, uniformly stirring, heating to 60-70 ℃, initiating reaction, mixing 10-20 parts of styrene, 5-10 parts of acrylonitrile and 5-10 parts of methyl methacrylate, and continuously dripping into long-chain acrylic ester emulsion. 0.25 to 0.4 part of accelerator is added 4 to 5 hours after the initiation of temperature rise. After the temperature rise is initiated, the reaction lasts for 16 to 18 hours, and a terminator is added to terminate the reaction. And carrying out post-treatment steps such as demulsification, dehydration, drying and the like on the emulsion to obtain the high-function plasticizer.
The medium-to-high polymerization degree PVC resin is preferably produced by a suspension method, and the average polymerization degree is between 1000 and 3000, more preferably between 2000 and 2100.
The processing aid can be ACR processing aid and MBS processing aid; the antioxidant is two or three compound antioxidants of hindered phenol antioxidants, thioester antioxidants and phosphite antioxidants; the filler is organic montmorillonite with surface modified by double long chain alkyl ammonium, and the particle size is 1200-2000 meshes.
The preparation method of the PVC composition comprises the following steps: the materials are accurately weighed according to the formula, added into a high-speed mixer for mixing, and discharged into a cooler for cooling. Granulating the cooled material in a double-screw extruder to obtain the migration-resistant precipitation-resistant aging-resistant PVC composition.
The invention also provides application of the PVC composition or the PVC composition obtained by the preparation method in cable materials, especially in insulating layers of automobile cables, charging pile cables and the like, and the PVC composition has the performances of migration and precipitation resistance, aging resistance, low temperature resistance, oil resistance, flame retardance and the like.
The invention has the following beneficial technical effects:
(1) The PVC cable material composition with migration and precipitation resistance, aging resistance and low temperature resistance is prepared by blending medium-high polymerization degree PVC resin, high-functional plasticizer, stabilizer, processing aid, antioxidant, lubricant, filler and the like according to requirements, and then shearing and granulating through double screws. The PVC resin with the medium and high polymerization degree has the advantages of processability and mechanical properties, and has good PVC performance in combination with high and low polymerization degrees.
(2) The high-functional plasticizer is random copolymer of methyl methacrylate, long-chain acrylic ester, acrylonitrile and styrene. The high-functional plasticizer is a high-molecular weight solid-phase plasticizer, has excellent precipitation migration resistance, and the long-chain acrylic ester chain segment can endow the PVC special cable with flexibility and heat resistance; methyl methacrylate, acrylonitrile and styrene chain segments can endow the PVC phase with good compatibility, nonpolar solvent resistance and good processability to long-chain acrylate chain segments, and the final performance of the PVC special cable is ensured.
(3) The high-functional plasticizer and the ACR PVC processing aid have a synergistic effect, and the migration and precipitation resistance of the PVC cable material is improved together.
(4) The composite antioxidant of the antioxidant 1076, 626 and DLTDP and the organic montmorillonite with the surface modified double long chain alkyl ammonium have the effect of synergistically improving the thermo-oxidative aging resistance of the PVC cable.
Drawings
Fig. 1 is a schematic diagram of evaluation of plasticizer migration performance of PVC cable material composition. Five layers are arranged from top to bottom, an upper layer and a lower layer are glass plates, a middle layer is a PMMA plate (acrylic sheet), and two sample sheets to be tested are sandwiched between the glass plates and the PMMA plate, and are specifically shown in the figure. The test conditions were 70℃for 72 hours, and the amount of plasticizer transferred from the PVC film to the acrylic film was measured.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The components of the materials of the examples and the comparative examples of the migration-precipitation-resistant and aging-resistant PVC cable material compositions are weighed according to the formulations shown in tables 1 and 2. Wherein the medium-high polymerization degree PVC resin is produced by a suspension method, and the average polymerization degree is 2000-2100 (such as the polymerization degree is 2050); the high-functional plasticizer is a random copolymer of methyl methacrylate, long-chain acrylic ester, acrylonitrile and styrene, and the mass part ratio of the methyl methacrylate to the long-chain acrylic ester to the acrylonitrile to the styrene is 0.5-1.0/5.0-7.0/0.5-1.0/1.0-2.0; the preparation method of the high-functional plasticizer comprises the following steps: at normal temperature, adding 5-8 parts of emulsifier potassium oleate, 50-70 parts of long-chain acrylic ester and 0.5-1.0 part of initiator into 100 parts of water in a reaction kettle, vacuumizing, filling nitrogen, uniformly stirring, heating to 60-70 ℃, initiating reaction, mixing 10-20 parts of styrene, 5-10 parts of acrylonitrile and 5-10 parts of methyl methacrylate, continuously dropwise adding into the long-chain acrylic ester emulsion, and continuously dropwise adding for 10 hours. 0.25 to 0.4 part of accelerator is added 4 to 5 hours after the initiation of temperature rise. After the temperature rise is initiated, the reaction lasts for 16 to 18 hours, and a terminator is added to terminate the reaction. And adding demulsifier into the emulsion to demulsify, centrifugally dehydrating, and drying in a drying bed to obtain the high-function plasticizer. The treated montmorillonite is organic montmorillonite with surface modified by double long chain alkyl ammonium, and the particle size is 1200-2000 meshes.
Table 1 examples of PVC Cable compositions (parts by weight)
Table 2 comparative examples (parts by mass) of PVC Cable compositions
The materials are accurately weighed according to the formula, added into a high-speed mixer, mixed for 10 minutes at 110 ℃, discharged into a cooler and cooled to 30-40 ℃. Granulating the cooled material in a double-screw extruder to obtain the migration-resistant precipitation-resistant aging-resistant PVC cable material composition.
And (3) carrying out open mill, hot mould pressing and sample cutting on the prepared migration-precipitation-resistant aging-resistant PVC cable material composition. The plasticizer migration performance of the composition was evaluated under the conditions of 70℃for 72 hours, as shown in FIG. 1, and the amount of plasticizer migrating from the PVC film to the acrylic film was measured. The properties are shown in Table 3. The composition was tested for its thermo-oxidative ageing properties according to GB/T8815-2008 at a temperature of 115℃for 240 hours.
Table 3 PVC cable material composition examples and comparative examples properties
As can be seen from the data of the corresponding examples and comparative examples and the effects thereof in tables 1 to 3, the high-functional plasticizer can bring excellent migration resistance and thermal oxidative aging resistance to PVC cable materials; while the component 1 of comparative example contains a common polyester plasticizer, which is poor in migration resistance and thermal oxidative aging resistance. The high-functional plasticizer and the ACR PVC processing aid have a synergistic effect, so that the migration and precipitation resistance of the PVC cable material is improved; whereas comparative example 2 contains a fatty acid ester-based processing aid, it does not have a synergistic effect with a high-functional plasticizer, and is inferior in migration resistance and thermal oxidative aging resistance, as compared with example 2. The composite antioxidant of the antioxidants 1076, 626 and DLTDP and the organic montmorillonite with the surface modified double-long-chain alkyl ammonium have the effect of synergistically improving the thermal oxidative aging resistance of the PVC cable, and the combination of the composite antioxidant without the antioxidants 1076, 626 and DLTDP and the organic montmorillonite with the surface modified double-long-chain alkyl ammonium in the comparative example 4 and the comparative example 5 has poor thermal oxidative aging resistance. In the lubrication system, as can be seen from comparative example 3, the migration resistance and the thermal oxidative aging resistance of the stearic acid and the polyethylene wax are not as good as those of the oxidized polyethylene (AC-316A) and the polyethylene wax.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. A PVC composition comprising, in parts by mass: 100 parts of medium-high polymerization degree PVC resin; 40-80 parts of high-functional plasticizer.
2. The PVC composition of claim 1, wherein the high functional plasticizer is a random copolymer of methyl methacrylate, long chain acrylate, acrylonitrile, styrene, the mass ratio of methyl methacrylate/long chain acrylate/acrylonitrile/styrene being 0.5 to 1.0/5.0 to 7.0/0.5 to 1.0/1.0 to 2.0.
3. The PVC composition of claim 2, wherein the long chain acrylate is one or more of butyl acrylate, hexyl acrylate, octyl acrylate, lauryl acrylate, and tetradecyl acrylate.
4. A PVC composition according to any one of claims 1 to 3, wherein the high functional plasticizer is prepared by: at normal temperature, adding 5-8 parts of emulsifier potassium oleate, 50-70 parts of long-chain acrylic ester and 0.5-1.0 part of initiator into 100 parts of water in a reaction kettle, vacuumizing, filling nitrogen, uniformly stirring, heating to 60-70 ℃, initiating reaction, mixing 10-20 parts of styrene, 5-10 parts of acrylonitrile and 5-10 parts of methyl methacrylate, and continuously dripping into long-chain acrylic ester emulsion; 0.25 to 0.4 part of accelerator is added 4 to 5 hours after the initiation of temperature rise; after the temperature rise is initiated, the reaction lasts for 16 to 18 hours, and a terminator is added to terminate the reaction; and carrying out post-treatment steps such as demulsification, dehydration, drying and the like on the emulsion to obtain the high-function plasticizer.
5. PVC composition according to any one of claims 1 to 4, wherein the medium to high degree of polymerization PVC resin is preferably produced by suspension process, with an average degree of polymerization between 1000 and 3000, more preferably between 2000 and 2100.
6. The PVC composition of any one of claims 1 to 5, which may further comprise the following components, respectively: calcium zinc stabilizer: 6-9 parts; processing aid: 1.0 to 3.0 parts; an antioxidant: 0.5 to 1.0 part; and (3) a lubricant: 1.0 to 2.0 parts; and (3) filling: 10-20 parts.
7. The PVC composition according to claim 6, wherein the processing aid is ACR processing aid or MBS processing aid; the antioxidant is two or three compound antioxidants of hindered phenol antioxidants, thioester antioxidants and phosphite antioxidants.
8. The PVC composition according to claim 6, wherein the filler is an organic montmorillonite surface-modified with a double long-chain alkyl ammonium, and has a particle size of 1200 to 2000 meshes.
9. A process for the preparation of a PVC composition as in claims 1-8 comprising: accurately weighing the materials according to the formula, adding the materials into a high-speed mixer for mixing, discharging the materials into a cooler for cooling; granulating the cooled material in a double-screw extruder to obtain the PVC composition.
10. Use of a PVC composition according to any one of claims 1 to 8 or a PVC composition obtained by the process according to claim 9 for insulation of automotive cables, charging pile cables and the like.
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