CN110903573A - PVC modified material and preparation method and application thereof - Google Patents
PVC modified material and preparation method and application thereof Download PDFInfo
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- CN110903573A CN110903573A CN201911274593.XA CN201911274593A CN110903573A CN 110903573 A CN110903573 A CN 110903573A CN 201911274593 A CN201911274593 A CN 201911274593A CN 110903573 A CN110903573 A CN 110903573A
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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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention provides a PVC modified material, a preparation method and application thereof. The PVC modified material comprises: PVC resin: 100 parts by weight; polyurethane: 20-40 parts by weight; primary plasticizer: 10-30 parts by weight; and (3) secondary plasticizer: 1-20 parts by weight; liquid flame retardant: 1-20 parts by weight; solid flame retardant: 20-50 parts by weight; cold resistance agent: 1-20 parts by weight; argil: 1-20 parts by weight. The PVC modified material disclosed by the invention not only has the performance completely meeting the related requirements of UL1581, but also has good mechanical property and electrical property, excellent cold resistance and flame retardance, and is more suitable for working in an ultralow temperature environment for a long time.
Description
Technical Field
The invention relates to a PVC modified material and a preparation method and application thereof, in particular to a PVC modified material with high cold resistance, high flame retardance and better flexibility in a low-temperature environment, belonging to the technical field of wires and cables.
Background
Polyvinyl chloride (PVC) resins are the second largest resin variety in the world today to polyethylene only. The PVC resin has the advantages of good rigidity, high strength, corrosion resistance, good electrical insulation, good processing performance and low price, and is widely applied to the cable industry. The PVC resin cable material is mainly used for sheath materials of various cables such as power cables, control cables, communication cables and the like. The PVC cable material is particles prepared by taking PVC resin as basic resin, adding a stabilizer, a plasticizer such as dioctyl phthalate, diisodecyl phthalate, dioctyl terephthalate, trioctyl trimellitate and the like, and an additive such as an inorganic filler such as calcium carbonate, an auxiliary agent, a lubricant and the like, and mixing, kneading and extruding the mixture.
PVC resin has poor stability to light and heat, has a softening point of only 80 ℃, and begins to decompose at 130 ℃. The cable often can cause cable burning by its self-heating, short circuit or conflagration etc. in the transmission electric energy process, causes the damage to the life property. At present, many high-flame-retardant PVC sheath materials exist in the field of domestic cables, but the high-flame-retardant PVC sheath materials are easy to carbonize during large-scale flame combustion, the materials are easy to fall off from the surfaces of the cables, and the high-flame-retardant PVC sheath materials cause great damage to the actual use of the cables and even interrupt the operation. And the cable can also produce a large amount of toxic flue gas, corrosive gas and can suffocate, be poisoned in the combustion process, not only cause very big harm and the polluted environment to fleeing person and rescue personnel.
Patent application CN107619560A discloses a high temperature resistant flame retardant PVC cable material, which is composed of the following components in parts by weight: 120-150 parts of polyvinyl chloride, 5-10 parts of magnesium aluminum alloy, 50-100 parts of flame retardant, 20-50 parts of dispersing agent and 5.2-10 parts of composite flame retardant synergist, wherein the flame retardant accounts for 25-31% of the raw materials by 50-100 parts, and although the flame retardant performance of the cable is improved, the mechanical property, the volume resistivity, the low temperature resistance and other properties of the cable are reduced due to the addition of a large amount of flame retardant.
Patent application CN105482296A discloses a light heat-resistant flame-retardant modified PVC resin compound cable material and a preparation method thereof, wherein the cable material is prepared from the following raw materials in parts by weight: 55-65 parts of PVC resin, 30-40 parts of ethylene-vinyl acetate copolymer, 0.01-0.02 part of tourmaline, 10-15 parts of expandable graphite, 5-8 parts of polytetramethylene glycol ether, 15-22 parts of aluminum silicate, 3-4 parts of eleostearic acid, 3-4 parts of hexamethyldisilazane, 22-30 parts of cotton pulp, 2-4 parts of zinc stearate, 14-18 parts of diethylene glycol dibenzoate, 8-10 parts of color masterbatch and 2-3 parts of auxiliary agent. However, the formula adds more expandable graphite in the resin base material, and because the expandable graphite is a conductor and is added into the cable material as a filler, the insulation performance of the cable material is greatly reduced, so that the risk of electric leakage, electric shock and the like is caused, and great potential safety hazard is caused.
Patent application CN110229443A discloses a flame retardant cable and a preparation method thereof, wherein the preparation method of the flame retardant cable comprises the following steps: twisting a conductive metal conductor on the periphery of the high-temperature resistant fiber, then coating an adhesive, and heating and curing to obtain a high-temperature resistant core; mixing polyvinyl chloride, nickel carbonate, expanded graphite, pentaerythritol, amino silicone oil, organic montmorillonite, magnesium hydroxide and ammonium polyphosphate, and drying to obtain a flame-retardant insulating blend; mixing polyvinyl chloride, dioctyl terephthalate, a solid calcium-zinc composite stabilizer, calcium carbonate, argil, tris (2-chloropropyl) phosphate and nano antimony trioxide, plasticizing, and vulcanizing to obtain a flame-retardant sheath blend material; extruding and wrapping the flame-retardant insulating blend on the outer layer of the high-temperature-resistant core to obtain a cable core; and extruding and wrapping the flame-retardant sheath blend on the outer layer of the cable core to obtain the flame-retardant cable. But the cold resistance and the low temperature resistance of the flame-retardant cable are poor.
Therefore, the research on a PVC modified material with excellent flame retardant performance, cold resistance and low temperature resistance is a technical problem to be solved.
Disclosure of Invention
Problems to be solved by the invention
In view of the technical problems in the prior art, for example: the PVC modified material has high-grade cold resistance and excellent self-extinguishing property, and is more suitable for cables working in an ultralow-temperature environment for a long time.
Furthermore, the invention also aims to provide a preparation method of the PVC modified material, which is simple and feasible, easily available in raw materials and mild in reaction conditions.
Means for solving the problems
The invention provides a PVC modified material, which comprises:
PVC resin: 100 parts by weight;
polyurethane: 20 to 40 parts by weight, preferably 25 to 35 parts by weight, more preferably 30 to 35 parts by weight;
primary plasticizer: 10 to 30 parts by weight, preferably 10 to 25 parts by weight, more preferably 15 to 20 parts by weight;
and (3) secondary plasticizer: 1 to 20 parts by weight, preferably 5 to 15 parts by weight, more preferably 10 to 15 parts by weight;
liquid flame retardant: 1 to 20 parts by weight, preferably 5 to 15 parts by weight, more preferably 5 to 10 parts by weight;
solid flame retardant: 20 to 50 parts by weight, preferably 25 to 45 parts by weight, more preferably 30 to 40 parts by weight;
cold resistance agent: 1 to 20 parts by weight, preferably 5 to 15 parts by weight, more preferably 5 to 10 parts by weight;
argil: 1 to 20 parts by weight, preferably 5 to 15 parts by weight, more preferably 5 to 10 parts by weight.
The PVC modified material provided by the invention has the polymerization degree of 1000-1500.
The PVC modifier comprises the main plasticizer, the main plasticizer and the plasticizer, wherein the main plasticizer comprises dioctyl sebacate; and/or
The secondary plasticizer includes a polyester plasticizer.
The PVC modified material comprises a liquid flame retardant, a flame retardant and a flame retardant, wherein the liquid flame retardant comprises tetrabromobenzene anhydride ester; and/or
The solid flame retardant comprises one or the combination of more than two of zinc borate, antimony trioxide and aluminum hydroxide.
The PVC modifying material provided by the invention is characterized in that the cold-resistant agent comprises ethylene/butyl acrylate/carbonyl copolymer.
The PVC modified material of the invention further comprises an additive, wherein the additive is added in an amount of 0.1-10 parts by weight, preferably 0.3-8 parts by weight, and more preferably 0.5-8 parts by weight.
The PVC modifier comprises a stabilizer and/or a lubricant; wherein the addition amount of the stabilizer is 1-10 parts by weight, preferably 2-8 parts by weight, more preferably 4-8 parts by weight; the lubricant is added in an amount of 0.1 to 1 part by weight, preferably 0.2 to 0.9 part by weight, more preferably 0.3 to 0.8 part by weight.
The PVC modifying material provided by the invention is characterized in that the stabilizer comprises a calcium zinc stabilizer; and/or
The lubricant comprises calcium stearate and/or PE wax.
The invention also provides a preparation method of the PVC modified material, which is characterized by comprising the step of mixing the components of the PVC modified material.
The invention also provides the application of the PVC modified material in preparing the cable.
ADVANTAGEOUS EFFECTS OF INVENTION
The PVC modified material disclosed by the invention not only has the performance completely meeting the related requirements of UL1581, but also has good mechanical property and electrical property, excellent cold resistance and flame retardance, and is more suitable for working in an ultralow temperature environment for a long time.
The preparation method of the PVC modified material is simple and feasible, the raw materials are easy to obtain, the reaction conditions are mild, and the PVC modified material is suitable for mass production.
Detailed Description
Various exemplary embodiments, features and aspects of the invention will be described in detail below. The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In other instances, methods, means, devices and steps which are well known to those skilled in the art have not been described in detail so as not to obscure the invention.
The invention provides a PVC modified material, which comprises:
PVC resin: 100 parts by weight;
polyurethane: 20 to 40 parts by weight, preferably 25 to 35 parts by weight, more preferably 30 to 35 parts by weight;
primary plasticizer: 10 to 30 parts by weight, preferably 10 to 25 parts by weight, more preferably 15 to 20 parts by weight;
and (3) secondary plasticizer: 1 to 20 parts by weight, preferably 5 to 15 parts by weight, more preferably 10 to 15 parts by weight;
liquid flame retardant: 1 to 20 parts by weight, preferably 5 to 15 parts by weight, more preferably 5 to 10 parts by weight;
solid flame retardant: 20 to 50 parts by weight, preferably 25 to 45 parts by weight, more preferably 30 to 40 parts by weight;
cold resistance agent: 1 to 20 parts by weight, preferably 5 to 15 parts by weight, more preferably 5 to 10 parts by weight;
argil: 1 to 20 parts by weight, preferably 5 to 15 parts by weight, more preferably 5 to 10 parts by weight.
The PVC modified material has better mechanical property and electrical property, has the greatest advantages of excellent cold resistance, low-temperature property and flame retardant property, and is more suitable for preparing cables working in an ultralow-temperature environment for a long time, such as: a cable operating in an environment below-50 ℃.
In the invention, in order to improve the low-temperature performance and the like of the PVC modified material, the PVC resin with the polymerization degree of 1000-1500 is used; preferably, the polymerization degree of the PVC resin is 1100-1450, more preferably 1200-1400, and even more preferably 1250-1350. When the polymerization degree of the PVC resin is in the range of 1000-1500, the PVC modified material with excellent low-temperature performance can be obtained. If the polymerization degree of the PVC resin is less than 1000, the required low-temperature performance is difficult to achieve, and if the polymerization degree of the PVC resin is higher than 1500, the flow performance of the PVC modified material is poor, and the production is difficult. For example, the PVC resin of the present invention may be a PVC resin having a trade name HG-1300 produced by Korea petrochemical company, a PVC resin having a trade name S-70 produced by Taizhou Co-Industrial Co., Ltd., a PVC resin having a trade name US-70 produced by Taizhou Co-Ltd., a PVC resin having a trade name HS-1300 produced by Qingdao Kaishao chemical Co., Ltd., or the like.
In the invention, the polyurethane can also play a role in resisting cold and low temperature. Specifically, in the present invention, the polyurethane is added in an amount of 20 to 40 parts by weight, preferably 25 to 35 parts by weight, and more preferably 30 to 35 parts by weight. When the amount of the added polyurethane is less than 20 parts by weight, the low temperature property is poor and the cold resistance grade cannot be improved, and when the amount of the added polyurethane is more than 40 parts by weight, the cold resistance cannot be improved and the cost is too high. For example, the polyurethane of the present invention may have a shore hardness of 80A to 90A.
In the present invention, the flexibility of the PVC modifier is also improved by using a plasticizer. Specifically, the plasticizer comprises a primary plasticizer and a secondary plasticizer, and the primary plasticizer and the secondary plasticizer have a synergistic effect, so that the low-temperature performance of the PVC modified material is further improved.
In the present invention, the primary plasticizer is added in an amount of 10 to 30 parts by weight, preferably 10 to 25 parts by weight, and more preferably 15 to 20 parts by weight. When the addition amount of the primary plasticizer is 10 to 30 parts by weight, the flexibility of the PVC modified material can be effectively improved, and the PVC modified material can have excellent low-temperature performance. When the addition amount of the main plasticizer is less than 10 parts by weight, the flexibility of the PVC modified material cannot be effectively improved, and the low-temperature performance of the PVC modified material is poor; when the addition amount of the primary plasticizer is more than 30 parts by weight, the flame retardant property of the PVC modifier may be affected.
Further, in the present invention, the secondary plasticizer is added in an amount of 1 to 20 parts by weight, preferably 5 to 15 parts by weight, more preferably 10 to 15 parts by weight. When the secondary plasticizer is added in an amount of 1 to 20 parts by weight, the flexibility of the PVC modifier can be further improved, and the PVC modifier can have more excellent low-temperature properties. When the addition amount of the secondary plasticizer is less than 1 part by weight, the flexibility of the PVC modified material cannot be effectively improved, and the low-temperature performance of the PVC modified material is poor; when the secondary plasticizer is added in an amount of more than 20 parts by weight, flame retardancy is affected and the cost is excessively high.
Specifically, in the present invention, the primary plasticizer includes dioctyl sebacate; and/or
The secondary plasticizer includes a polyester plasticizer, the viscosity of the polyester plasticizer may be 87 to 117mpa.s, and/or the density of the polyester plasticizer may be 0.968 to 0.985g/ml at 20 ℃, and/or the refractive index of the polyester plasticizer may be 1.479 to 1.485; for example: polyester plasticizers under the designation W-797-ZHI and/or TM 8-10.
The inventor of the present invention found that the use of dioctyl sebacate as a primary plasticizer enables the PVC modifier of the present invention to have more excellent technical effects than the use of dioctyl adipate as a primary plasticizer, for example, the low temperature performance of the PVC modifier can be further improved.
In the invention, the flame retardant is added to improve the flame retardant property of the PVC modified material. Specifically, the flame retardant comprises a liquid flame retardant and a solid flame retardant, and the liquid flame retardant and the solid flame retardant have a synergistic effect, so that the flame retardant property of the PVC modified material is further improved.
Further, the liquid flame retardant is added in an amount of 1 to 20 parts by weight, preferably 5 to 15 parts by weight, more preferably 5 to 10 parts by weight. When the addition amount of the liquid flame retardant is 1-20 parts by weight, the flame retardant property of the PVC modified material can be effectively improved. When the addition amount of the liquid flame retardant is less than 1 part by weight, the flame retardant effect is poor; when the amount of the liquid flame retardant added is more than 20 parts by weight, the cost is excessively high and the low temperature performance is affected.
Further, the solid flame retardant is added in an amount of 20 to 50 parts by weight, preferably 25 to 45 parts by weight, more preferably 30 to 40 parts by weight. When the addition amount of the solid flame retardant is 20-50 parts by weight, the flame retardant property of the PVC modified material can be further effectively improved. When the addition amount of the solid flame retardant is less than 20 parts by weight, the flame retardant effect is poor; when the solid flame retardant is added in an amount of more than 50 parts by weight, the flame retardancy cannot be further improved, and the low-temperature properties may be affected.
Specifically, the liquid flame retardant includes tetrabromobenzene anhydride ester; and/or
The solid flame retardant comprises one or the combination of more than two of zinc borate, antimony trioxide and aluminum hydroxide.
The invention has better flame retardant effect compared with halogen-free phosphorus flame retardant (such as brand K-520) and phosphate flame retardant (such as brand K-905).
In the invention, some cold-resistant agents can be properly added to further increase the low-temperature performance of the PVC modified material. In the present invention, the cold resistant agent is added in an amount of 1 to 20 parts by weight, preferably 5 to 15 parts by weight, more preferably 5 to 10 parts by weight. When the addition amount of the cold-resistant agent is less than 1 part by weight, the cold resistance is poor, namely the low-temperature performance of the PVC modified material is poor; when the amount of the cold-resistant agent added is more than 20 parts by weight, the cold-resistant property is not further improved and the cost is too high.
The inventor of the present invention finds that the ethylene/butyl acrylate/carbonyl copolymer has excellent cold resistance and can be used as the cold resistant agent of the present invention. Preferably, the ethylene/butyl acrylate/carbonyl copolymer is a terpolymer, the molecular weight of the ethylene/butyl acrylate/carbonyl copolymer is equivalent to that of PVC resin, the ethylene/butyl acrylate/carbonyl copolymer can be well compatible with the PVC resin, the low-temperature resistance of the ethylene/butyl acrylate/carbonyl copolymer can be improved by blending the ethylene/butyl acrylate/carbonyl copolymer with the PVC resin, the product quality of the PVC modified material is improved, the service life of the PVC modified material is prolonged, and the PVC modified material is endowed with excellent durability and low-temperature. The ethylene/butyl acrylate/carbonyl copolymer of the present invention has a melt flow index of 10 to 15g/10min measured at 190 ℃ under a 2.16kg load according to ASTM D1238-2004; and/or the Shore hardness of the ethylene/butyl acrylate/carbonyl copolymer is 65-75A.
The PVC modified material also contains argil. The compatibility of the system components can be well improved by adding the argil, and the plasticization is promoted. In the present invention, the amount of the kaolin added is 1 to 20 parts by weight, preferably 5 to 15 parts by weight, more preferably 5 to 10 parts by weight. If the addition amount of the kaolin is less than 1 part by weight, the compatibility of the system components is affected, and if the addition amount of the kaolin is more than 20 parts by weight, signal attenuation in communication transmission may result.
In some specific embodiments, the PVC modifier further comprises an additive, and the additive is added in an amount of 0.1 to 10 parts by weight, preferably 0.3 to 8 parts by weight, and more preferably 0.5 to 8 parts by weight.
Further, the additives include stabilizers and/or lubricants; wherein the addition amount of the stabilizer is 1-10 parts by weight, preferably 2-8 parts by weight, more preferably 4-8 parts by weight; the lubricant is added in an amount of 0.1 to 1 part by weight, preferably 0.2 to 0.9 part by weight, more preferably 0.3 to 0.8 part by weight. Wherein, the stabilizer can increase the thermal stability, the light stability and the like of the PVC modified material; lubricants can improve flow and processability.
Specifically, the stabilizers include calcium zinc stabilizers, such as those sold under the trade designations: CZ-302, CZ-9051, MC-90224, MC-92179, A-300P, A-590, etc.; the calcium-zinc stabilizer is synthesized by using calcium salt, zinc salt, lubricant, antioxidant and the like as main components through a compounding process. It can replace toxic stabilizer of lead-cadmium salt and organic tin, and has excellent heat stability, light stability, transparency and coloring power.
In the present invention, the lubricant comprises calcium stearate and/or PE wax.
The invention also provides a preparation method of the PVC modified material, which is characterized by comprising the step of mixing and granulating the components of the PVC modified material.
Specifically, the preparation method of the PVC modified material of the invention can comprise the following steps:
mixing PVC resin, polyurethane, a main plasticizer, an auxiliary plasticizer, a liquid flame retardant, a solid flame retardant, a cold-resistant agent and argil, and then carrying out color matching to obtain a premix;
extruding the premix by a double-screw extruder and/or a single-screw extruder, and then pelletizing to obtain particles;
and cooling, conveying and packaging the particles to obtain a finished product of the PVC modified material.
Specifically, the mixing temperature is 95-115 ℃ and the mixing time is 5-20min, so that the raw materials can be plasticized. The temperature of the double-screw extruder is 145-155 ℃, 150-160 ℃, 155-165 ℃, 160-170 ℃, 165-175 ℃, 170-180 ℃ and 165-175 ℃ in sequence; the temperature of the single-screw extruder is 115-125 ℃, 125-135 ℃ and 130-140 ℃ in sequence.
The invention also provides an application of the PVC modified material in preparing cables, the PVC modified material is particularly suitable for working in an ultralow temperature environment, and the ultralow temperature environment can be-50-75 ℃, for example: -50 ℃, -40 ℃, -30 ℃, -20 ℃, -10 ℃, 0 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃ and the like.
Examples
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. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
PVC resin powder: the manufacturer: a plastic group; the trade mark is as follows: and S-70.
Polyurethane: the manufacturer: basf, germany; the trade mark is as follows: c85a 10.
Polyester plasticizer: the manufacturer: DIC corporation; the trade mark is as follows: W-797-ZHI.
Calcium zinc stabilizer: the manufacturer: suzhou Langchan chemical Co., Ltd; the trade mark is as follows: CZ-302.
Ethylene/butyl acrylate/carbonyl copolymer: the manufacturer: DuPont corporation; the trade mark is as follows: HP-661.
Example 1
The cold-resistant flame-retardant PVC modified material for the cable is prepared from the following raw materials in parts by weight: 100 parts of PVC resin powder, 30 parts of polyurethane, 10 parts of polyester plasticizer, 20 parts of dioctyl sebacate, 8 parts of tetrabromophthalic anhydride ester, 5 parts of calcium-zinc stabilizer, 12.5 parts of zinc borate, 12 parts of antimony trioxide, 7.5 parts of aluminum hydroxide, 0.3 part of calcium stearate, 0.4 part of PE wax, 8 parts of ethylene/butyl acrylate/carbonyl copolymer and 5 parts of argil.
The preparation method of the PVC modified material of the example 1 can comprise the following steps:
the components of example 1 were mixed at 105 ℃ for 10min to plasticize the raw materials to give a premix;
extruding the premix by a double-screw extruder and a single-screw extruder in sequence, and then pelletizing to obtain particles; wherein the temperature of the double-screw extruder is 150-155-160-165-170-175-170 ℃, and the temperature of the single-screw extruder is 120-130-135 ℃;
and cooling, conveying and packaging the particles to obtain a finished product of the PVC modified material.
Example 2
An oil-resistant flame-retardant PVC modified material for cables is prepared from the following raw materials in parts by weight: 100 parts of PVC resin powder, 35 parts of polyurethane, 10 parts of polyester plasticizer, 15 parts of dioctyl sebacate, 8 parts of tetrabromophthalic anhydride ester, 5 parts of calcium-zinc stabilizer, 12.5 parts of zinc borate, 12 parts of antimony trioxide, 7.5 parts of aluminum hydroxide, 0.3 part of calcium stearate, 0.4 part of PE wax, 8 parts of ethylene/butyl acrylate/carbonyl copolymer and 5 parts of argil.
The preparation method of the PVC modified material of the embodiment 2 can comprise the following steps:
the components of example 2 were mixed at 105 ℃ for 10min to plasticize the raw materials to give a premix;
extruding the premix by a double-screw extruder and a single-screw extruder in sequence, and then pelletizing to obtain particles; wherein the temperature of the double-screw extruder is 150-155-160-165-170-175-170 ℃, and the temperature of the single-screw extruder is 120-130-135 ℃;
and cooling, conveying and packaging the particles to obtain a finished product of the PVC modified material.
Example 3
An oil-resistant flame-retardant PVC modified material for cables is prepared from the following raw materials in parts by weight: 100 parts of PVC resin powder, 33 parts of polyurethane, 15 parts of polyester plasticizer, 17 parts of dioctyl sebacate, 5 parts of tetrabromophthalic anhydride ester, 5 parts of calcium-zinc stabilizer, 12.5 parts of zinc borate, 12 parts of antimony trioxide, 7.5 parts of aluminum hydroxide, 0.3 part of calcium stearate, 0.4 part of PE wax, 8 parts of ethylene/butyl acrylate/carbonyl copolymer and 5 parts of argil.
The preparation method of the PVC modified material of the embodiment 3 can comprise the following steps:
the components of example 3 were mixed at 105 ℃ for 10min to plasticize the raw materials to give a premix;
extruding the premix by a double-screw extruder and a single-screw extruder in sequence, and then pelletizing to obtain particles; wherein the temperature of the double-screw extruder is 150-155-160-165-170-175-170 ℃, and the temperature of the single-screw extruder is 120-130-135 ℃;
and cooling, conveying and packaging the particles to obtain a finished product of the PVC modified material.
Example 4
An oil-resistant flame-retardant PVC modified material for cables is prepared from the following raw materials in parts by weight: 100 parts of PVC resin powder, 33 parts of polyurethane, 15 parts of polyester plasticizer, 17 parts of dioctyl sebacate, 10 parts of tetrabromophthalic anhydride ester, 5 parts of calcium-zinc stabilizer, 12.5 parts of zinc borate, 12 parts of antimony trioxide, 7.5 parts of aluminum hydroxide, 0.3 part of calcium stearate, 0.4 part of PE wax, 8 parts of ethylene/butyl acrylate/carbonyl copolymer and 10 parts of argil.
The preparation method of the PVC modified material of the embodiment 4 can comprise the following steps:
the components of example 4 were mixed at 105 ℃ for 10min to plasticize the raw materials to give a premix;
extruding the premix by a double-screw extruder and a single-screw extruder in sequence, and then pelletizing to obtain particles; wherein the temperature of the double-screw extruder is 150-155-160-165-170-175-170 ℃, and the temperature of the single-screw extruder is 120-130-135 ℃;
and cooling, conveying and packaging the particles to obtain a finished product of the PVC modified material.
Comparative example 1
The cold-resistant flame-retardant PVC modified material for the cable is prepared from the following raw materials in parts by weight: 100 parts of PVC resin powder, 30 parts of polyurethane, 10 parts of polyester plasticizer, 24 parts of dioctyl sebacate, 5 parts of calcium-zinc stabilizer, 12.5 parts of zinc borate, 12 parts of antimony trioxide, 7.5 parts of aluminum hydroxide, 0.3 part of calcium stearate, 0.4 part of PE wax, 8 parts of ethylene/butyl acrylate/carbonyl copolymer and 5 parts of argil.
The preparation method of the PVC modifier of comparative example 1 may include the following steps:
mixing the components of comparative example 1 at 105 ℃ for 10min to plasticize the raw materials to obtain a premix;
extruding the premix by a double-screw extruder and a single-screw extruder in sequence, and then pelletizing to obtain particles; wherein the temperature of the double-screw extruder is 150-155-160-165-170-175-170 ℃, and the temperature of the single-screw extruder is 120-130-135 ℃;
and cooling, conveying and packaging the particles to obtain a finished product of the PVC modified material.
Comparative example 2
The cold-resistant flame-retardant PVC modified material for the cable is prepared from the following raw materials in parts by weight: 100 parts of PVC resin powder, 30 parts of polyurethane, 30 parts of dioctyl sebacate, 8 parts of tetrabromophthalic anhydride ester, 5 parts of calcium-zinc stabilizer, 12.5 parts of zinc borate, 12 parts of antimony trioxide, 7.5 parts of aluminum hydroxide, 0.3 part of calcium stearate, 0.4 part of PE wax, 8 parts of ethylene/butyl acrylate/carbonyl copolymer and 5 parts of argil.
The preparation method of the PVC modifier of comparative example 2 may include the following steps:
mixing the components of comparative example 2 at 105 ℃ for 10min to plasticize the raw materials to obtain a premix;
extruding the premix by a double-screw extruder and a single-screw extruder in sequence, and then pelletizing to obtain particles; wherein the temperature of the double-screw extruder is 150-155-160-165-170-175-170 ℃, and the temperature of the single-screw extruder is 120-130-135 ℃;
and cooling, conveying and packaging the particles to obtain a finished product of the PVC modified material.
Comparative example 3
The cold-resistant flame-retardant PVC modified material for the cable is prepared from the following raw materials in parts by weight: 100 parts of PVC resin powder, 30 parts of polyurethane, 10 parts of polyester plasticizer, 24 parts of dioctyl sebacate, 8 parts of tetrabromophthalic anhydride ester, 5 parts of calcium-zinc stabilizer, 12.5 parts of zinc borate, 12 parts of antimony trioxide, 7.5 parts of aluminum hydroxide, 0.3 part of calcium stearate, 0.4 part of PE wax and 5 parts of argil.
The preparation method of the PVC modifier of comparative example 3 can comprise the following steps:
mixing the components of comparative example 3 at 105 ℃ for 10min to plasticize the raw materials to obtain a premix;
extruding the premix by a double-screw extruder and a single-screw extruder in sequence, and then pelletizing to obtain particles; wherein the temperature of the double-screw extruder is 150-155-160-165-170-175-170 ℃, and the temperature of the single-screw extruder is 120-130-135 ℃;
and cooling, conveying and packaging the particles to obtain a finished product of the PVC modified material.
Comparative example 4
The cold-resistant flame-retardant PVC modified material for the cable is prepared from the following raw materials in parts by weight: 100 parts of PVC resin powder, 10 parts of polyester plasticizer, 35 parts of dioctyl sebacate, 8 parts of tetrabromophthalic anhydride ester, 5 parts of calcium-zinc stabilizer, 12.5 parts of zinc borate, 12 parts of antimony trioxide, 7.5 parts of aluminum hydroxide, 0.3 part of calcium stearate, 0.4 part of PE wax, 8 parts of ethylene/butyl acrylate/carbonyl copolymer and 5 parts of argil.
The preparation method of the PVC modifier of comparative example 4 may include the following steps:
mixing the components of comparative example 4 at 105 ℃ for 10min to plasticize the raw materials to obtain a premix;
extruding the premix by a double-screw extruder and a single-screw extruder in sequence, and then pelletizing to obtain particles; wherein the temperature of the double-screw extruder is 150-155-160-165-170-175-170 ℃, and the temperature of the single-screw extruder is 120-130-135 ℃;
and cooling, conveying and packaging the particles to obtain a finished product of the PVC modified material.
Performance testing
The examples were subjected to the test methods shown in Table 1 below, and the results are shown in Table 2 below.
TABLE 1
TABLE 2
As can be seen from Table 2, the PVC modified materials of examples 1-4 of the present application are excellent in various properties.
The comparative examples were subjected to the same test methods as in examples, and the results are shown in Table 3 below.
TABLE 3
As can be seen from Table 3, comparative example 1 does not contain a liquid flame retardant, but has an oxygen index of only 29 and a CMR hard fire test of more than 3.66, failing to meet the industrial requirements.
Comparative example 2, which does not contain a secondary plasticizer, has a pass rate of only 10/30 at the impact catalysis temperature and is poor in low-temperature performance.
Comparative example 3 does not contain a cold resistance agent, and the pass rate at the impact catalysis temperature is only 20/30, and the low temperature performance is poor.
Comparative example 4, which does not contain polyurethane, has a pass rate of only 25/30 at the impact catalysis temperature and is poor in low-temperature performance.
As can be seen from the data in the table, the performance of each PVC modified material obtained in the example completely meets the requirement in UL1581, and the cold resistance and flame retardance of each modified material are better than those of the conventional PVC modified material and are better than those of the comparative example. In practical application, the cold-resistant and flame-retardant performance of the PVC modified material is completely higher than that of the conventional PVC modified material, and the market demand is completely met.
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A PVC modifier is characterized by comprising:
PVC resin: 100 parts by weight;
polyurethane: 20 to 40 parts by weight, preferably 25 to 35 parts by weight, more preferably 30 to 35 parts by weight;
primary plasticizer: 10 to 30 parts by weight, preferably 10 to 25 parts by weight, more preferably 15 to 20 parts by weight;
and (3) secondary plasticizer: 1 to 20 parts by weight, preferably 5 to 15 parts by weight, more preferably 10 to 15 parts by weight;
liquid flame retardant: 1 to 20 parts by weight, preferably 5 to 15 parts by weight, more preferably 5 to 10 parts by weight;
solid flame retardant: 20 to 50 parts by weight, preferably 25 to 45 parts by weight, more preferably 30 to 40 parts by weight;
cold resistance agent: 1 to 20 parts by weight, preferably 5 to 15 parts by weight, more preferably 5 to 10 parts by weight;
argil: 1 to 20 parts by weight, preferably 5 to 15 parts by weight, more preferably 5 to 10 parts by weight.
2. The PVC modifier according to claim 1, wherein the degree of polymerization of the PVC resin is 1000-1500.
3. The PVC modifier according to claim 1 or 2, characterized in that the primary plasticizer comprises dioctyl sebacate; and/or
The secondary plasticizer includes a polyester plasticizer.
4. The PVC modifier according to any one of claims 1 to 3, wherein the liquid flame retardant comprises tetrabromobenzene anhydride ester; and/or
The solid flame retardant comprises one or the combination of more than two of zinc borate, antimony trioxide and aluminum hydroxide.
5. The PVC modifier according to any one of claims 1 to 4, wherein the cold-resistant agent comprises an ethylene/butyl acrylate/carbonyl copolymer.
6. The PVC modifier according to any one of claims 1 to 5, further comprising an additive in an amount of 0.1 to 10 parts by weight, preferably 0.3 to 8 parts by weight, more preferably 0.5 to 8 parts by weight.
7. The PVC modifier of claim 6, wherein the additives comprise stabilizers and/or lubricants; wherein the addition amount of the stabilizer is 1-10 parts by weight, preferably 2-8 parts by weight, more preferably 4-8 parts by weight; the lubricant is added in an amount of 0.1 to 1 part by weight, preferably 0.2 to 0.9 part by weight, more preferably 0.3 to 0.8 part by weight.
8. The PVC modifier of claim 7, wherein the stabilizer comprises a calcium zinc stabilizer; and/or
The lubricant comprises calcium stearate and/or PE wax.
9. The preparation method of the PVC modifier according to any one of claims 1 to 8, which comprises the step of mixing and granulating the components of the PVC modifier.
10. Use of the PVC modifier according to any one of claims 1 to 8 for the preparation of cables.
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| CN112321983A (en) * | 2020-10-13 | 2021-02-05 | 浙江万马高分子材料集团有限公司 | Sheath rubber material for 105 ℃ CMP (chemical mechanical polishing) level security cable and preparation method thereof |
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