CN104893152B - A kind of preparation method of environment-friendly cold polyvinyl chloride elastic composition - Google Patents
A kind of preparation method of environment-friendly cold polyvinyl chloride elastic composition Download PDFInfo
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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
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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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
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L31/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
- C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C08L31/04—Homopolymers or copolymers of vinyl acetate
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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
- 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
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
Abstract
The invention discloses a kind of preparation methods of environment-friendly cold polyvinyl chloride elastic composition, Corvic, dimethyl terephthalate ester, synthesis vegetable oil esters, polar rubber, nm-class active calcium carbonate, calcium zinc system compound stabilizer, lubricant, antioxidant and pigment are mixed in kneader, material temperature to be mixed discharges after reaching 90-100 DEG C and cools down, mixture after cooling is placed in extruding pelletization in twin-screw extruder again to form, elastic composition shore hardness at -5 DEG C is lower than 80.The beneficial effects of the invention are as follows with excellent in low temperature toughness, the advantages that mechanical strength is high, heat-resistant aging is good, environment-protecting and non-poisonous, excellent combination property, particularly useful for making elevator balanced compensated chain sheath, door and window and vehicle window strip of paper used for sealing and the insulating sheath of wire and cable etc..
Description
[technical field]
The present invention relates to Material Field more particularly to a kind of preparation sides of environment-friendly cold polyvinyl chloride elastic composition
Method.
[background technique]
Polyvinyl chloride elastomer has the characteristics that cheap, mechanical property can reconcile good flame resistance, is suitable for preparation electricity
Terraced balanced compensated chain sheath, the insulating sheath of wire and cable and numerous occasions such as door and window and vehicle window strip of paper used for sealing.But polyvinyl chloride bullet
Property body the feature of environmental protection and in terms of there are certain defects.
So far, have that many patent reports are low temperature resistant or composition and the preparation side of cold resistance polyvinyl chloride elastomeric material
Method.Such as application No. is CN201210569416.6, CN201410284632.5, CN200810023863.5 Chinese patents.On
Although stating polyvinyl chloride elastomeric material described in patent with certain resistance to low temperature, low-temperature good toughness, however its
Primary plasticizer used is phthalic ester plasticizer, and this kind of plasticizer can be detrimental to health, and environmental requirement is not achieved.
For meet the requirement of environmental protection, has the environmentally friendly polyvinyl chloride elastomer of patent report.Application No. is
CN200910102369.2、CN201310464355.1、CN201010508484.2、CN201310754691.X、
The patents such as CN201110199511.7, CN201310242694.5 and CN201210106293.2 disclose environment-friendly type polychlorostyrene second
The composition and preparation method of alkene elastomer, prepared elastomer has the excellent feature of environmental protection, very few to human body and environmental pollution,
However its used toughener and plasticizer cryogenic property are poor, so that elastomer meeting under the conditions of low temperature (- 40 DEG C or less)
Embrittlement seriously affects service life of the elastomer under extremely cold environment.Meanwhile there are also patents to disclose the poly- of environment-friendly cold
Vinyl chloride elastomer.As being silicon rubber application No. is toughener used in CN201310473887.1 patent, with polychlorostyrene second
Compatibility in alkenyl body is poor, causes the room temperature toughness of elastomer and low-temperature flexibility to be affected, resistance to low temperature is paid no attention to
Think.Application No. is CN201210161975.3 to disclose a kind of cold-resistant environment-friendly polyvinyl chloride base Special cable material, used
Diethylene glycol dibenzoate plasticizer cost of material is high, limits its application in civilian sphere.Therefore a kind of ring is developed
The polyvinyl chloride elastomer for protecting the excellent combination properties such as nontoxic, cold-resistant, mechanical strength is high is particularly important.
[summary of the invention]
The purpose of the present invention is to provide a kind of preparation methods of environment-friendly cold polyvinyl chloride elastic composition, have peace
Loopful is protected, resists cold the advantages that heat-resisting, anti-aging, mechanical strength is high, can still keep higher under low temp operation environment
Toughness.
To solve the above-mentioned problems, the technical solution of the invention is as follows: a kind of environment-friendly cold polyvinyl chloride elastomer group
Close object, including Corvic, the compound Plasticising system of environmental protection, toughener, calcium zinc system compound stabilizer, lubricant, antioxidant
And pigment, the compound Plasticising system of environmental protection include dimethyl terephthalate ester and synthesis vegetable oil esters, the toughener packet
Polar rubber and nm-class active calcium carbonate are included, elastic composition shore hardness at -5 DEG C is described to benzene two lower than 80
Alkyl includes 7~12 carbon atoms in formic acid dialkyl ester.
Further, the elastic composition each component calculate by weight include: 100 parts by weight polyvinyl chloride tree
Rouge, the dimethyl terephthalate ester of 50~90 parts by weight, the synthesis vegetable oil esters of 10~40 parts by weight, 5~20 parts by weight
Polar rubber, the nm-class active calcium carbonate of 5~30 parts by weight, the calcium-zinc composite stabilizing agent of 4~8 parts by weight, 1~2 parts by weight
The pigment of lubricant, the antioxidant of 0.2~1 parts by weight and 0.5~3 parts by weight.
Further, the synthesis vegetable oil esters are formed by vegetable oil through epoxidation or epoxy group esterification modification, the plant
Oil is one of soybean oil, linseed oil, castor oil, safflower oil and sunflower oil or a variety of compositions.
Further, the polar rubber is ethylene-vinyl acetate copolymer rubber, polyurethane rubber and polyacrylate
One of rubber.
Further, in the ethylene-vinyl acetate copolymer rubber vinylacetate weight percent content be 40~
70%.
Further, the average diameter of the nm-class active calcium carbonate is between 60~100nm.
Further, the lubricant is one of zinc stearate, stearic acid and polyethylene wax.
Further, the antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, 2,
2'- methylene-bis- (4- methyl-6-tert-butylphenol), three [2.4- di-tert-butyl-phenyl] phosphite esters, in triphenyl phosphite
One or two kinds of compositions.
Further, the pigment is one of high-carbon black pigment and rutile titanium dioxide.
The present invention also provides the preparation methods of above-mentioned environment-friendly cold polyvinyl chloride elastic composition, include the following steps:
Step 1: each component is uniformly mixed in kneader, makes mixture temperature using the frictional heat that stirring generates
Degree increases；
Step 2: each component mixture temperature discharges after rising to 90-100 DEG C in kneader, and it is cold to be sent into cooling and stirring device
But to 45 DEG C or less；
Step 3: mixture after cooling is placed in squeeze out in twin-screw extruder and makes material, double rank Screw Extrusions
Machine includes double screw extruder and single screw extrusion machine, the temperature point of four heating zones of the double screw extruder and extrusion die
Not are as follows: T1=85~100 DEG C, T2=100~120 DEG C, T3=120~140 DEG C, T4=130~150 DEG C, mould=130~150 T
℃；The temperature of the single screw extrusion machine heating zone and extrusion die is controlled respectively in 110~130 DEG C and 120~140 DEG C, is obtained
To polyvinyl chloride elastic composition, at -5 DEG C, shore hardness is lower than 80.
Polyvinyl chloride elastomer prepared by the present invention has excellent in low temperature toughness, mechanical strength is high, heat-resistant aging is good,
The advantages that environment-protecting and non-poisonous, excellent combination property, particularly useful for making elevator balanced compensated chain sheath, door and window and vehicle window strip of paper used for sealing with
And insulating sheath of wire and cable etc..
Above-mentioned polyvinyl chloride elastic composition has the following beneficial effects:
(1) meet environmental requirement to environment and human body without security risk by using safe environment protection type plasticizer, to benzene
Diformazan acid dialkyl ester has and phthalic ester plasticizer equally excellent plasticization effect and excellent cold tolerance,
It will not be inactivated under cryogenic conditions；Synthesis vegetable fat has the characteristics that low volatility, can also be used as heat stabilizer；Two kinds of plasticizer
By being reasonably used cooperatively, playing respective performance advantage can assign polyvinyl chloride superior plasticization effect；
(2) make elastomer in low temperature as toughener using the polar rubber and nm-class active calcium carbonate with cold resistance
Under the conditions of be still able to maintain good toughness；Nm-class active calcium carbonate is as toughener and filler in PVC base system
Can be fully dispersed, the toughness and intensity of elastomer are greatly improved, the double effect of toughening and enhancing is played.Two kinds of toughenings
Agent is applied in combination, and generates synergistic effect, has remarkable result to room temperature toughness, the holding low-temperature flexibility of raising elastomer；
(3) environment-friendly type liquid state calcium zinc system compound stabilizer is used, to environment and human body to there is no hidden danger is endangered, meets ring
Guaranteed request.
[specific embodiment]
The present invention will be further described in detail with reference to the specific embodiments.
In order to which those skilled in the art better understood when technical solution provided by the present invention, below with reference to specific
Embodiment is illustrated.
A kind of environment-friendly cold polyvinyl chloride elastic composition of the present invention, including Corvic, environmental protection are multiple
Close Plasticising system, toughener, calcium zinc system compound stabilizer, lubricant, antioxidant and pigment, the compound Plasticising system packet of environmental protection
Dimethyl terephthalate ester and synthesis vegetable oil esters are included, the toughener includes polar rubber and nm-class active calcium carbonate, institute
It states elastic composition shore hardness at -5 DEG C and is lower than 80, alkyl includes 7~12 in the dimethyl terephthalate ester
Carbon atom.
Elastic composition each component calculate by weight include: 100 parts by weight Corvic, 50~90 weight
The dimethyl terephthalate ester of part, the synthesis vegetable oil esters of 10~40 parts by weight, the polar rubber of 5~20 parts by weight, 5~30
The nm-class active calcium carbonate of parts by weight, the calcium-zinc composite stabilizing agent of 4~8 parts by weight, the lubricant of 1~2 parts by weight, 0.2~1 weight
Measure the antioxidant of part and the pigment of 0.5~3 parts by weight.
Synthesis vegetable oil esters formed by vegetable oil through epoxidation or epoxy group esterification modification, the vegetable oil be soybean oil,
One of linseed oil, castor oil, safflower oil and sunflower oil or a variety of compositions；The polar rubber is ethylene-vinyl acetate
One of copolymer rubber, polyurethane rubber and lactoprene；In the ethylene-vinyl acetate copolymer rubber
Vinylacetate weight percent content is 40~70%；The average diameter of the nm-class active calcium carbonate 60~100nm it
Between；The lubricant is one of zinc stearate, stearic acid and polyethylene wax；The antioxidant is four [β-(the tertiary fourths of 3,5- bis-
Base -4- hydroxy phenyl) propionic acid] pentaerythritol ester, 2,2'- methylene-bis- (4- methyl-6-tert-butylphenol), three [bis- uncles of 2.4-
Butyl phenyl] phosphite ester, one or both of triphenyl phosphite composition；The pigment is high-carbon black pigment and rutile
One of type titanium dioxide.
The present invention also provides the preparation methods of above-mentioned environment-friendly cold polyvinyl chloride elastic composition, include the following steps:
Step 1: each component is uniformly mixed in kneader, makes mixture temperature using the frictional heat that stirring generates
Degree increases；
Step 2: each component mixture temperature discharges after rising to 90-100 DEG C in kneader, and it is cold to be sent into cooling and stirring device
But to 45 DEG C or less；
Step 3: mixture after cooling is placed in squeeze out in twin-screw extruder and makes material, double rank Screw Extrusions
Machine includes double screw extruder and single screw extrusion machine, the temperature point of four heating zones of the double screw extruder and extrusion die
Not are as follows: T1=85~100 DEG C, T2=100~120 DEG C, T3=120~140 DEG C, T4=130~150 DEG C, mould=130~150 T
℃；The temperature of the single screw extrusion machine heating zone and extrusion die is controlled respectively in 110~130 DEG C and 120~140 DEG C, is obtained
To polyvinyl chloride elastic composition, at -5 DEG C, shore hardness is lower than 80.
Embodiment one:
The Corvic of 100 parts by weight, the dioctyl terephthalate of 75 parts by weight, the epoxy of 25 parts by weight is big
Soya-bean oil, the polyurethane rubber of 10 parts by weight, the nm-class active calcium carbonate of 15 parts by weight, 5 parts by weight calcium-zinc composite stabilizing agent,
Four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters of the zinc stearate of 1.5 parts by weight, 0.6 parts by weight
It is stirred with the high-carbon black pigment of 1 parts by weight in kneader high speed, the frictional heat for stirring generation makes mixed material temperature liter
It discharges after to 90-100 DEG C, mixed material is sent into cooling and stirring device and is cooled to 45 DEG C hereinafter, again setting mixed material after cooling
In extruding pelletization in twin-screw extruder, wherein the temperature of four heating zones of double screw extruder and extrusion die is respectively as follows:
T1=85~100 DEG C, T2=100~120 DEG C, T3=120~140 DEG C, T4=130~150 DEG C, TMould=130~150 DEG C；Single spiral shell
The temperature of bar extruder heating zone and extrusion die is controlled respectively in 110~130 DEG C and 120~140 DEG C.The pellet of extrusion is existed
It is hot pressed on vulcanizing press with a thickness of 2mm or 6mm print, and cuts into satisfactory batten.
Embodiment two:
By the Corvic of 100 parts by weight, two heptyl ester of terephthalic acid (TPA) of 90 parts by weight, 10 parts by weight epoxy group
It is esterified linseed oil, the ethylene-vinyl acetate copolymer (vinyl acetate weight percent is 40%) of 20 parts by weight, 5 parts by weight
Nm-class active calcium carbonate, the calcium-zinc composite stabilizing agent of 8 parts by weight, the polyethylene wax of 1 parts by weight, 0.2 parts by weight four [β-
(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and 3 parts by weight rutile titanium dioxide in kneader
High-speed stirred mixing, stir generation frictional heat so that mixed material temperature is risen to 90-100 DEG C after discharge, mixed material be sent into it is cold
But blender is cooled to 45 DEG C hereinafter, mixed material after cooling is placed in extruding pelletization in twin-screw extruder again, wherein
The temperature of four heating zones of double screw extruder and extrusion die is respectively as follows: T1=85~100 DEG C, T2=100~120 DEG C, T3=
120~140 DEG C,T4=130~150 DEG C, TMould=130~150 DEG C；The temperature of single screw extrusion machine heating zone and extrusion die point
It Kong Zhi not be in 110~130 DEG C and 120~140 DEG C.The pellet of extrusion is hot pressed into a thickness of 2mm or 6mm on vulcanizing press
Print, and cut into satisfactory batten.
Embodiment three:
By the Corvic of 100 parts by weight, terephthalic acid (TPA) two (dodecyl) ester of 70 parts by weight, 40 parts by weight
Epoxy safflower oil, the lactoprene of 5 parts by weight, the nm-class active calcium carbonate of 30 parts by weight, the calcium zinc of 8 parts by weight it is multiple
Close stabilizer, the zinc stearate of 2 parts by weight, 0.5 parts by weight four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] seasons penta
The high-carbon black pigment of four alcohol esters, three [2.4- di-tert-butyl-phenyl] phosphite esters of 0.2 parts by weight and 1.5 parts by weight is in kneader
High speed is stirred, stir generation frictional heat so that mixed material temperature is risen to 90-100 DEG C after discharge, mixed material be sent into
Cooling and stirring device is cooled to 45 DEG C hereinafter, mixed material after cooling is placed in extruding pelletization in twin-screw extruder again,
The temperature of four heating zones of middle double screw extruder and extrusion die is respectively as follows: T1=85~100 DEG C, T2=100~120 DEG C, T3
=120~140 DEG C, T4=130~150 DEG C, TMould=130~150 DEG C；The temperature of single screw extrusion machine heating zone and extrusion die
It is controlled respectively in 110~130 DEG C and 120~140 DEG C.The pellet of extrusion is hot pressed into a thickness of 2mm on vulcanizing press or
6mm print, and cut into satisfactory batten.
Example IV:
By the Corvic of 100 parts by weight, the epoxy castor of the dioctyl terephthalate of 70 parts by weight, 30 parts by weight
Sesame oil, the polyurethane rubber of 20 parts by weight, the nm-class active calcium carbonate of 20 parts by weight, the calcium-zinc composite stabilizing agent of 6 parts by weight, 1
The zinc stearate of parts by weight, three [2.4- di-tert-butyl-phenyl] phosphite esters of 0.6 parts by weight, 0.2 parts by weight phosphorous acid three
Phenyl ester and the high-carbon black pigment of 1 parts by weight are stirred in kneader high speed, and the frictional heat for stirring generation makes mixture material temperature
Degree discharges after rising to 90-100 DEG C, and mixed material is sent into cooling and stirring device and is cooled to 45 DEG C hereinafter, again by mixture after cooling
Material is placed in extruding pelletization in twin-screw extruder, and wherein the temperature of four heating zones of double screw extruder and extrusion die is distinguished
Are as follows: T1=85~100 DEG C, T2=100~120 DEG C, T3=120~140 DEG C, T4=130~150 DEG C, TMould=130~150 DEG C；
The temperature of single screw extrusion machine heating zone and extrusion die is controlled respectively in 110~130 DEG C and 120~140 DEG C.By the grain of extrusion
Material is hot pressed into a thickness of 2mm or 6mm print on vulcanizing press, and cuts into satisfactory batten.
Embodiment five:
By the Corvic of 100 parts by weight, terephthalic acid (TPA) two (dodecyl) ester of 75 parts by weight, 20 parts by weight
Epoxy sunflower oil, the ethylene-vinyl acetate copolymer (vinyl acetate weight percent be 70%) of 15 parts by weight, 10 parts by weight
Nm-class active calcium carbonate, the calcium-zinc composite stabilizing agent of 5 parts by weight, the polyethylene wax of 1 parts by weight, 0.6 parts by weight three [2.4-
Di-tert-butyl-phenyl] high-carbon black pigments of phosphite ester and 0.5 parts by weight is stirred in kneader high speed, stir generation
Frictional heat discharges after so that mixed material temperature is risen to 90-100 DEG C, mixed material be sent into cooling and stirring device be cooled to 45 DEG C hereinafter,
Mixed material after cooling is placed in extruding pelletization in twin-screw extruder again, wherein four heating zones of double screw extruder and
The temperature of extrusion die is respectively as follows: T1=85~100 DEG C, T2=100~120 DEG C, T3=120~140 DEG C, T4=130~150
DEG C, TMould=130~150 DEG C；The temperature of single screw extrusion machine heating zone and extrusion die is controlled respectively at 110~130 DEG C and 120
~140 DEG C.The pellet of extrusion is hot pressed into a thickness of 2mm or 6mm print on vulcanizing press, and is cut into satisfactory
Batten.
Comparative example one:
The Corvic of 100 parts by weight, the dioctyl terephthalate of 75 parts by weight, the epoxy of 25 parts by weight is big
Soya-bean oil, the haloflex of 10 parts by weight, the precipitated calcium carbonate that 15 parts by weight mesh numbers are 1200, the Ca Zn composite of 5 parts by weight are steady
Determine agent, the lubricant of 1.5 parts by weight, 0.6 parts by weight three [2.4- di-tert-butyl-phenyl] phosphite esters and 1 parts by weight high color
Plain carbon black is stirred in kneader high speed, stir generation frictional heat so that mixed material temperature is risen to 90-100 DEG C after go out
Material, mixed material are sent into cooling and stirring device and are cooled to 45 DEG C hereinafter, mixed material after cooling is placed in double rank Screw Extrusions again
Extruding pelletization on machine, wherein the temperature of four heating zones of double screw extruder and extrusion die is respectively as follows: T1=85~100 DEG C, T2
=100~120 DEG C, T3=120~140 DEG C, T4=130~150 DEG C, TMould=130~150 DEG C；Single screw extrusion machine heating zone and
The temperature of extrusion die is controlled respectively in 110~130 DEG C and 120~140 DEG C.The hot pressing on vulcanizing press by the pellet of extrusion
At with a thickness of 2mm or 6mm print, and cut into satisfactory batten.
Comparative example two:
The Corvic of 100 parts by weight, the dioctyl terephthalate of 75 parts by weight, the epoxy of 25 parts by weight is big
Soya-bean oil, the polyurethane rubber of 10 parts by weight, the precipitated calcium carbonate that 15 parts by weight mesh numbers are 1200, the Ca Zn composite of 5 parts by weight are steady
Determine agent, the lubricant of 1.5 parts by weight, 0.6 parts by weight three [2.4- di-tert-butyl-phenyl] phosphite esters and 1 parts by weight high color
Plain carbon black is stirred in kneader high speed, stir generation frictional heat so that mixed material temperature is risen to 90-100 DEG C after go out
Material, mixed material are sent into cooling and stirring device and are cooled to 45 DEG C hereinafter, mixed material after cooling is placed in double rank Screw Extrusions again
Extruding pelletization on machine, wherein the temperature of four heating zones of double screw extruder and extrusion die is respectively as follows: T1=85~100 DEG C, T2
=100~120 DEG C,T3=120~140 DEG C, T4=130~150 DEG C, TMould=130~150 DEG C；Single screw extrusion machine heating zone and
The temperature of extrusion die is controlled respectively in 110~130 DEG C and 120~140 DEG C.The hot pressing on vulcanizing press by the pellet of extrusion
At with a thickness of 2mm or 6mm print, and cut into satisfactory batten.
Comparative example three:
By the Corvic of 100 parts by weight, terephthalic acid (TPA) two (dodecyl) ester of 75 parts by weight, 20 parts by weight
Epoxy sunflower oil, the ethylene-vinyl acetate copolymer (vinyl acetate weight percent be 50%) of 3 parts by weight, 10 parts by weight
Nm-class active calcium carbonate, the calcium-zinc composite stabilizing agent of 5 parts by weight, the lubricant of 1 parts by weight, 0.6 parts by weight three [2.4- bis-
Tert-butyl-phenyl] high-carbon black pigments of phosphite ester and 0.5 parts by weight is stirred in kneader high speed, stir rubbing for generation
Chafing discharges after so that mixed material temperature is risen to 90-100 DEG C, and mixed material is sent into cooling and stirring device and is cooled to 45 DEG C hereinafter, again
Mixed material after cooling is placed in extruding pelletization in twin-screw extruder, wherein four heating zones of double screw extruder and squeeze
The temperature of die head is respectively as follows: T out1=85~100 DEG C, T2=100~120 DEG C, T3=120~140 DEG C, T4=130~150 DEG C,
TMould=130~150 DEG C；The temperature of single screw extrusion machine heating zone and extrusion die control respectively 110~130 DEG C and 120~
140℃.The pellet of extrusion is hot pressed into a thickness of 2mm or 6mm print on vulcanizing press, and cuts into satisfactory sample
Item.
Comparative example four:
By the Corvic of 100 parts by weight, terephthalic acid (TPA) two (dodecyl) ester of 75 parts by weight, 20 parts by weight
Epoxy sunflower oil, the polyurethane rubber of 25 parts by weight, the nm-class active calcium carbonate of 10 parts by weight, 5 parts by weight Ca Zn composite
Stabilizer, the lubricant of 1 parts by weight, 0.6 parts by weight three [2.4- di-tert-butyl-phenyl] phosphite esters and 0.5 parts by weight height
Colour carbon black is stirred in kneader high speed, stir generation frictional heat so that mixed material temperature is risen to 90-100 DEG C after go out
Material, mixed material are sent into cooling and stirring device and are cooled to 45 DEG C hereinafter, mixed material after cooling is placed in double rank Screw Extrusions again
Extruding pelletization on machine, wherein the temperature of four heating zones of double screw extruder and extrusion die is respectively as follows: T1=85~100 DEG C, T2
=100~120 DEG C, T3=120~140 DEG C, T4=130~150 DEG C, TMould=130~150 DEG C；Single screw extrusion machine heating zone and
The temperature of extrusion die is controlled respectively in 110~130 DEG C and 120~140 DEG C.The hot pressing on vulcanizing press by the pellet of extrusion
At with a thickness of 2mm or 6mm print, and cut into satisfactory batten.
Comparative example five:
By the Corvic of 100 parts by weight, terephthalic acid (TPA) two (dodecyl) ester of 75 parts by weight, 20 parts by weight
Epoxy sunflower oil, the lactoprene of 15 parts by weight, the nm-class active calcium carbonate of 3 parts by weight, the calcium zinc of 5 parts by weight it is multiple
Close stabilizer, the lubricant of 1 parts by weight, three [2.4- di-tert-butyl-phenyl] phosphite esters of 0.6 parts by weight and 0.5 parts by weight
High-carbon black pigment is stirred in kneader high speed, stir generation frictional heat so that mixed material temperature is risen to 90-100 DEG C after
Discharging, mixed material feeding cooling and stirring device are cooled to 45 DEG C and squeeze hereinafter, mixed material after cooling is placed in double rank screw rods again
Extruding pelletization on machine out, wherein the temperature of four heating zones of double screw extruder and extrusion die is respectively as follows: T1=85~100
DEG C, T2=100~120 DEG C, T3=120~140 DEG C, T4=130~150 DEG C, TMould=130~150 DEG C；Single screw extrusion machine adds
The temperature of hot-zone and extrusion die is controlled respectively in 110~130 DEG C and 120~140 DEG C.By the pellet of extrusion in vulcanizing press
On be hot pressed into a thickness of 2mm or 6mm print, and cut into satisfactory batten.
Comparative example six:
By the Corvic of 100 parts by weight, terephthalic acid (TPA) two (dodecyl) ester of 75 parts by weight, 20 parts by weight
Epoxy sunflower oil, the ethylene-vinyl acetate copolymer (vinyl acetate weight percent be 60%) of 15 parts by weight, 35 parts by weight
Nm-class active calcium carbonate, the calcium-zinc composite stabilizing agent of 5 parts by weight, the lubricant of 1 parts by weight, 0.6 parts by weight three [2.4- bis-
Tert-butyl-phenyl] high-carbon black pigments of phosphite ester and 0.5 parts by weight is stirred in kneader high speed, stir rubbing for generation
Chafing discharges after so that mixed material temperature is risen to 90-100 DEG C, and mixed material is sent into cooling and stirring device and is cooled to 45 DEG C hereinafter, again
Mixed material after cooling is placed in extruding pelletization in twin-screw extruder, wherein four heating zones of double screw extruder and squeeze
The temperature of die head is respectively as follows: T out1=85~100 DEG C, T2=100~120 DEG C, T3=120~140 DEG C, T4=130~150 DEG C,
TMould=130~150 DEG C；The temperature of single screw extrusion machine heating zone and extrusion die control respectively 110~130 DEG C and 120~
140℃.The pellet of extrusion is hot pressed into a thickness of 2mm or 6mm print on vulcanizing press, and cuts into satisfactory sample
Item.
It is instantaneously hard that batten in above-described embodiment and comparative example is subjected to tensile strength, elongation at break, heat ageing, low temperature
Degree and the test of ballistic method brittle temperature, obtain out following result:
From test result as can be seen that shore hardness of the comparative example at -5 DEG C is 80 or more, resist cold, resistant to thermal aging,
Mechanical strength etc. is poorer than embodiment.
The preferred embodiment of the present invention has shown and described in above description, as previously described, it should be understood that the present invention is not office
Be limited to form disclosed herein, should not be regarded as an exclusion of other examples, and can be used for various other combinations, modification and
Environment, and can be changed within that scope of the inventive concept describe herein by the above teachings or related fields of technology or knowledge
It is dynamic.And changes and modifications made by those skilled in the art do not depart from the spirit and scope of the present invention, then it all should be appended by the present invention
In scope of protection of the claims.
Claims (5)
1. a kind of preparation method of environment-friendly cold polyvinyl chloride elastic composition, which comprises the steps of: step
One: each component being uniformly mixed in kneader, increases mixture temperature using the frictional heat that stirring generates；
Step 2: each component mixture temperature discharges after rising to 90-100 DEG C in kneader, is sent into cooling and stirring device and is cooled to
45 DEG C or less；
Step 3: mixture after cooling is placed in squeeze out in twin-screw extruder and makes material, the twin-screw extruder packet
Include double screw extruder and single screw extrusion machine, the temperature difference of four heating zones of the double screw extruder and extrusion die
Are as follows: T1=85~100 DEG C, T2=100~120 DEG C, T3=120~140 DEG C, T4=130~150 DEG C, mould=130~150 T
℃；The temperature of the single screw extrusion machine heating zone and extrusion die is controlled respectively in 110~130 DEG C and 120~140 DEG C, is obtained
To polyvinyl chloride elastic composition, at -5 DEG C, shore hardness is lower than 80；
A kind of environment-friendly cold polyvinyl chloride elastic composition includes Corvic, the compound Plasticising system of environmental protection, increasing
Tough dose, calcium zinc system compound stabilizer, lubricant, antioxidant and pigment, the compound Plasticising system of environmental protection includes terephthalic acid (TPA)
Dialkyl ester and synthesis vegetable oil esters, the toughener includes polar rubber and nm-class active calcium carbonate, the terephthalic acid (TPA)
Alkyl includes 7~12 carbon atoms in dialkyl ester；
The elastic composition each component calculate by weight include: 100 parts by weight Corvic, 50~90 weight
The dimethyl terephthalate ester of part, the synthesis vegetable oil esters of 10~40 parts by weight, the polar rubber of 5~20 parts by weight, 5~30
The nm-class active calcium carbonate of parts by weight, the calcium-zinc composite stabilizing agent of 4~8 parts by weight, the lubricant of 1~2 parts by weight, 0.2~1 weight
Measure the antioxidant of part and the pigment of 0.5~3 parts by weight；The polar rubber is ethylene-vinyl acetate copolymer rubber, poly- ammonia
One of ester rubber and lactoprene；
Vinylacetate weight percent content is 40~70% in the ethylene-vinyl acetate copolymer rubber；
The average diameter of the nm-class active calcium carbonate is between 60~100nm.
2. the preparation method of environment-friendly cold polyvinyl chloride elastic composition as described in claim 1, which is characterized in that described
Synthesis vegetable oil esters are formed by vegetable oil through epoxidation or epoxy group esterification modification, and the vegetable oil is soybean oil, linseed oil, castor
One of sesame oil, safflower oil and sunflower oil or a variety of compositions.
3. the preparation method of environment-friendly cold polyvinyl chloride elastic composition as described in claim 1, which is characterized in that described
Lubricant is one of zinc stearate, stearic acid and polyethylene wax.
4. the preparation method of environment-friendly cold polyvinyl chloride elastic composition as described in claim 1, which is characterized in that described
Antioxidant is four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters, 2,2'- methylene-bis- (4- methyl-
6- tert-butyl phenol), three [2.4- di-tert-butyl-phenyl] phosphite esters, one or both of triphenyl phosphite composition.
5. the preparation method of environment-friendly cold polyvinyl chloride elastic composition as described in claim 1, which is characterized in that described
Pigment is one of high-carbon black pigment and rutile titanium dioxide.
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| PCT/CN2015/093269 WO2016192292A1 (en) | 2015-05-29 | 2015-10-29 | Environmentally friendly and cold-resistant polyvinyl chloride elastomer composition and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104893152B (en) * | 2015-05-29 | 2019-03-26 | 江苏兴华胶带股份有限公司 | A kind of preparation method of environment-friendly cold polyvinyl chloride elastic composition |
| CN105348841B (en) * | 2015-12-14 | 2018-05-18 | 湖南工业大学 | A kind of Chinese Fir for Fibre based biomass composite material and preparation method thereof |
| CN105802060A (en) * | 2016-03-24 | 2016-07-27 | 江苏兴华胶带股份有限公司 | Balance compensation cable for high-speed elevator |
| CN106436394A (en) * | 2016-09-13 | 2017-02-22 | 宣城市华菱精工科技股份有限公司 | Cold-resistant compensating cable for elevator |
| CN106519498A (en) * | 2016-10-28 | 2017-03-22 | 无锡市永兴金属软管有限公司 | Blended toughened PVC (polyvinyl chloride) elastomer and preparation method thereof |
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| CN113292801A (en) * | 2021-05-20 | 2021-08-24 | 重庆泰山高分子材料有限责任公司 | Cold-resistant cable material and preparation method thereof |
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| CN114591578A (en) * | 2022-01-19 | 2022-06-07 | 广州广日电气设备有限公司 | Cold-resistant and bending-resistant material, preparation method thereof and cold-resistant and bending-resistant cable |
| CN115093655A (en) * | 2022-07-11 | 2022-09-23 | 杭州万瑞达新材料有限公司 | Heat-resistant cold-resistant high-electrical-property polyvinyl chloride cable material and preparation method thereof |
| CN117247609B (en) * | 2023-11-17 | 2024-02-23 | 河南恒发科技股份有限公司 | Low-damping high-performance rubber for new energy automobile suspension and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5776993A (en) * | 1996-03-12 | 1998-07-07 | Korea Institute Of Footwear & Leather Technology | Thermoplastic PVC foam composition |
| CN102660089A (en) * | 2012-05-04 | 2012-09-12 | 宁波敏禾机械有限公司 | Low-volatile-separation PVC (Polyvinyl Chloride) particle composition and preparation method and application thereof |
| CN103289222A (en) * | 2012-03-01 | 2013-09-11 | 远东电缆有限公司 | High-fluidity PVC (polyvinyl chloride) sheath material |
| CN104194230A (en) * | 2014-09-24 | 2014-12-10 | 湖北科普达实业有限公司 | High-temperature-resistant, low-shrinkage, oil-proof and flame retardant polyvinyl chloride cable material and preparation method thereof |
| CN104403225A (en) * | 2013-12-19 | 2015-03-11 | 惠州乐庭电子线缆有限公司 | Wear-resistant oil-resistant flame-retardant polyvinyl chloride wire and cable material and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101948596B (en) * | 2010-10-27 | 2012-07-25 | 康泰塑胶科技集团有限公司 | Polyvinyl chloride composite material and preparation method thereof |
| CN103205070A (en) * | 2013-04-12 | 2013-07-17 | 江苏领瑞新材料科技有限公司 | Cold-resistant oilproof flame-retardant PVC (Polyvinyl Chloride) cable material and preparation method thereof |
| CN104558880B (en) * | 2013-10-09 | 2018-03-09 | 北京化工大学 | Transparent polyvinyl chloride material, it is prepared and application |
| CN104893152B (en) * | 2015-05-29 | 2019-03-26 | 江苏兴华胶带股份有限公司 | A kind of preparation method of environment-friendly cold polyvinyl chloride elastic composition |
-
2015
- 2015-05-29 CN CN201510290016.5A patent/CN104893152B/en active Active
- 2015-10-29 WO PCT/CN2015/093269 patent/WO2016192292A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5776993A (en) * | 1996-03-12 | 1998-07-07 | Korea Institute Of Footwear & Leather Technology | Thermoplastic PVC foam composition |
| CN103289222A (en) * | 2012-03-01 | 2013-09-11 | 远东电缆有限公司 | High-fluidity PVC (polyvinyl chloride) sheath material |
| CN102660089A (en) * | 2012-05-04 | 2012-09-12 | 宁波敏禾机械有限公司 | Low-volatile-separation PVC (Polyvinyl Chloride) particle composition and preparation method and application thereof |
| CN104403225A (en) * | 2013-12-19 | 2015-03-11 | 惠州乐庭电子线缆有限公司 | Wear-resistant oil-resistant flame-retardant polyvinyl chloride wire and cable material and preparation method thereof |
| CN104194230A (en) * | 2014-09-24 | 2014-12-10 | 湖北科普达实业有限公司 | High-temperature-resistant, low-shrinkage, oil-proof and flame retardant polyvinyl chloride cable material and preparation method thereof |
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