CN110951189B - Polyvinyl chloride material and preparation method thereof - Google Patents
Polyvinyl chloride material and preparation method thereof Download PDFInfo
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- CN110951189B CN110951189B CN201911276882.3A CN201911276882A CN110951189B CN 110951189 B CN110951189 B CN 110951189B CN 201911276882 A CN201911276882 A CN 201911276882A CN 110951189 B CN110951189 B CN 110951189B
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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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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 discloses a polyvinyl chloride material and a preparation method thereof, wherein the polyvinyl chloride material comprises the following components in parts by weight: 100 parts of PVC resin, 10-30 parts of plasticizer A, 5-20 parts of plasticizer B, 5-20 parts of plasticizer C, 5-15 parts of plasticizer D, 10-25 parts of flame retardant A, 15-30 parts of flame retardant B, 10-20 parts of flame retardant C, 12-20 parts of heat stabilizer, 10-25 parts of modifier, 1.0-2.5 parts of processing aid and 0.8-2.0 parts of antioxidant; the obtained polyvinyl chloride material has the balance of high temperature resistance, cold resistance and flame retardance, can resist the high temperature of 125 ℃ and the low temperature of-50 ℃, has an oxygen index of more than 40, can be used in extremely hot and cold environments, and has excellent flame retardance.
Description
Technical Field
The invention relates to the technical field of wire and cable materials, in particular to a high-temperature-resistant cold-resistant high-flame-retardant polyvinyl chloride material and a preparation method thereof.
Background
At present, polyvinyl chloride is widely applied to various electric wires in the electric wire and cable industry due to excellent performance, high production efficiency, low price and the like. However, the common polyvinyl chloride plastic has cold resistance and high temperature resistance which cannot support the use in special environments, such as regions with extremely cold temperature as low as-50 ℃ in winter, or the temperature of the positions for motors, engines and the like in hot weather in summer can reach 125 ℃. Therefore, the cold resistance and high temperature resistance of the polyvinyl chloride cable material are required to be further improved.
In addition, by researching a plurality of fire accident examples, the results show that: except natural disasters, most of fires are caused by poor flame retardant property of electrical appliance materials and building materials. Although the PVC material contains chlorine element and has certain flame retardant property, the PVC material still cannot reach the flame retardant standard as a cable material. The existing cold-resistant polyvinyl chloride material mainly resists low temperature of minus 40 ℃, the high-temperature resistant polyvinyl chloride mainly resists high temperature of 90 ℃, the oxygen index of the material can only reach 30-32, and the material cannot meet the requirements of class A of bundled combustion.
Therefore, how to provide a polyvinyl chloride material with excellent performance and a preparation method thereof is a problem which needs to be solved urgently by the technical personnel in the field.
Disclosure of Invention
In view of the above, the invention provides a high temperature resistant, cold resistant and high flame retardant polyvinyl chloride material, and a preparation method and an application thereof, the prepared polyvinyl chloride material has balance of high temperature resistance, cold resistance and flame retardant property, can resist high temperature of 125 ℃ and low temperature of-50 ℃, has an oxygen index of more than 40, can be used in extremely hot and cold environments, has excellent flame retardant property, and can pass a bundled combustion type A test.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high-temperature-resistant cold-resistant high-flame-retardant polyvinyl chloride material comprises the following components in parts by weight:
the beneficial effects of the preferred technical scheme are as follows: the prepared polyvinyl chloride material has the balance of high temperature resistance, cold resistance and flame retardance, can resist the high temperature of 125 ℃ and the low temperature of-50 ℃, has an oxygen index of more than 40, can be used in extremely hot and extremely cold environments, has excellent flame retardance, and can pass a bundling combustion A-type test.
Preferably, the PVC resin is one or two of PVC resins with 1100-1800 polymerization degrees.
The beneficial effects of the preferred technical scheme are as follows: the PVC resin adopted by the invention has excellent processing performance, is easy to carry out industrial production, and has excellent mechanical performance, so that the finally prepared polyvinyl chloride material has excellent mechanical performance, and has wide application prospect.
Preferably, the plasticizer A is phthalate, the plasticizer B is phosphate, the plasticizer C is dipentaerythritol ester, and the plasticizer D is dioctyl sebacate.
The beneficial effects of the preferred technical scheme are as follows: the plasticizer A, the plasticizer B and the plasticizer C adopted by the invention can be matched with each other and used in combination with the stabilizer, so that the high temperature resistance and cold resistance of the polyvinyl chloride material can be obviously improved, and the effects of resisting 125 ℃ high temperature and-50 ℃ low temperature are achieved.
Preferably, the flame retardant A is antimony trioxide, the flame retardant B is modified magnesium hydroxide, and the flame retardant C is a phosphorus-nitrogen composite flame retardant.
The beneficial effects of the preferred technical scheme are as follows: the flame retardant A, the flame retardant B and the flame retardant C are compounded for use, so that the oxygen index of the finally obtained polyvinyl chloride material is over 40, and the prepared cable can pass the bundled combustion A-type test of IEC 60332-3 standard.
Preferably, the heat stabilizer is a calcium-zinc composite heat stabilizer.
The beneficial effects of the preferred technical scheme are as follows: the heat stabilizer, the plasticizer A, the plasticizer B and the plasticizer C adopted by the invention can be matched with each other, so that the high temperature resistance of the polyvinyl chloride material can be obviously improved, and the effect of resisting the high temperature of 125 ℃ is achieved.
Preferably, the modifier is one or two of chlorinated polyethylene and acrylate copolymer.
The beneficial effects of the preferred technical scheme are as follows: the modifier adopted by the invention is matched with the raw material, so that the processability and the low-temperature resistance of the composite material can be improved.
Preferably, the processing aid is a combination of two or more of calcium stearate, stearic acid and polyethylene wax.
The beneficial effects of the preferred technical scheme are as follows: the processing aid adopted by the invention can improve the processability of the raw material.
Preferably, the antioxidant is one or a combination of two of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester (antioxidant 1010) and tris (2, 4-di-tert-butylphenyl) phosphite (antioxidant 168).
The beneficial effects of the preferred technical scheme are as follows: the antioxidant is adopted, so that the antioxidant performance of the material can be improved, and the high-temperature resistance of the material can be enhanced.
The invention also provides a preparation method of the high-temperature-resistant cold-resistant high-flame-retardant polyvinyl chloride material, which comprises the following steps:
(1) weighing the raw materials according to the high-temperature-resistant cold-resistant high-flame-retardant polyvinyl chloride material for later use;
(2) uniformly mixing PVC resin, a plasticizer A, a plasticizer B, a plasticizer C, a plasticizer D, a flame retardant A, a flame retardant B, a flame retardant C and a heat stabilizer, controlling the temperature to 125-135 ℃ and mixing for 8-15 min; adding a modifier, a processing aid and an antioxidant, and mixing for 30-90 s to obtain a uniform mixture;
(3) and extruding and granulating the mixture, and drying the obtained plastic to obtain the polyvinyl chloride material.
Further preferably, the mixture is added into a high-speed kneader in the step (2) to be stirred and mixed, and the temperature of a jacket of the mixer is set to 125-135 ℃.
Further preferably, the winning mixture in the step (3) is added into a double-stage extrusion granulator consisting of a double screw and a single screw, the heating temperature of each section of the double screw granulator is uniformly increased from 120-150 ℃, the heating temperature of each section of the single screw granulator is uniformly increased from 90-150 ℃, and the temperature of a machine head is 150 ℃.
Preferably, the drying in the step (3) is drying in a drying barrel at 50-60 ℃ for 1 h.
The beneficial effects of the preferred technical scheme are as follows: the invention can obtain the polyvinyl chloride material with uniform particles and good plasticization, and the performance of the polyvinyl chloride material has the balance of high temperature resistance, cold resistance and flame retardance.
The invention also provides application of the high-temperature-resistant cold-resistant high-flame-retardant polyvinyl chloride material in a cable material.
The beneficial effects of the preferred technical scheme are as follows: the cable made of the high-temperature-resistant cold-resistant high-flame-retardant polyvinyl chloride material disclosed by the invention can be used in extremely hot and cold environments, has excellent flame-retardant performance and can pass a bundled combustion A-type test.
According to the technical scheme, compared with the prior art, the invention discloses a high-temperature-resistant cold-resistant high-flame-retardant polyvinyl chloride material, and a preparation method and application thereof, and the high-temperature-resistant cold-resistant high-flame-retardant polyvinyl chloride material has the following beneficial effects:
the obtained polyvinyl chloride material has the balance of high temperature resistance, cold resistance and flame retardance, can resist the high temperature of 125 ℃ and the low temperature of minus 50 ℃, has an oxygen index of more than 40, can be used in extremely hot and cold environments, has excellent flame retardance, and can pass a bundling combustion A-type test.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a high-temperature-resistant cold-resistant high-flame-retardant polyvinyl chloride material which comprises the following components in parts by weight: 100 parts of PVC resin, 10-30 parts of plasticizer A, 5-20 parts of plasticizer B, 5-20 parts of plasticizer C, 5-15 parts of plasticizer D, 10-25 parts of flame retardant A, 15-30 parts of flame retardant B, 10-20 parts of flame retardant C, 12-20 parts of heat stabilizer, 10-25 parts of modifier, 1.0-2.5 parts of processing aid and 0.8-2.0 parts of antioxidant;
wherein the PVC resin is one or two combinations of PVC resins with 1100-1800 polymerization degrees.
Plasticizer A is phthalate, plasticizer B is phosphate, plasticizer C is dipentaerythritol ester, and plasticizer D is dioctyl sebacate.
The flame retardant A is antimony trioxide, the flame retardant B is modified magnesium hydroxide, and the flame retardant C is a phosphorus-nitrogen composite flame retardant.
The heat stabilizer is a calcium-zinc composite heat stabilizer.
The modifier is one or two of chlorinated polyethylene and acrylate copolymer.
The processing aid is two or more of calcium stearate, stearic acid and polyethylene wax.
The antioxidant is one or the combination of two of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tri (2, 4-di-tert-butylphenyl) phosphite.
The embodiment of the invention also discloses a preparation method of the high-temperature-resistant cold-resistant high-flame-retardant polyvinyl chloride material, which comprises the following steps:
(1) weighing the raw materials for later use according to the high-temperature-resistant cold-resistant high-flame-retardant polyvinyl chloride material;
(2) adding PVC resin, a plasticizer A, a plasticizer B, a plasticizer C, a plasticizer D, a flame retardant A, a flame retardant B, a flame retardant C and a heat stabilizer into a high-speed kneader to stir and mix, setting the jacket temperature of a mixer at 125-135 ℃, and mixing for 8-15 min; adding a modifier, a processing aid and an antioxidant into the high-speed kneading machine, and mixing for 30-90 s to obtain a uniform mixture;
(3) and (3) putting the mixture into a double-stage extrusion granulator consisting of a double screw and a single screw, wherein the heating temperature of each section of the double screw granulator is uniformly increased from 120-plus-150 ℃, the heating temperature of each section of the single screw granulator is uniformly increased from 90-150 ℃, and the obtained plastic is dried for 1h by a drying barrel at 50-60 ℃ to obtain the high-temperature-resistant, cold-resistant and high-flame-retardant polyvinyl chloride material.
Examples 1 to 6
The embodiment 1-6 of the invention discloses a preparation method of a high-temperature-resistant, cold-resistant and high-flame-retardant polyvinyl chloride material, which specifically comprises the following steps, wherein the composition and the mixture ratio of raw materials are shown in table 1, and various technical parameters are shown in table 2 below:
(1) weighing the raw materials for later use;
wherein the PVC resin is available from Ningbo Temmin; plasticizers were purchased from Jiangsu Senhe company; flame retardant a was purchased from murphy antimony; flame retardant B was purchased from yabao, usa; flame retardant C was purchased from clariant corporation; the calcium-zinc composite heat stabilizer is purchased from German bear brand company.
(2) Adding PVC resin, a plasticizer A, a plasticizer B, a plasticizer C, a plasticizer D, a flame retardant A, a flame retardant B, a flame retardant C and a heat stabilizer into a high-speed kneader to stir and mix, setting the jacket temperature of a mixer to be 125-135 ℃, and setting the first mixing time to be 8-15 min; adding a modifier, a processing aid and an antioxidant into the high-speed kneading machine, wherein the second mixing time is 30-90 s, so as to obtain a uniform mixture;
(3) feeding the mixture into a double-stage extrusion granulator composed of double screws and single screws, wherein the heating temperature of each section of the double-screw granulator is 120 +/-10 ℃, 130 +/-10 ℃, 140 +/-10 ℃, 150 +/-10 ℃ and the head temperature is 150 +/-10 ℃; heating temperature of each section of the single-screw granulator is 90 +/-10 ℃, 110 +/-20 ℃, 130 +/-20 ℃ and 150 +/-10 ℃, and drying the obtained plastic in a drying barrel at 50-60 ℃ for 1h to obtain the high-temperature-resistant, cold-resistant and high-flame-retardant polyvinyl chloride material.
TABLE 1
TABLE 2
Performance detection
The high temperature, cold and flame resistant polyvinyl chloride materials prepared in examples 1-6 were tested with reference to GB/T8815-2008 standard for material performance, and compared with the existing 90 ℃ high flame resistant and cold resistant polyvinyl chloride plastic in the prior art, CVC9012F34S40 produced by Shanghai Kaybolt cable plant Co., Ltd. the results are shown in Table 3.
TABLE 3
From the above table 3 results it is evident that: the high temperature resistant, cold resistant and high flame retardant polyvinyl chloride materials prepared in the above examples 1 to 6 can pass the strict aging test of 150 ℃ x 240h on the basis of keeping the original polyvinyl chloride material performance, and simultaneously the oxygen index is all up to 40, and the low temperature impact embrittlement temperature is up to-50 ℃. The temperature resistant grade of the comparative example in the prior art can only reach 90 ℃, and the comparative example is completely embrittled under the aging condition of 150 ℃ multiplied by 240 h; the low temperature can only reach-40 ℃, the oxygen index can reach 34, and the requirements of cable bundle burning A-class tests cannot be met. The high-temperature-resistant cold-resistant high-flame-retardant polyvinyl chloride material can meet the requirement that a cable is used in extremely hot and cold environments, and a YJV 3 x 50 cable made of the material serving as a sheath can pass a bundling combustion class A test according to IEC 60332-3 detection.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (3)
1. The high-temperature-resistant cold-resistant high-flame-retardant polyvinyl chloride material is characterized by comprising the following components in parts by weight:
100 portions of PVC resin
10-30 parts of plasticizer A
5-20 parts of plasticizer B
Plasticizer C5-20 parts
5-15 parts of plasticizer D
10-25 parts of flame retardant A
15-30 parts of flame retardant B
10-20 parts of flame retardant C
12-20 parts of heat stabilizer
10-25 parts of modifier
1.0-2.5 parts of processing aid
0.8-2.0 parts of antioxidant;
the PVC resin is selected from one or two combinations of PVC resins with the polymerization degree of 1100-1800;
the plasticizer A is phthalate, the plasticizer B is phosphate, the plasticizer C is dipentaerythritol ester, and the plasticizer D is dioctyl sebacate;
the flame retardant A is antimony trioxide, the flame retardant B is modified magnesium hydroxide, and the flame retardant C is a phosphorus-nitrogen composite flame retardant;
the heat stabilizer is a calcium-zinc composite heat stabilizer;
the modifier is one or the combination of two of chlorinated polyethylene and acrylate copolymer;
the processing aid is a combination of two or more of calcium stearate, stearic acid and polyethylene wax;
the antioxidant is one or the combination of two of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and tri (2, 4-di-tert-butylphenyl) phosphite ester.
2. The preparation method of the high-temperature-resistant cold-resistant high-flame-retardant polyvinyl chloride material is characterized by comprising the following steps of:
(1) the high temperature resistant, cold resistant and high flame retardant polyvinyl chloride material according to claim 1, wherein the raw materials are weighed for later use;
(2) uniformly mixing PVC resin, a plasticizer A, a plasticizer B, a plasticizer C, a plasticizer D, a flame retardant A, a flame retardant B, a flame retardant C and a heat stabilizer, controlling the temperature to be 125-135 ℃ and mixing for 8-15 min; adding a modifier, a processing aid and an antioxidant, and mixing for 30-90 s to obtain a uniform mixture;
(3) and extruding and granulating the mixture, and drying the obtained plastic to obtain the polyvinyl chloride material.
3. The use of the high temperature resistant, cold resistant and high flame retardant polyvinyl chloride material of claim 1 in cable materials.
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| CN201911276882.3A CN110951189B (en) | 2019-12-12 | 2019-12-12 | Polyvinyl chloride material and preparation method thereof |
| PCT/CN2020/113339 WO2021114759A1 (en) | 2019-12-12 | 2020-09-03 | Polyvinyl chloride material and preparation method therefor |
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| CN110951189B (en) * | 2019-12-12 | 2021-05-14 | 上海凯波电缆特材股份有限公司 | Polyvinyl chloride material and preparation method thereof |
| CN112143131A (en) * | 2020-09-21 | 2020-12-29 | 上海凯波电缆特材股份有限公司 | Flexible oil-resistant flame-retardant polyvinyl chloride material and preparation method thereof |
| CN113912963A (en) * | 2021-11-19 | 2022-01-11 | 宝胜科技创新股份有限公司 | High-flame-retardant polyvinyl chloride sheath material and preparation method thereof |
| CN114058139A (en) * | 2021-12-08 | 2022-02-18 | 上海凯波电缆特材股份有限公司 | PVC sheath material for photoelectric composite cable suitable for 5G communication base station and preparation method thereof |
| CN114933766B (en) * | 2022-06-29 | 2023-08-29 | 百通赫思曼工业（苏州）有限公司 | Ultralow-temperature-resistant heat-resistant oil-resistant pressure-resistant polyvinyl chloride cable material and preparation method thereof |
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| WO2021114759A1 (en) | 2021-06-17 |
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