CN104893152A - Environment-friendly cold-resistant polyvinyl chloride elastomer composition and preparation method thereof - Google Patents
Environment-friendly cold-resistant polyvinyl chloride elastomer composition and preparation method thereof Download PDFInfo
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- CN104893152A CN104893152A CN201510290016.5A CN201510290016A CN104893152A CN 104893152 A CN104893152 A CN 104893152A CN 201510290016 A CN201510290016 A CN 201510290016A CN 104893152 A CN104893152 A CN 104893152A
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Abstract
The invention discloses an environment-friendly cold-resistant polyvinyl chloride elastomer composition and a preparation method thereof. The preparation method comprises the following steps: mixing a polyvinyl chloride resin, dialkyl terephthalate, synthetic vegetable oil, polar rubber, nano activated calcium carbonate, a calcium zinc composite stabilizer, a lubricant, an antioxidant and a pigment in a kneader; after the temperature of the mixture reaches 90-100 DEG C, discharging, cooling, and carrying out extrusion granulation on the cooled mixture in a double screw extruder, wherein the Shore hardness of the elastomer composition at -5 DEG C is lower than 80. The elastomer composition has the advantages of excellent low-temperature toughness, high mechanical strength, high thermal aging resistance, environment friendliness, no toxicity, excellent comprehensive properties and the like, and is especially suitable for preparing escalator balance compensation chain sheaths, door/window and vehicle window seals, insulation sheaths of wires and cables and the like.
Description
[technical field]
The present invention relates to Material Field, particularly relate to a kind of environment-friendly cold polyvinyl chloride elastic composition and preparation method thereof.
[background technology]
Polyvinyl chloride elastomerics has cheap, mechanical property can be in harmonious proportion the features such as good flame resistance, is applicable to prepare elevator balanced compensated chain sheath, the insulating sheath of electric wire and numerous occasion such as door and window and vehicle window strip of paper used for sealing.But there is certain defect in polyvinyl chloride elastomerics in the feature of environmental protection and low-temperature flexibility etc.
So far, existing many composition and preparation methods that patent reports low temperature resistant or winter hardiness polyvinyl chloride elastomer material.If application number is the Chinese patents such as CN201210569416.6, CN201410284632.5, CN200810023863.5.Although the polyvinyl chloride elastomer material described by above-mentioned patent has certain resistance to low temperature, low-temperature flexibility is good, but its primary plasticizer used is phthalic ester plasticizer, and this kind of softening agent can be detrimental to health, and does not reach environmental requirement.
In order to meet the requirement of environmental protection, have and patent reports environmentally friendly polyvinyl chloride elastomerics.Application number is CN200910102369.2, CN201310464355.1, CN201010508484.2, CN201310754691.X, CN201110199511.7, the patents such as CN201310242694.5 and CN201210106293.2 all disclose the elastomeric composition of environmental protection polyvinyl chloride and preparation method, prepared elastomerics has the excellent feature of environmental protection, to human body and environmental pollution very few, but its toughner used and softening agent low-temperature performance poor, make elastomerics meeting under low temperature (less than-40 DEG C) condition brittle, have a strong impact on the work-ing life of elastomerics under extremely cold environment.Meanwhile, the polyvinyl chloride elastomerics some patents disclosing environment-friendly cold is also had.As application number in CN201310473887.1 patent the toughner that uses be silicon rubber, poor with the consistency in PVC base system, cause elastomeric normal temperature toughness and low-temperature flexibility to be all affected, resistance to low temperature is undesirable.Application number is that CN201210161975.3 discloses a kind of cold-resistant environment-friendly polyvinyl chloride base Special cable material, and the diethylene glycol dibenzoate softening agent raw materials cost used is high, limits its application in civilian sphere.Therefore the polyvinyl chloride elastomerics developing the excellent combination properties such as a kind of environment-protecting asepsis, cold-resistant, mechanical strength is high seems particularly important.
[summary of the invention]
The object of the present invention is to provide a kind of environment-friendly cold polyvinyl chloride elastic composition, have safety and environmental protection, cold-resistant heat-resisting, anti-aging, mechanical strength advantages of higher, it can still keep higher toughness under low temp operation environment.
In order to solve the problem, technical solution of the present invention is: a kind of environment-friendly cold polyvinyl chloride elastic composition, comprise polyvinyl chloride (PVC) RESINS, environmental protection compound Plasticising system, toughner, calcium zinc system one package stabilizer, lubricant, oxidation inhibitor and pigment, described environmental protection compound Plasticising system comprises dimethyl terephthalate ester and synthesis vegetable oil esters, described toughner comprises polar rubber and nm-class active calcium carbonate, shore hardness is lower than 80-5 DEG C time for described elastic composition, and in described dimethyl terephthalate ester, alkyl comprises 7 ~ 12 carbon atoms.
Further, described elastic composition each component calculates by weight and comprises: the pigment of the nm-class active calcium carbonate of the synthesis vegetable oil esters of the polyvinyl chloride (PVC) RESINS of 100 weight parts, the dimethyl terephthalate ester of 50 ~ 90 weight parts, 10 ~ 40 weight parts, the polar rubber of 5 ~ 20 weight parts, 5 ~ 30 weight parts, the calcium-zinc composite stabilizing agent of 4 ~ 8 weight parts, the lubricant of 1 ~ 2 weight part, the oxidation inhibitor of 0.2 ~ 1 weight part and 0.5 ~ 3 weight part.
Further, described synthesis vegetable oil esters is formed through epoxidation or epoxy group(ing) esterification modification by vegetables oil, and described vegetables oil is one or more compositions in soybean oil, oleum lini, Viscotrol C, Thistle oil and Trisun Oil R 80.
Further, described polar rubber is the one in ethylene-vinyl acetate copolymer rubber, urethanes and polyacrylic rubber.
Further, in described ethylene-vinyl acetate copolymer rubber, vinyl acetate weight percent content is 40 ~ 70%.
Further, the mean diameter of described nm-class active calcium carbonate is between 60 ~ 100nm.
Further, described lubricant is the one in Zinic stearas, stearic acid and polyethylene wax.
Further, described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 2,2'-methylene radical-bis-(4-methyl-6-tert-butylphenol), three [2.4-di-tert-butyl-phenyl] phosphorous acid ester, one or both compositions in triphenyl phosphite.
Further, described pigment is the one in high-carbon black pigment and rutile titanium dioxide.
The present invention also provides the preparation method of above-mentioned environment-friendly cold polyvinyl chloride elastic composition, comprises the steps:
Step one: be uniformly mixed in kneader by each component, utilizes the heat of friction stirring generation that mixture temperature is raised;
Step 2: discharging after each component mixture temperature rises to 90-100 DEG C in kneader, sends into cooling and stirring device and is cooled to less than 45 DEG C;
Step 3: cooled mixture is placed in two rank screw extrusion press extrudes and makes material, described pair of rank screw extrusion press comprises twin screw extruder and single screw extrusion machine, the temperature of described twin screw extruder four heating zone and extrusion die is respectively: T1=85 ~ 100 DEG C, T2=100 ~ 120 DEG C, T3=120 ~ 140 DEG C, T4=130 ~ 150 DEG C, T mould=130 ~ 150 DEG C; The temperature of described single screw extrusion machine heating zone and extrusion die controls, at 110 ~ 130 DEG C and 120 ~ 140 DEG C, to obtain polyvinyl chloride elastic composition respectively, its-5 DEG C time shore hardness lower than 80.
Polyvinyl chloride elastomerics prepared by the present invention has excellent in low temperature toughness, the advantages such as mechanical strength is high, heat-resistant aging good, environment-protecting asepsis, excellent combination property, is particularly useful for making the insulating sheath etc. of elevator balanced compensated chain sheath, door and window and vehicle window strip of paper used for sealing and electric wire.
Above-mentioned polyvinyl chloride elastic composition has following beneficial effect:
(1) by adopting safe environment protection type softening agent, to environment and human body without potential safety hazard, meet environmental requirement, the plasticization effect that dimethyl terephthalate ester has and phthalic ester plasticizer is same excellent and excellent cold tolerance, under cryogenic can not inactivation; Synthesis Vegetable oil lipoprotein has low volatility, also can be used as the feature of thermo-stabilizer; Two kinds of softening agent by reasonably with the use of, play respective performance advantage and can give polyvinyl chloride more excellent plasticization effect;
(2) adopt the polar rubber with winter hardiness and nm-class active calcium carbonate as toughner, make elastomerics still can keep good toughness under cryogenic; Nm-class active calcium carbonate can fully disperse in PVC base system as toughner and weighting agent, greatly improves elastomeric toughness and intensity, plays double effect that is toughness reinforcing and that strengthen.Two kinds of toughner combinationally use, and produce synergistic effect, to the elastomeric normal temperature toughness of raising, keep low-temperature flexibility to have unusual effect;
(3) using environment-friendly type liquid state calcium zinc system one package stabilizer, to environment and human body to there is not harm hidden danger, meeting environmental requirement.
[embodiment]
Below in conjunction with embodiment, the present invention is further detailed explanation.
In order to those skilled in the art can understand technical scheme provided by the present invention better, set forth below in conjunction with specific embodiment.
A kind of environment-friendly cold polyvinyl chloride elastic composition that the present invention relates to, comprise polyvinyl chloride (PVC) RESINS, environmental protection compound Plasticising system, toughner, calcium zinc system one package stabilizer, lubricant, oxidation inhibitor and pigment, described environmental protection compound Plasticising system comprises dimethyl terephthalate ester and synthesis vegetable oil esters, described toughner comprises polar rubber and nm-class active calcium carbonate, shore hardness is lower than 80-5 DEG C time for described elastic composition, and in described dimethyl terephthalate ester, alkyl comprises 7 ~ 12 carbon atoms.
Elastic composition each component calculates by weight and comprises: the pigment of the nm-class active calcium carbonate of the synthesis vegetable oil esters of the polyvinyl chloride (PVC) RESINS of 100 weight parts, the dimethyl terephthalate ester of 50 ~ 90 weight parts, 10 ~ 40 weight parts, the polar rubber of 5 ~ 20 weight parts, 5 ~ 30 weight parts, the calcium-zinc composite stabilizing agent of 4 ~ 8 weight parts, the lubricant of 1 ~ 2 weight part, the oxidation inhibitor of 0.2 ~ 1 weight part and 0.5 ~ 3 weight part.
Synthesis vegetable oil esters is formed through epoxidation or epoxy group(ing) esterification modification by vegetables oil, and described vegetables oil is one or more compositions in soybean oil, oleum lini, Viscotrol C, Thistle oil and Trisun Oil R 80; Described polar rubber is the one in ethylene-vinyl acetate copolymer rubber, urethanes and polyacrylic rubber; In described ethylene-vinyl acetate copolymer rubber, vinyl acetate weight percent content is 40 ~ 70%; The mean diameter of described nm-class active calcium carbonate is between 60 ~ 100nm; Described lubricant is the one in Zinic stearas, stearic acid and polyethylene wax; Described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 2,2'-methylene radical-bis-(4-methyl-6-tert-butylphenol), three [2.4-di-tert-butyl-phenyl] phosphorous acid ester, one or both compositions in triphenyl phosphite; Described pigment is the one in high-carbon black pigment and rutile titanium dioxide.
The present invention also provides the preparation method of above-mentioned environment-friendly cold polyvinyl chloride elastic composition, comprises the steps:
Step one: be uniformly mixed in kneader by each component, utilizes the heat of friction stirring generation that mixture temperature is raised;
Step 2: discharging after each component mixture temperature rises to 90-100 DEG C in kneader, sends into cooling and stirring device and is cooled to less than 45 DEG C;
Step 3: cooled mixture is placed in two rank screw extrusion press extrudes and makes material, described pair of rank screw extrusion press comprises twin screw extruder and single screw extrusion machine, the temperature of described twin screw extruder four heating zone and extrusion die is respectively: T1=85 ~ 100 DEG C, T2=100 ~ 120 DEG C, T3=120 ~ 140 DEG C, T4=130 ~ 150 DEG C, T mould=130 ~ 150 DEG C; The temperature of described single screw extrusion machine heating zone and extrusion die controls, at 110 ~ 130 DEG C and 120 ~ 140 DEG C, to obtain polyvinyl chloride elastic composition respectively, its-5 DEG C time shore hardness lower than 80.
Embodiment one:
By the polyvinyl chloride (PVC) RESINS of 100 weight parts, the dioctyl terephthalate of 75 weight parts, the epoxy soybean oil of 25 weight parts, the urethanes of 10 weight parts, the nm-class active calcium carbonate of 15 weight parts, the calcium-zinc composite stabilizing agent of 5 weight parts, the Zinic stearas of 1.5 weight parts, four [β-(3 of 0.6 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic acid] high-carbon black pigment of pentaerythritol ester and 1 weight part is uniformly mixed in kneader high speed, discharging after the heat of friction that stirring produces makes mixture temperature rise to 90-100 DEG C, mixture is sent into cooling and stirring device and is cooled to less than 45 DEG C, again cooled mixture is placed in extruding pelletization on the screw extrusion press of two rank, wherein the temperature of twin screw extruder four heating zone and extrusion die is respectively: T
1=85 ~ 100 DEG C, T
2=100 ~ 120 DEG C, T
3=120 ~ 140 DEG C, T
4=130 ~ 150 DEG C, T
mould=130 ~ 150 DEG C, the temperature of single screw extrusion machine heating zone and extrusion die controls respectively at 110 ~ 130 DEG C and 120 ~ 140 DEG C.It is 2mm or 6mm print that the pellet extruded is hot pressed into thickness on vulcanizing press, and cuts into satisfactory batten.
Embodiment two:
By the polyvinyl chloride (PVC) RESINS of 100 weight parts, terephthalic acid two heptyl ester of 90 weight parts, the epoxy group(ing) esterification oleum lini of 10 weight parts, the ethylene-vinyl acetate copolymer (vinyl acetate between to for plastic weight percent is 40%) of 20 weight parts, the nm-class active calcium carbonate of 5 weight parts, the calcium-zinc composite stabilizing agent of 8 weight parts, the polyethylene wax of 1 weight part, four [β-(3 of 0.2 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic acid] rutile titanium dioxide of pentaerythritol ester and 3 weight parts is uniformly mixed in kneader high speed, discharging after the heat of friction that stirring produces makes mixture temperature rise to 90-100 DEG C, mixture is sent into cooling and stirring device and is cooled to less than 45 DEG C, again cooled mixture is placed in extruding pelletization on the screw extrusion press of two rank, wherein the temperature of twin screw extruder four heating zone and extrusion die is respectively: T
1=85 ~ 100 DEG C, T
2=100 ~ 120 DEG C, T
3=120 ~ 140 DEG C,
t4=130 ~ 150 DEG C, T
mould=130 ~ 150 DEG C, the temperature of single screw extrusion machine heating zone and extrusion die controls respectively at 110 ~ 130 DEG C and 120 ~ 140 DEG C.It is 2mm or 6mm print that the pellet extruded is hot pressed into thickness on vulcanizing press, and cuts into satisfactory batten.
Embodiment three:
By the polyvinyl chloride (PVC) RESINS of 100 weight parts, terephthalic acid two (dodecyl) ester of 70 weight parts, the epoxy Thistle oil of 40 weight parts, the polyacrylic rubber of 5 weight parts, the nm-class active calcium carbonate of 30 weight parts, the calcium-zinc composite stabilizing agent of 8 weight parts, the Zinic stearas of 2 weight parts, four [β-(3 of 0.5 weight part, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, three [2.4-di-tert-butyl-phenyl] phosphorous acid esters of 0.2 weight part and the high-carbon black pigment of 1.5 weight parts are uniformly mixed in kneader high speed, discharging after the heat of friction that stirring produces makes mixture temperature rise to 90-100 DEG C, mixture is sent into cooling and stirring device and is cooled to less than 45 DEG C, again cooled mixture is placed in extruding pelletization on the screw extrusion press of two rank, wherein the temperature of twin screw extruder four heating zone and extrusion die is respectively: T
1=85 ~ 100 DEG C, T
2=100 ~ 120 DEG C, T
3=120 ~ 140 DEG C, T
4=130 ~ 150 DEG C, T
mould=130 ~ 150 DEG C, the temperature of single screw extrusion machine heating zone and extrusion die controls respectively at 110 ~ 130 DEG C and 120 ~ 140 DEG C.It is 2mm or 6mm print that the pellet extruded is hot pressed into thickness on vulcanizing press, and cuts into satisfactory batten.
Embodiment four:
By the polyvinyl chloride (PVC) RESINS of 100 weight parts, the dioctyl terephthalate of 70 weight parts, the epoxy castor oil of 30 weight parts, the urethanes of 20 weight parts, the nm-class active calcium carbonate of 20 weight parts, the calcium-zinc composite stabilizing agent of 6 weight parts, the Zinic stearas of 1 weight part, three [2.4-di-tert-butyl-phenyl] phosphorous acid ester of 0.6 weight part, the triphenyl phosphite of 0.2 weight part and the high-carbon black pigment of 1 weight part are uniformly mixed in kneader high speed, discharging after the heat of friction that stirring produces makes mixture temperature rise to 90-100 DEG C, mixture is sent into cooling and stirring device and is cooled to less than 45 DEG C, again cooled mixture is placed in extruding pelletization on the screw extrusion press of two rank, wherein the temperature of twin screw extruder four heating zone and extrusion die is respectively: T
1=85 ~ 100 DEG C, T
2=100 ~ 120 DEG C, T
3=120 ~ 140 DEG C, T
4=130 ~ 150 DEG C, T
mould=130 ~ 150 DEG C, the temperature of single screw extrusion machine heating zone and extrusion die controls respectively at 110 ~ 130 DEG C and 120 ~ 140 DEG C.It is 2mm or 6mm print that the pellet extruded is hot pressed into thickness on vulcanizing press, and cuts into satisfactory batten.
Embodiment five:
By the polyvinyl chloride (PVC) RESINS of 100 weight parts, terephthalic acid two (dodecyl) ester of 75 weight parts, the epoxy Trisun Oil R 80 of 20 weight parts, the ethylene-vinyl acetate copolymer (vinyl acetate between to for plastic weight percent is 70%) of 15 weight parts, the nm-class active calcium carbonate of 10 weight parts, the calcium-zinc composite stabilizing agent of 5 weight parts, the polyethylene wax of 1 weight part, three [2.4-di-tert-butyl-phenyl] phosphorous acid esters of 0.6 weight part and the high-carbon black pigment of 0.5 weight part are uniformly mixed in kneader high speed, discharging after the heat of friction that stirring produces makes mixture temperature rise to 90-100 DEG C, mixture is sent into cooling and stirring device and is cooled to less than 45 DEG C, again cooled mixture is placed in extruding pelletization on the screw extrusion press of two rank, wherein the temperature of twin screw extruder four heating zone and extrusion die is respectively: T
1=85 ~ 100 DEG C, T
2=100 ~ 120 DEG C, T
3=120 ~ 140 DEG C, T
4=130 ~ 150 DEG C, T
mould=130 ~ 150 DEG C, the temperature of single screw extrusion machine heating zone and extrusion die controls respectively at 110 ~ 130 DEG C and 120 ~ 140 DEG C.It is 2mm or 6mm print that the pellet extruded is hot pressed into thickness on vulcanizing press, and cuts into satisfactory batten.
Comparative example one:
By the polyvinyl chloride (PVC) RESINS of 100 weight parts, the dioctyl terephthalate of 75 weight parts, the epoxy soybean oil of 25 weight parts, the chlorinatedpolyethylene of 10 weight parts, 15 weight part order numbers are the light calcium carbonate of 1200, the calcium-zinc composite stabilizing agent of 5 weight parts, the lubricant of 1.5 weight parts, three [2.4-di-tert-butyl-phenyl] phosphorous acid esters of 0.6 weight part and the high-carbon black pigment of 1 weight part are uniformly mixed in kneader high speed, discharging after the heat of friction that stirring produces makes mixture temperature rise to 90-100 DEG C, mixture is sent into cooling and stirring device and is cooled to less than 45 DEG C, again cooled mixture is placed in extruding pelletization on the screw extrusion press of two rank, wherein the temperature of twin screw extruder four heating zone and extrusion die is respectively: T
1=85 ~ 100 DEG C, T
2=100 ~ 120 DEG C, T
3=120 ~ 140 DEG C, T
4=130 ~ 150 DEG C, T
mould=130 ~ 150 DEG C, the temperature of single screw extrusion machine heating zone and extrusion die controls respectively at 110 ~ 130 DEG C and 120 ~ 140 DEG C.It is 2mm or 6mm print that the pellet extruded is hot pressed into thickness on vulcanizing press, and cuts into satisfactory batten.
Comparative example two:
By the polyvinyl chloride (PVC) RESINS of 100 weight parts, the dioctyl terephthalate of 75 weight parts, the epoxy soybean oil of 25 weight parts, the urethanes of 10 weight parts, 15 weight part order numbers are the light calcium carbonate of 1200, the calcium-zinc composite stabilizing agent of 5 weight parts, the lubricant of 1.5 weight parts, three [2.4-di-tert-butyl-phenyl] phosphorous acid esters of 0.6 weight part and the high-carbon black pigment of 1 weight part are uniformly mixed in kneader high speed, discharging after the heat of friction that stirring produces makes mixture temperature rise to 90-100 DEG C, mixture is sent into cooling and stirring device and is cooled to less than 45 DEG C, again cooled mixture is placed in extruding pelletization on the screw extrusion press of two rank, wherein the temperature of twin screw extruder four heating zone and extrusion die is respectively: T
1=85 ~ 100 DEG C, T
2=100 ~ 120 DEG C,
t3=120 ~ 140 DEG C, T
4=130 ~ 150 DEG C, T
mould=130 ~ 150 DEG C, the temperature of single screw extrusion machine heating zone and extrusion die controls respectively at 110 ~ 130 DEG C and 120 ~ 140 DEG C.It is 2mm or 6mm print that the pellet extruded is hot pressed into thickness on vulcanizing press, and cuts into satisfactory batten.
Comparative example three:
By the polyvinyl chloride (PVC) RESINS of 100 weight parts, terephthalic acid two (dodecyl) ester of 75 weight parts, the epoxy Trisun Oil R 80 of 20 weight parts, the ethylene-vinyl acetate copolymer (vinyl acetate between to for plastic weight percent is 50%) of 3 weight parts, the nm-class active calcium carbonate of 10 weight parts, the calcium-zinc composite stabilizing agent of 5 weight parts, the lubricant of 1 weight part, three [2.4-di-tert-butyl-phenyl] phosphorous acid esters of 0.6 weight part and the high-carbon black pigment of 0.5 weight part are uniformly mixed in kneader high speed, discharging after the heat of friction that stirring produces makes mixture temperature rise to 90-100 DEG C, mixture is sent into cooling and stirring device and is cooled to less than 45 DEG C, again cooled mixture is placed in extruding pelletization on the screw extrusion press of two rank, wherein the temperature of twin screw extruder four heating zone and extrusion die is respectively: T
1=85 ~ 100 DEG C, T
2=100 ~ 120 DEG C, T
3=120 ~ 140 DEG C, T
4=130 ~ 150 DEG C, T
mould=130 ~ 150 DEG C, the temperature of single screw extrusion machine heating zone and extrusion die controls respectively at 110 ~ 130 DEG C and 120 ~ 140 DEG C.It is 2mm or 6mm print that the pellet extruded is hot pressed into thickness on vulcanizing press, and cuts into satisfactory batten.
Comparative example four:
By the polyvinyl chloride (PVC) RESINS of 100 weight parts, terephthalic acid two (dodecyl) ester of 75 weight parts, the epoxy Trisun Oil R 80 of 20 weight parts, the urethanes of 25 weight parts, the nm-class active calcium carbonate of 10 weight parts, the calcium-zinc composite stabilizing agent of 5 weight parts, the lubricant of 1 weight part, three [2.4-di-tert-butyl-phenyl] phosphorous acid esters of 0.6 weight part and the high-carbon black pigment of 0.5 weight part are uniformly mixed in kneader high speed, discharging after the heat of friction that stirring produces makes mixture temperature rise to 90-100 DEG C, mixture is sent into cooling and stirring device and is cooled to less than 45 DEG C, again cooled mixture is placed in extruding pelletization on the screw extrusion press of two rank, wherein the temperature of twin screw extruder four heating zone and extrusion die is respectively: T
1=85 ~ 100 DEG C, T
2=100 ~ 120 DEG C, T
3=120 ~ 140 DEG C, T
4=130 ~ 150 DEG C, T
mould=130 ~ 150 DEG C, the temperature of single screw extrusion machine heating zone and extrusion die controls respectively at 110 ~ 130 DEG C and 120 ~ 140 DEG C.It is 2mm or 6mm print that the pellet extruded is hot pressed into thickness on vulcanizing press, and cuts into satisfactory batten.
Comparative example five:
By the polyvinyl chloride (PVC) RESINS of 100 weight parts, terephthalic acid two (dodecyl) ester of 75 weight parts, the epoxy Trisun Oil R 80 of 20 weight parts, the polyacrylic rubber of 15 weight parts, the nm-class active calcium carbonate of 3 weight parts, the calcium-zinc composite stabilizing agent of 5 weight parts, the lubricant of 1 weight part, three [2.4-di-tert-butyl-phenyl] phosphorous acid esters of 0.6 weight part and the high-carbon black pigment of 0.5 weight part are uniformly mixed in kneader high speed, discharging after the heat of friction that stirring produces makes mixture temperature rise to 90-100 DEG C, mixture is sent into cooling and stirring device and is cooled to less than 45 DEG C, again cooled mixture is placed in extruding pelletization on the screw extrusion press of two rank, wherein the temperature of twin screw extruder four heating zone and extrusion die is respectively: T
1=85 ~ 100 DEG C, T
2=100 ~ 120 DEG C, T
3=120 ~ 140 DEG C, T
4=130 ~ 150 DEG C, T
mould=130 ~ 150 DEG C, the temperature of single screw extrusion machine heating zone and extrusion die controls respectively at 110 ~ 130 DEG C and 120 ~ 140 DEG C.It is 2mm or 6mm print that the pellet extruded is hot pressed into thickness on vulcanizing press, and cuts into satisfactory batten.
Comparative example six:
By the polyvinyl chloride (PVC) RESINS of 100 weight parts, terephthalic acid two (dodecyl) ester of 75 weight parts, the epoxy Trisun Oil R 80 of 20 weight parts, the ethylene-vinyl acetate copolymer (vinyl acetate between to for plastic weight percent is 60%) of 15 weight parts, the nm-class active calcium carbonate of 35 weight parts, the calcium-zinc composite stabilizing agent of 5 weight parts, the lubricant of 1 weight part, three [2.4-di-tert-butyl-phenyl] phosphorous acid esters of 0.6 weight part and the high-carbon black pigment of 0.5 weight part are uniformly mixed in kneader high speed, discharging after the heat of friction that stirring produces makes mixture temperature rise to 90-100 DEG C, mixture is sent into cooling and stirring device and is cooled to less than 45 DEG C, again cooled mixture is placed in extruding pelletization on the screw extrusion press of two rank, wherein the temperature of twin screw extruder four heating zone and extrusion die is respectively: T
1=85 ~ 100 DEG C, T
2=100 ~ 120 DEG C, T
3=120 ~ 140 DEG C, T
4=130 ~ 150 DEG C, T
mould=130 ~ 150 DEG C, the temperature of single screw extrusion machine heating zone and extrusion die controls respectively at 110 ~ 130 DEG C and 120 ~ 140 DEG C.It is 2mm or 6mm print that the pellet extruded is hot pressed into thickness on vulcanizing press, and cuts into satisfactory batten.
Batten in above-described embodiment and comparative example is carried out the test of tensile strength, elongation at break, thermal ageing, the instantaneous hardness of low temperature and ballistic method embrittlement temperature, obtains out following result:
As can be seen from test result, the shore hardness of comparative example-5 DEG C time is all more than 80, cold-resistant, resistant to thermal aging, mechanical strength etc. are all poor than embodiment.
Above-mentioned explanation illustrate and describes the preferred embodiments of the present invention, as previously mentioned, be to be understood that the present invention is not limited to the form disclosed by this paper, should not regard the eliminating to other embodiments as, and can be used for other combinations various, amendment and environment, and can in invention contemplated scope described herein, changed by the technology of above-mentioned instruction or association area or knowledge.And the change that those skilled in the art carry out and change do not depart from the spirit and scope of the present invention, then all should in the protection domain of claims of the present invention.
Claims (10)
1. an environment-friendly cold polyvinyl chloride elastic composition, it is characterized in that, comprise polyvinyl chloride (PVC) RESINS, environmental protection compound Plasticising system, toughner, calcium zinc system one package stabilizer, lubricant, oxidation inhibitor and pigment, described environmental protection compound Plasticising system comprises dimethyl terephthalate ester and synthesis vegetable oil esters, described toughner comprises polar rubber and nm-class active calcium carbonate, shore hardness is lower than 80-5 DEG C time for described elastic composition, and in described dimethyl terephthalate ester, alkyl comprises 7 ~ 12 carbon atoms.
2. environment-friendly cold polyvinyl chloride elastic composition as claimed in claim 1, it is characterized in that, described elastic composition each component calculates by weight and comprises: the pigment of the nm-class active calcium carbonate of the synthesis vegetable oil esters of the polyvinyl chloride (PVC) RESINS of 100 weight parts, the dimethyl terephthalate ester of 50 ~ 90 weight parts, 10 ~ 40 weight parts, the polar rubber of 5 ~ 20 weight parts, 5 ~ 30 weight parts, the calcium-zinc composite stabilizing agent of 4 ~ 8 weight parts, the lubricant of 1 ~ 2 weight part, the oxidation inhibitor of 0.2 ~ 1 weight part and 0.5 ~ 3 weight part.
3. environment-friendly cold polyvinyl chloride elastic composition as claimed in claim 1 or 2, it is characterized in that, described synthesis vegetable oil esters is formed through epoxidation or epoxy group(ing) esterification modification by vegetables oil, and described vegetables oil is one or more compositions in soybean oil, oleum lini, Viscotrol C, Thistle oil and Trisun Oil R 80.
4. environment-friendly cold polyvinyl chloride elastic composition as claimed in claim 1 or 2, it is characterized in that, described polar rubber is the one in ethylene-vinyl acetate copolymer rubber, urethanes and polyacrylic rubber.
5. environment-friendly cold polyvinyl chloride elastic composition as claimed in claim 4, it is characterized in that, in described ethylene-vinyl acetate copolymer rubber, vinyl acetate weight percent content is 40 ~ 70%.
6. environment-friendly cold polyvinyl chloride elastic composition as claimed in claim 1 or 2, it is characterized in that, the mean diameter of described nm-class active calcium carbonate is between 60 ~ 100nm.
7. environment-friendly cold polyvinyl chloride elastic composition as claimed in claim 1 or 2, it is characterized in that, described lubricant is the one in Zinic stearas, stearic acid and polyethylene wax.
8. environment-friendly cold polyvinyl chloride elastic composition as claimed in claim 1 or 2, it is characterized in that, described oxidation inhibitor is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 2,2'-methylene radical-bis-(4-methyl-6-tert-butylphenol), three [2.4-di-tert-butyl-phenyl] phosphorous acid ester, one or both compositions in triphenyl phosphite.
9. environment-friendly cold polyvinyl chloride elastic composition as claimed in claim 1 or 2, is characterized in that, described pigment is the one in high-carbon black pigment and rutile titanium dioxide.
10. the preparation method of environment-friendly cold polyvinyl chloride elastic composition as claimed in claim 1 or 2, is characterized in that, comprise the steps:
Step one: be uniformly mixed in kneader by each component, utilizes the heat of friction stirring generation that mixture temperature is raised;
Step 2: discharging after each component mixture temperature rises to 90-100 DEG C in kneader, sends into cooling and stirring device and is cooled to less than 45 DEG C;
Step 3: cooled mixture is placed in two rank screw extrusion press extrudes and makes material, described pair of rank screw extrusion press comprises twin screw extruder and single screw extrusion machine, the temperature of described twin screw extruder four heating zone and extrusion die is respectively: T1=85 ~ 100 DEG C, T2=100 ~ 120 DEG C, T3=120 ~ 140 DEG C, T4=130 ~ 150 DEG C, T mould=130 ~ 150 DEG C; The temperature of described single screw extrusion machine heating zone and extrusion die controls, at 110 ~ 130 DEG C and 120 ~ 140 DEG C, to obtain polyvinyl chloride elastic composition respectively, its-5 DEG C time shore hardness lower than 80.
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