CN111471246B - Environment-friendly toughening type PVC electrical casing processing modifier and preparation method thereof - Google Patents
Environment-friendly toughening type PVC electrical casing processing modifier and preparation method thereof Download PDFInfo
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- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—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
- C08F214/02—Monomers containing chlorine
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- C08F214/06—Vinyl chloride
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- 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
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- C08K5/00—Use of organic ingredients
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- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
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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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
- C08L2203/18—Applications used for pipes
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Abstract
The invention relates to the technical field of cables, in particular to an environment-friendly toughening type PVC electrical casing processing modifier and a preparation method thereof. The PVC electrical casing produced by the traditional processing modifier formula of the PVC electrical casing has the advantages of high brittleness, easy cracking due to low-temperature bending, low toughness and compressive strength, easy flattening and deformation of concrete grouting, and easy hardening and embrittlement of the pipe and pollution to living environment due to plasticizer migration in the long-term use process. Aiming at the problems, the invention provides an environment-friendly toughening type PVC electrical casing processing modifier, which is prepared by compounding a vinyl chloride-vinyl acetate copolymer and an acrylic acid-2-ethylhexyl ester modified vinyl chloride-vinyl acetate copolymer to completely replace chlorinated polyethylene and o-phthalic plasticizer in the traditional formula.
Description
Technical Field
The invention relates to the technical field of cables, in particular to an environment-friendly toughening type PVC electrical casing processing modifier and a preparation method thereof.
Background
The insulating electrical casing for building is mainly used for protecting the wires and cables inside the building, and polyvinyl chloride (PVC) plastics have the advantages of insulation, flame retardancy, corrosion resistance and the like, so that the performance of the pipe can better meet the use requirement of the pipe. However, the PVC electrical casing produced by the formula of the traditional processing modifier for the PVC electrical casing has the advantages of high brittleness, easy cracking after low-temperature bending, low toughness and compressive strength, easy flattening and deformation of concrete grouting, and easy hardening and embrittlement of the pipe and pollution to living environment caused by plasticizer migration in the long-term use process.
On the other hand, in recent years, the environmental protection requirement is getting tighter and tighter, the traditional modifier chlorinated polyethylene of the original PVC electrical casing needs to use hazardous chemicals such as chlorine gas due to the production method, the transportation safety and environmental protection problems of liquid chlorine and the large production amount of three wastes in the production process, the production enterprises are in a micro-profit or loss state, the chlorinated polyethylene project belongs to an investment product project which is not encouraged by local governments, a large number of medium and small production enterprises are shut down and modified, the market supply is in shortage, the price is greatly increased, and the market demand can not be met. For the reasons, China PVC electrical casing production enterprises begin to seek solutions in the aspect, and the Chinese invention patent CN 106280072A discloses a cold-resistant cable material sheath, wherein an organic cold-resistant plasticizer and a toughening modifier are added into a PVC base material, so that the low-temperature resistance and toughness of the prepared cable material sheath are greatly improved, and the mechanical property at-40 ℃ can still meet the use requirements. Therefore, the brittleness and low-temperature resistance of the cable material sheath can be improved to a great extent by adding the low-temperature-resistant and high-toughness processing modifier into the PVC base material, so that the development of more processing aids of the PVC electrical casing with high toughness, high compressive strength and low-temperature bending resistance is a necessary development trend in order to meet the strategic target of the current social sustainable development and meet the market demand.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the PVC electrical casing produced by the formula of the traditional processing modifier for the PVC electrical casing has the advantages of high brittleness, easy breakage after low-temperature bending, low toughness and compressive strength, and easy flattening and deformation of concrete grouting. The invention provides an environment-friendly toughening type PVC electrical casing processing modifier, which is prepared by compounding a vinyl chloride-vinyl acetate copolymer and an acrylic acid-2-ethylhexyl modified vinyl chloride-vinyl acetate copolymer to completely replace chlorinated polyethylene and o-benzene plasticizer in the traditional formula, so that the prepared PVC electrical casing has good low-temperature bending property and high wall-buried compressive strength.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides an environment-friendly toughening type PVC electrical casing processing modifier which is characterized by comprising the following components in parts by weight:
3-4.5 parts of calcium-zinc stabilizer
3-5 parts of toughening modifier
0.1 to 1 portion of stearic acid
0.1-1 part of Fischer-Tropsch wax.
Specifically, the environment-friendly toughening type PVC electrical casing processing modifier comprises the following components in parts by weight:
3.1 to 3.9 portions of calcium zinc stabilizer
3.2 to 4.6 portions of toughening modifier
0.2 to 0.9 portion of stearic acid
0.2 to 0.8 portion of Fischer-Tropsch wax.
Specifically, the environment-friendly toughening type PVC electrical casing processing modifier comprises the following components in parts by weight:
3.5 portions of calcium zinc stabilizer
4.0 parts of toughening modifier
Stearic acid 0.5 part
0.4 part of Fischer-Tropsch wax.
Specifically, the toughening modifier is a compound of a chloroethylene-vinyl acetate copolymer and an acrylic acid-2-ethylhexyl ester modified chloroethylene-vinyl acetate copolymer.
Specifically, the mass ratio of the chloroethylene-vinyl acetate copolymer to the 2-ethylhexyl acrylate modified chloroethylene-vinyl acetate copolymer is 1.5-2.0: 2.0-2.5.
Specifically, the mass ratio of the vinyl chloride-vinyl acetate copolymer to the 2-ethylhexyl acrylate modified vinyl chloride-vinyl acetate copolymer is 1.7: 2.3.
Specifically, the vinyl chloride-vinyl acetate copolymer is Honghui new material UM 55.
Specifically, the preparation method of the 2-ethylhexyl acrylate modified vinyl chloride-vinyl acetate copolymer comprises the following steps:
(1) pre-emulsifying monomers: stirring and emulsifying 10 parts of deionized water, 7 parts of acrylic acid-2-ethylhexyl ester and 2 parts of a dispersing agent in a pre-emulsifying kettle for 2 hours to obtain a pre-emulsion for later use;
(2) reaction: adding 100 parts of deionized water, 35 parts of chloroethylene, 8 parts of vinyl acetate, 1.8 parts of dispersing agent, 4 parts of chain regulator and 0.8 part of initiator into a reaction kettle, stirring for 60min, heating to 63 ℃ to initiate polymerization reaction, adding 25 parts of chloroethylene and the pre-emulsion obtained in the step (1) within 5 hours when the pressure in the kettle is reduced to 0.55MPa, continuing the reaction, adding 0.1 part of terminator and 0.1 part of organic silicon defoaming agent when the reaction pressure in the polymerization kettle is lower than 0.2MPa, vacuumizing to-0.06 MPa, recovering unreacted chloroethylene into a chloroethylene recovery storage tank through condensation, stopping a vacuum pump, and discharging;
(3) and (3) dehydrating and drying: dehydrating the product obtained in the step (2) to obtain a semi-finished resin with the water content of 15%, drying at 120 ℃, and finally screening by a 40-mesh stainless steel screen to obtain the 2-ethylhexyl acrylate modified vinyl chloride-vinyl acetate copolymer with the particle size distribution of 85 mu m, the K value of 57, the glass transition temperature of 65 ℃ and the number average molecular weight of 5.2 ten thousand, wherein the 2-ethylhexyl acrylate modified vinyl chloride-vinyl acetate copolymer comprises the following components in parts by weight: 81 parts of vinyl chloride, 10 parts of vinyl acetate and 9 parts of 2-ethylhexyl acrylate.
Specifically, the dispersant in the step (2) is a compound of polyvinylpyrrolidone and hydroxypropyl methyl cellulose ether in a weight ratio of 1: 1.
Specifically, the chain regulator in the step (2) is trichloromethane.
Specifically, the initiator in the step (2) is bis (3, 5, 5) trimethylhexanoyl peroxide.
Specifically, the terminator in the step (2) is N, N-diethylhydroxylamine.
Specifically, the environment-friendly toughening type PVC electrical casing processing modifier further comprises the following components in parts by weight:
0.01 to 0.02 portion of whitening agent
1.0-1.5 parts of titanium dioxide.
An environment-friendly toughening type PVC electrical casing processing modifier is prepared according to the following steps:
(1) preparation of toughening modifier
Adding the chloroethylene-vinyl acetate copolymer and the acrylic acid-2-ethylhexyl modified chloroethylene-vinyl acetate copolymer into a mixer, stirring at normal temperature and normal pressure, uniformly stirring, and discharging for later use;
(2) weighing calcium zinc stabilizer, toughening modifier, stearic acid, Fischer-Tropsch wax, whitening agent and titanium dioxide according to the proportion for later use;
(3) mixing the materials weighed in the step (2), putting the materials into a kneader to be mixed and stirred uniformly, and heating to 120-130 ℃ within 30min to stop heating for later use;
(4) cooling the material obtained in the step (3) to normal temperature, putting the material into a crushing stirrer, crushing the material to 40 meshes, and stirring uniformly to stop the process for later use;
(5) and (4) cooling the material obtained in the step (4) to normal temperature, and then unloading and packaging to obtain the processing modifier.
The invention has the beneficial effects that:
(1) the production process of the modifier for processing the PVC electrical casing is simple, healthy and environment-friendly, has low addition amount, is low-carbon and energy-saving;
(2) the PVC electrical casing processing modifier prepared by the method replaces chlorinated polyethylene in the traditional PVC electrical casing formula, and under the condition that the PVC electrical casings achieve the same effect, the addition amount of the PVC electrical casing processing modifier prepared by the method is half of the weight of the chlorinated polyethylene serving as the traditional plasticizing modifier, so that the raw material cost for PVC electrical casing production is effectively reduced, the low-temperature bending property and the wall-buried compressive strength of the electrical casings are improved, and the product quality is improved;
(3) compared with the traditional PVC electrical casing pipe formula system, the processing modifier prepared by the method has low melt viscosity and good fluidity, the screw extruder has low current torque and small machine abrasion, can be industrially produced in batches, and has wide application in the technical field of processing of PVC electrical casings.
(4) The 2-ethylhexyl acrylate is the species with the lowest glass transition temperature in the acrylate monomers, can improve the low temperature resistance of the vinyl chloride-vinyl acetate copolymer resin by reducing the glass transition temperature of the copolymer by the minimum proportion, and simultaneously provides a branched chain structure, increases intermolecular entanglement to increase intermolecular force, and macroscopically increases tensile strength and elongation at break.
Detailed Description
The present invention will now be described in further detail with reference to examples.
Examples
The environment-friendly toughening type PVC electrical casing processing modifier is prepared according to the following steps:
(1) preparation of toughening modifier
Adding the chloroethylene-vinyl acetate copolymer and the acrylic acid-2-ethylhexyl modified chloroethylene-vinyl acetate copolymer into a mixer, stirring at normal temperature and normal pressure, uniformly stirring, and discharging for later use;
(2) weighing calcium zinc stabilizer, toughening modifier, stearic acid, Fischer-Tropsch wax, whitening agent and titanium dioxide according to the proportion for later use;
(3) mixing the materials weighed in the step (2), putting the materials into a kneader to be mixed and stirred uniformly, and heating to 120-130 ℃ within 30min to stop heating for later use;
(4) cooling the material obtained in the step (3) to normal temperature, putting the material into a crushing stirrer, crushing the material to 40 meshes, and stirring uniformly to stop the process for later use;
(5) and (4) cooling the material obtained in the step (4) to normal temperature, and then unloading and packaging to obtain the processing modifier.
Examples 1-5 an environmentally friendly toughening type PVC electrical casing processing modifier was prepared as described above, with the components shown in table 1:
TABLE 1
Note: a: vinyl chloride-vinyl acetate copolymers; b: 2-ethylhexyl acrylate-modified vinyl chloride-vinyl acetate copolymer; A/B: a compound of vinyl chloride-vinyl acetate copolymer and 2-ethylhexyl acrylate modified vinyl chloride-vinyl acetate copolymer; wherein, the plasticizing modifier 1.5/2 in Table 1 represents: the compound of the chloroethylene-vinyl acetate copolymer and the acrylic acid-2-ethylhexyl modified chloroethylene-vinyl acetate copolymer contains 1.5 weight parts of chloroethylene-vinyl acetate copolymer and 2 weight parts of acrylic acid-2-ethylhexyl modified chloroethylene-vinyl acetate copolymer.
Wherein the temperature of mixing and stirring the materials in the kneader of the example 1 is 120 ℃;
the temperature for mixing and stirring the materials of the example 2 in a kneader is 130 ℃;
the temperature for mixing and stirring the materials of the example 3 in the kneader is 122 ℃;
the temperature for mixing and stirring the materials of example 4 in a kneader is 128 ℃;
the temperature at which the materials of example 5 were mixed and stirred in the kneader was 125 ℃.
Comparative examples 1-4 are the same as example 1 except for the following Table 2:
TABLE 2
The processing modifier prepared in examples 1-5 and comparative examples 1-4 is added into a formula of a PVC electrical casing to prepare a PVC electrical casing material, and the PVC electrical casing material comprises the following components in parts by weight:
100 portions of PVC resin base material (PVC SG-5)
10 parts of processing modifier prepared in examples 1-5 or comparative examples 1-4
Comparative example 5 formulation, in parts by weight, comprising the following ingredients:
100 portions of PVC resin base material (PVC SG-5)
Chlorinated polyethylene (CPE135A)8 parts
2 portions of dioctyl phthalate
3 portions of calcium zinc stabilizer (SZ-78)
Stearic acid 0.1 part
Fischer-Tropsch wax 0.1
Whitening agent 0.01
The titanium dioxide powder 1 is prepared by the following steps,
wherein, the Fischer-Tropsch wax is Sasolwax Spray 105G-EF.
The materials of examples 1-5 and comparative examples 1-5 were mixed uniformly, and added into a twin-screw extruder to melt and blend at 120 ℃ to be extruded and molded to produce the PVC electrical bushing.
And (3) performance testing:
the results of the performance tests on the PVC electrical casing materials prepared in examples 1-5 and comparative examples 1-5 are shown in table 3 below:
TABLE 3
Note: the dimensional tests in Table 3 were carried out according to GB/T8806-2008 "determination of dimensions of Plastic parts for Plastic pipe systems"; the conventional mechanical properties are tested according to GB/T1040-; the compression resistance, impact resistance, bending and flattening performance and drop performance tests were carried out according to the temperature grade-25 type in JG3050-1998 insulating electrical casing and fittings for buildings.
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.
Claims (8)
1. The environment-friendly toughening type PVC electrical casing processing modifier is characterized by comprising the following components in parts by weight:
3-4.5 parts of calcium-zinc stabilizer
3-5 parts of toughening modifier
0.1 to 1 portion of stearic acid
0.1-1 part of Fischer-Tropsch wax;
the toughening modifier is a compound of vinyl chloride-vinyl acetate copolymer and acrylic acid-2-ethylhexyl ester modified vinyl chloride-vinyl acetate copolymer; the mass ratio of the chloroethylene-vinyl acetate copolymer to the 2-ethylhexyl acrylate modified chloroethylene-vinyl acetate copolymer in the compound is 1.5-2.0: 2.0-2.5.
2. The environment-friendly toughening type PVC electrical casing processing modifier according to claim 1, which comprises the following components in parts by weight:
3.1 to 3.9 portions of calcium zinc stabilizer
3.2 to 4.6 portions of toughening modifier
0.2 to 0.9 portion of stearic acid
0.2 to 0.8 portion of Fischer-Tropsch wax.
3. The environment-friendly toughening type PVC electrical casing processing modifier according to claim 1, which comprises the following components in parts by weight:
3.5 portions of calcium zinc stabilizer
4.0 parts of toughening modifier
Stearic acid 0.5 part
0.4 part of Fischer-Tropsch wax.
4. The environment-friendly toughening type PVC electrical casing processing modifier according to claim 1, wherein: the mass ratio of the chloroethylene-vinyl acetate copolymer to the 2-ethylhexyl acrylate modified chloroethylene-vinyl acetate copolymer is 1.7: 2.3.
5. The environment-friendly toughening type PVC electrical casing processing modifier according to claim 1, wherein: the vinyl chloride-vinyl acetate copolymer is Honghui Xin material UM 55.
6. The environment-friendly toughening type PVC electrical casing processing modifier according to claim 1, wherein: the 2-ethylhexyl acrylate modified vinyl chloride-vinyl acetate copolymer comprises the following components in parts by weight: 81 parts of vinyl chloride, 10 parts of vinyl acetate and 9 parts of 2-ethylhexyl acrylate.
7. The environment-friendly toughening type PVC electrical casing processing modifier according to claim 1, further comprising, in parts by weight:
0.01 to 0.02 portion of whitening agent
1.0-1.5 parts of titanium dioxide.
8. The environment-friendly toughening type PVC electrical casing processing modifier according to any one of claims 1 to 7, which is prepared by the following steps:
(1) preparation of toughening modifier
Adding the chloroethylene-vinyl acetate copolymer and the acrylic acid-2-ethylhexyl modified chloroethylene-vinyl acetate copolymer into a mixer, stirring at normal temperature and normal pressure, uniformly stirring, and discharging for later use;
(2) weighing a calcium-zinc stabilizer, a toughening modifier, stearic acid, Fischer-Tropsch wax, light calcium carbonate, a whitening agent and titanium dioxide according to a proportion for later use;
(3) mixing the materials weighed in the step (2), putting the materials into a kneader to be mixed and stirred uniformly, and heating to 120-130 ℃ within 30min to stop heating for later use;
(4) cooling the material obtained in the step (3) to normal temperature, putting the material into a crushing stirrer, crushing the material to 40 meshes, and stirring uniformly to stop the process for later use;
(5) and (4) cooling the material obtained in the step (4) to normal temperature, then discharging and packaging to obtain the plasticizing modifier.
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| CN102532748A (en) * | 2011-12-07 | 2012-07-04 | 湖北众联塑业有限公司 | Processing modifier for polyvinyl chloride electrical casing |
| CN103467886A (en) * | 2013-09-10 | 2013-12-25 | 新疆石河子中发化工有限责任公司 | PVC (Poly Vinyl Chloride) profile added with chloroethylene-acrylate copolymer resin and preparation method thereof |
| CN105985479A (en) * | 2015-02-02 | 2016-10-05 | 北京化工大学 | Preparation of acrylate modified vinyl chloride-vinyl acetate copolymerized resin through microsuspension polymerization |
| JP2017105966A (en) * | 2015-11-26 | 2017-06-15 | 東ソー株式会社 | Vinyl chloride-vinyl acetate copolymer composition particle and application thereof |
| CN108484813A (en) * | 2018-02-10 | 2018-09-04 | 无锡洪汇新材料科技股份有限公司 | A kind of vinyl chloride high polymer and preparation method thereof |
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| CN102532748A (en) * | 2011-12-07 | 2012-07-04 | 湖北众联塑业有限公司 | Processing modifier for polyvinyl chloride electrical casing |
| CN103467886A (en) * | 2013-09-10 | 2013-12-25 | 新疆石河子中发化工有限责任公司 | PVC (Poly Vinyl Chloride) profile added with chloroethylene-acrylate copolymer resin and preparation method thereof |
| CN105985479A (en) * | 2015-02-02 | 2016-10-05 | 北京化工大学 | Preparation of acrylate modified vinyl chloride-vinyl acetate copolymerized resin through microsuspension polymerization |
| JP2017105966A (en) * | 2015-11-26 | 2017-06-15 | 東ソー株式会社 | Vinyl chloride-vinyl acetate copolymer composition particle and application thereof |
| CN108484813A (en) * | 2018-02-10 | 2018-09-04 | 无锡洪汇新材料科技股份有限公司 | A kind of vinyl chloride high polymer and preparation method thereof |
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