A kind of heat-resistant polyvinyl chloride material and preparation method thereof and electric wire
Technical field
The present invention relates to pvc material technical field, more particularly, to a kind of heat-resistant polyvinyl chloride material and electric wire.
Background technology
The insulant that domestic electric wire adopts is generally heat-resistant polyvinyl chloride (pvc) material, as the insulant of electric wire,
Thermostability to heat-resistant polyvinyl chloride material can have high requirements, and heat-resisting pvc material meets insulating properties again and requires simultaneously,
10 need to be reached in 30 DEG C of specific insulations12More than ω cm.
The Chinese patent of Application No. 201410284164.1 disclose a kind of heat-resisting 105 DEG C of polyvinyl chloride cable materials and its
Preparation method, is prepared by the raw materials in: 100 parts of s-70 Corvic, and 15 parts~20 parts of Bisphenol A Type gathers
Carbonic ester, 8 parts~12 parts of chlorinated polyethylene, 25 parts~35 parts of trioctyl trimellitate (TOTM), 10 parts~15 parts of O-phthalic
Sour two isodecyl esters, 5 parts~10 parts of pentaerythritol stearate, 10 parts~15 parts of barium sulfate, 5 parts~10 parts of nanometer silicon ash
Stone, 4 parts~8 parts of compounded mix, 1 part~2 parts of anilinomethyl triethoxysilane, 5 parts~8 parts of Ca Zn composite is stable
Agent, 1 part~2 parts of barium stearate, 1 part~2 parts of ethylene bis stearamide, 10 parts~15 parts of Firebrake ZB, 5 parts~10 parts
Deca-BDE, 0.5 part~1 part of antioxidant 1035.
This Heat-resistant polyvinyl chloride cable material that prior art provides has excellent mechanical strength, heat stability, weather-proof
The performance such as ageing-resistant, wear-resisting, and good flame retardation effect, after flame extinction, flare can extinguish rapidly, will not prolong combustion other materials, burning
Shi Fayan amount is few, can at 105 DEG C life-time service, improve the service life of electric wire;But this heat-resistant polyvinyl chloride
The black brittleness of material is poor, simultaneously relatively costly, limits it and extensively applies.
Content of the invention
In view of this, it is an object of the invention to provide a kind of heat-resistant polyvinyl chloride material and preparation method thereof and electric wire,
The heat-resistant polyvinyl chloride material that the present invention provides has preferable black brittleness, and cost is relatively low simultaneously.
The invention provides a kind of heat-resistant polyvinyl chloride material, in parts by weight, the system of described heat-resistant polyvinyl chloride material
Standby raw material includes:
100 parts of polyvinyl chloride resin powder;
45 parts~52 parts of trioctyl trimellitate (TOTM);
22 parts~31 parts of filler, described filler includes Calcium Carbonate and Kaolin;
3 parts~8 parts of ca-zn complex stabilizer;
4 parts~7 parts of ethylene/n-butyl acrylate-hydroxyl elastomer;
1.5 parts~5 parts of fire retardant, described fire retardant includes sb2o3And/or sb2o3Succedaneum, described sb2o3Succedaneum
In parts by weight, comprising:
45 parts~46 parts of silicon dioxide;
30 parts~35 parts of magnesium oxide;
8 parts~9 parts of montmorillonite;
2 parts~2.5 parts of zinc oxide;
5 parts~5.5 parts of aluminium sesquioxide;
1 part~1.5 parts of copper oxide.
Preferably, described Calcium Carbonate and kaolinic mass ratio are (18~25): (4~6).
Preferably, described sb2o3Succedaneum is in parts by weight, comprising:
45.1 parts of silicon dioxide;
33.22 the magnesium oxide of part;
8.39 parts of montmorillonite;
2.05 parts of zinc oxide;
5.04 parts of aluminium sesquioxide;
1.05 parts of copper oxide.
Preferably, described sb2o3Succedaneum substitutes the sb of 30%~100% mass2o3.
Preferably, the degree of polymerization >=1300 of described polyvinyl chloride resin powder.
Preferably, described kaolinic granularity is 2000 mesh~3000 mesh.
Preferably, heating loss≤2% of described ca-zn complex stabilizer.
Preferably, the tensile break strength of described ethylene/n-butyl acrylate-hydroxyl elastomer be 480mpa~
500mpa.
The invention provides a kind of preparation method of heat-resistant polyvinyl chloride material, comprising:
By polyvinyl chloride resin powder, trioctyl trimellitate (TOTM), filler, ca-zn complex stabilizer, ethylene-acrylic acid just
Butyl ester-hydroxyl elastomer and fire retardant mixing, obtain mixture;Described filler includes Calcium Carbonate and Kaolin, described fire-retardant
Agent includes sb2o3And/or sb2o3Succedaneum, described sb2o3Succedaneum is in parts by weight, comprising: 45 parts~46 parts of titanium dioxide
Silicon;30 parts~35 parts of magnesium oxide;8 parts~9 parts of montmorillonite;2 parts~2.5 parts of zinc oxide;5 parts~5.5 parts of three oxidations
Two aluminum;1 part~1.5 parts of copper oxide;
Described mixture is kneaded, is obtained intermediate product;
Described intermediate product is vulcanized, is obtained heat-resistant polyvinyl chloride material.
In the preparing raw material of the heat-resistant polyvinyl chloride material that the present invention provides and preparation method thereof, the positive fourth of ethylene-acrylic acid
Ester-hydroxyl elastomer can improve the black brittleness of material, but elastomer is relatively costly;Kaolin can improve material
Electrical property simultaneously effective reduces the cost of product, but can reduce the mechanical performance of material, such as tensile property;The present invention is in system
Add the higher fire retardant of a small amount of cost performance in standby raw material, by the interaction of elastomer, Kaolin and fire retardant, with
When with the using cooperatively of other preparing raw materials, finally make the heat-resistant polyvinyl chloride material that the present invention provides have preferable low temperature crisp
Cost is relatively low simultaneously for property.Test result indicate that, the present invention provide heat-resistant polyvinyl chloride material black brittleness be -11 DEG C~-
21℃.
Additionally, the heat-resistant polyvinyl chloride material that the present invention provides also has preferable mechanical and physical performance and heat is stable
Property.Test result indicate that, the thermostability of the heat-resistant polyvinyl chloride material that the present invention provides is 136min~198min;Shore is hard
Degree a is 94~95, d is 60.
The invention provides a kind of electric wire, the heat-resistant polyvinyl chloride material described in technique scheme prepares, or
The heat-resistant polyvinyl chloride material that method described in technique scheme prepares prepares.
Heat-resistant polyvinyl chloride material described in technique scheme for the electric wire that the present invention provides prepares, therefore this
Electric wire also has preferable black brittleness, and cost is relatively low simultaneously.Additionally, the electric wire that the present invention provides also has preferable physical machine
Tool, electrical insulation capability and thermostability.
Specific embodiment
The enforcement it is clear that described will be clearly and completely described to the technical scheme in the embodiment of the present invention below
Example is only a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under the premise of not making creative work, broadly falls into the model of present invention protection
Enclose.
The invention provides a kind of heat-resistant polyvinyl chloride material, in parts by weight, preparing of described heat-resistant polyvinyl chloride is former
Material includes:
100 parts of polyvinyl chloride resin powder;
45 parts~52 parts of trioctyl trimellitate (TOTM);
22 parts~31 parts of filler, described filler includes Calcium Carbonate and Kaolin;
3 parts~8 parts of ca-zn complex stabilizer;
4 parts~7 parts of ethylene/n-butyl acrylate-hydroxyl elastomer;
1.5 parts~5 parts of fire retardant, described fire retardant includes sb2o3And/or sb2o3Succedaneum;Described sb2o3Succedaneum
In parts by weight, comprising:
45 parts~46 parts of silicon dioxide;
30 parts~35 parts of magnesium oxide;
8 parts~9 parts of montmorillonite;
2 parts~2.5 parts of zinc oxide;
5 parts~5.5 parts of aluminium sesquioxide;
1 part~1.5 parts of copper oxide.
In the present invention, described polrvinyl chloride (pvc) resin-oatmeal is the main component of heat-resisting pvc material.The present invention's
In embodiment, the degree of polymerization >=1300 of described pvc resin-oatmeal.In an embodiment of the present invention, described pvc resin-oatmeal is apparent close
Degree can be 0.45g/ml~0.53g/ml.In an embodiment of the present invention, the fish-eye number of described pvc resin-oatmeal be 20/
400cm2~40/400cm2.In an embodiment of the present invention, the viscosity of described pvc resin-oatmeal is 107ml/g~118ml/g.
In an embodiment of the present invention, the residual vinyl chloride content in described pvc resin-oatmeal is 8ppm~10ppm.Reality in the present invention
Apply in example, the granularity of described pvc resin-oatmeal is 60 μm~250 μm;In other examples, the granularity of described pvc resin-oatmeal
For 100 μm~200 μm.In an embodiment of the present invention, the volatile content of described pvc resin-oatmeal is 0.4%~0.5%.?
In embodiments of the invention, in described pvc resin-oatmeal, number of impurity particles is 16~30.The present invention is to described pvc resin-oatmeal
Source there is no special restriction, using pvc resin-oatmeal well known to those skilled in the art, can by market buy obtain,
As the pvc resin-oatmeal that can be provided using Taiwan Plastic Group.
In the present invention, on the basis of the parts by weight of described pvc resin-oatmeal, described trioctyl trimellitate (TOTM) (totm)
Parts by weight are 45 parts~52 parts.In an embodiment of the present invention, the parts by weight of described totm are 48 parts~50 parts.
In an embodiment of the present invention, ester content >=99% in described totm.In an embodiment of the present invention, described
Color and luster number≤40 of totm.In an embodiment of the present invention, described totm 20 DEG C density be 0.987g/cm3~0.997g/
cm3.In an embodiment of the present invention, the acid number of described totm≤0.15mg koh/g.In an embodiment of the present invention, described
Specific insulation >=8 × 10 of totm11ω·cm.In an embodiment of the present invention, moisture≤0.15% of described totm.At this
In inventive embodiment, flash-point >=240 DEG C of described totm.The present invention does not have special restriction to the source of described totm, adopts
With the totm of mentioned kind well known to those skilled in the art, can be bought by market and obtain, such as Australia's ring can be praised using Zhejiang
Protect the totm that Science and Technology Co., Ltd. provides.
In the present invention, on the basis of the parts by weight of described pvc resin-oatmeal, the parts by weight of described filler are 22 parts
~31 parts.In an embodiment of the present invention, the parts by weight of described filler are 24 parts~28 parts.In the present invention, described fill out
Fill agent and include Calcium Carbonate and Kaolin.In an embodiment of the present invention, described Calcium Carbonate and kaolinic mass ratio be (18~
25): (4~6);In other examples, described Calcium Carbonate and kaolinic mass ratio are (20~22): (4.5~5.5).
In an embodiment of the present invention, described Calcium Carbonate is ground calcium carbonate.In an embodiment of the present invention, described carbonic acid
Purity >=98% of calcium.In an embodiment of the present invention, the whiteness of described Calcium Carbonate is 88~96.In embodiments of the invention
In, the granularity of described Calcium Carbonate is 2000 mesh~2500 mesh.In an embodiment of the present invention, the ph value of described Calcium Carbonate for 9~
9.5.In an embodiment of the present invention, in described Calcium Carbonate ferric oxide content≤0.03.In an embodiment of the present invention, institute
State content≤0.04 of silicon dioxide in Calcium Carbonate.In an embodiment of the present invention, in described Calcium Carbonate magnesium oxide content <
0.1.In an embodiment of the present invention, in described Calcium Carbonate alchlor content≤0.01.The present invention is to described Calcium Carbonate
Source does not have special restriction, using the Calcium Carbonate of mentioned kind well known to those skilled in the art, can be bought by market
Obtain, the ground calcium carbonate that such as can be provided using Fuyang Xin Chao Calcium Carbonate company limited.
In the present invention, described Kaolin is obtained by kaolinite calcining, and kaolinic structural formula is al4
[si4o10]·(oh)8, chemical skeleton symbol is al2o3·2sio2·2h2O, kaolinite is by [sio4] tetrahedral six side's stratum reticulares with
The layer structure that the octahedral layer of " oxyhydrogen aluminum stone " is combined in the ratio of 1:1, belongs to the octahedral phyllosilicate of 1:1 type,
Become the Kaolin of undefined structure after 600 DEG C~700 DEG C calcinings, at this moment the silicon oxide in Kaolin, aluminium oxide have very
Big activity;Layered crystal structure is changed into forming the powder body of porous fluffy pore structure after unformed shape crystal structure so as to table
Area is very big, has the ability of very strong adion, can adsorb the foreign ion in pvc resin-oatmeal, so that the present invention is provided
Heat-resisting pvc material there is preferable electrical insulation capability;Meanwhile, kaolinic proportion in the heat-resisting pvc material that the present invention provides
Higher, kaolinic cheap, the electrical insulation capability of heat-resisting pvc material can be improved after adding Kaolin, also can be largely
Reduce the cost of the heat-resisting pvc material that the present invention provides.
In an embodiment of the present invention, in described Kaolin, the content of silicon dioxide is 46%~47%.The present invention's
In embodiment, described kaolinic granularity is 2000 mesh~3000 mesh;In other examples, described kaolinic granularity is
2400 mesh~2600 mesh;In a further embodiment, described kaolinic granularity is 2500 mesh.The present invention is to described kaolinic
Source does not have special restriction, using Kaolin well known to those skilled in the art, can be bought by market and obtain.
In the present invention, on the basis of the parts by weight of described pvc resin-oatmeal, the weight of described ca-zn complex stabilizer
Number is 3 parts~8 parts.In an embodiment of the present invention, the parts by weight of described ca-zn complex stabilizer are 4 parts~6 parts.
In the present invention, the cost performance of described ca-zn complex stabilizer is higher, makes the heat-resisting pvc material that the present invention provides
There is cost while preferable thermostability relatively low.
In an embodiment of the present invention, the density of described ca-zn complex stabilizer is 1.7g/cm3~1.9g/cm3;At it
In his embodiment, the density of described ca-zn complex stabilizer is 1.8g/cm3.In an embodiment of the present invention, described ca-zn
The flash-point of complex stabilizer is 128 DEG C~132 DEG C.In an embodiment of the present invention, the heating of described ca-zn complex stabilizer subtracts
Amount≤2%.In an embodiment of the present invention, total metal content > 6% of described ca-zn complex stabilizer.Reality in the present invention
Apply in example, described ca-zn complex stabilizer includes calcium stearate, zinc stearate, beta diketone, nontoxic phosphite ester, antioxidant, water
Talcum, pe wax, ope, ebs.The present invention does not have special restriction to the source of described ca-zn complex stabilizer, using this area
The ca-zn complex stabilizer that can be used for pvc material known to technical staff, can be bought by market and obtain.
In the present invention, on the basis of the parts by weight of described pvc resin-oatmeal, described ethylene/n-butyl acrylate-hydroxyl
The parts by weight of elastomer are 4 parts~7 parts.In an embodiment of the present invention, described ethylene/n-butyl acrylate-hydroxyl elasticity
The parts by weight of body are 5 parts~6 parts.
In the present invention, described ethylene/n-butyl acrylate-hydroxyl elastomer has preferable cryogenic property, polarity, resists
The performance of uv, anti-chemistry and microbiologic(al) corrosion;Described ethylene/n-butyl acrylate-hydroxyl elastomer also can improve pvc's simultaneously
Thermostability, improves mobility, improves shock proof ability;The heat-resisting pvc material that the present invention provides is made to have preferable low temperature
Fragility.
In an embodiment of the present invention, the density of described ethylene/n-butyl acrylate-hydroxyl elastomer is 0.96g/cm3
~0.98g/cm3.In an embodiment of the present invention, described ethylene/n-butyl acrylate-hydroxyl elastomer is in 190 DEG C/2.16kg
Under conditions of melt flow rate (MFR) be 7.5g/10min~8.5g/10min;In other examples, described ethylene-acrylic acid
N-butyl-hydroxyl elastomer melt flow rate (MFR) under conditions of 190 DEG C/2.16kg is 8g/10min.
In an embodiment of the present invention, the tensile break strength of described ethylene/n-butyl acrylate-hydroxyl elastomer is
480mpa~500mpa.In an embodiment of the present invention, the tension failure of described ethylene/n-butyl acrylate-hydroxyl elastomer
Percentage elongation is 1200%~1250%;In other examples, the drawing of described ethylene/n-butyl acrylate-hydroxyl elastomer
Stretching elongation at break is 1230%.In an embodiment of the present invention, Shao of described ethylene/n-butyl acrylate-hydroxyl elastomer
Family name's hardness (a) is 55~60;In other examples, the shore hardness of described ethylene/n-butyl acrylate-hydroxyl elastomer
A () is 59.
In an embodiment of the present invention, the fusing point of described ethylene/n-butyl acrylate-hydroxyl elastomer is 55 DEG C~60
℃;In other examples, the fusing point of described ethylene/n-butyl acrylate-hydroxyl elastomer is 59 DEG C.Reality in the present invention
Apply in example, the heat distortion temperature of described ethylene/n-butyl acrylate-hydroxyl elastomer is -50 DEG C~-55 DEG C;Other real
Apply in example, the heat distortion temperature of described ethylene/n-butyl acrylate-hydroxyl elastomer is -54 DEG C.In embodiments of the invention
In, the melt temperature of described ethylene/n-butyl acrylate-hydroxyl elastomer is 55 DEG C~60 DEG C;In other examples, institute
The melt temperature stating ethylene/n-butyl acrylate-hydroxyl elastomer is 59 DEG C.
The present invention does not have special restriction to the source of described ethylene/n-butyl acrylate-hydroxyl elastomer, using ability
The ethylene/n-butyl acrylate of the mentioned kind known to field technique personnel-hydroxyl elastomer, can be bought by market, such as can
The product of the hp441 model being provided using Du Pont.
In the present invention, on the basis of the parts by weight of described pvc resin-oatmeal, the parts by weight of described fire retardant are 1.5
Part~5 parts.In an embodiment of the present invention, the parts by weight of described fire retardant are 2 parts~4 parts;In other examples, institute
The parts by weight stating fire retardant are 3 parts.
In the present invention, described fire retardant includes sb2o3And/or sb2o3Substitute.In an embodiment of the present invention, described
sb2o3The sb of alternative 30%~100% mass of substitute2o3;In other examples, described sb2o3Substitute is alternative
The sb of 40%~90% mass2o3;In a further embodiment, described sb2o3Alternative 50%~80% mass of substitute
sb2o3.
In the present invention, using sb2o3As fire retardant, it is possible to reduce the consumption of fire retardant, so that what the present invention provided
Pvc heat proof material has preferable mechanical and physical performance;And sb2o3Can have synergism with the halogen in pvc resin-oatmeal,
The black brittleness of the heat-resisting pvc material of present invention offer is be provided;Simultaneously as the amount of flame-retardant agent that the present invention adopts
Less, effect is good, reduces the cost of the heat-resisting pvc material of present invention offer.
In an embodiment of the present invention, described sb2o3Content >=99.9% of middle stibate.In an embodiment of the present invention,
Described sb2o3Whiteness be 96%~97%.In the present invention is in example, described sb2o3Granularity be 0.3 μm~0.6 μm.
The present invention is to described sb2o3Source there is no special restriction, using sb well known to those skilled in the art2o3, can be by city
Field is bought and is obtained, such as can be using the sb of 998 models of Shanghai Niu Weisi chemical industry offer2o3.
In the present invention, sb can be adopted2o3Substitute substitutes sb2o3As fire retardant, fire retardant equally can also be reduced
Consumption, so that the pvc heat proof material that the present invention provides has preferable mechanical and physical performance;And sb2o3Substitute can be with
Halogen in pvc resin-oatmeal has synergism, improves the black brittleness of the heat-resisting pvc material of present invention offer;Meanwhile, by
The amount of flame-retardant agent adopting in the present invention is few, effect is good, and adopts sb2o3Substitute substitutes all or part of sb2o3, can
Reduce the cost of the heat-resisting pvc material that the present invention provides further.
In the present invention, described sb2o3Substitute is a kind of inorganic fire-retarded assistance agent, can be used in combination with halogen, also can be used as antimony
Adjuvant, with sb2o3Compound, sb can be greatly reduced2o3Consumption.In the present invention, in parts by weight, described sb2o3Substitute
Thing includes:
45 parts~46 parts of silicon dioxide;
30 parts~35 parts of magnesium oxide;
8 parts~9 parts of montmorillonite;
2 parts~2.5 parts of zinc oxide;
5 parts~5.5 parts of aluminium sesquioxide;
1 part~1.5 parts of copper oxide.
In an embodiment of the present invention, in parts by weight, described sb2o3Substitute includes 45.1 parts of silicon dioxide,
33.22 parts of magnesium oxide, 8.39 parts of montmorillonite, 2.05 parts of zinc oxide, 5.04 parts of aluminium sesquioxide, 1.05 parts of oxidation
Copper.
In an embodiment of the present invention, described sb2o3The particle diameter of substitute is 0.3 micron~0.9 micron.The present invention's
In embodiment, described sb2o3The whiteness of substitute is 99%.In an embodiment of the present invention, described sb2o3The ph value of substitute
For 8~9.In an embodiment of the present invention, described sb2o3The moisture of substitute is 0.4%.In an embodiment of the present invention, described
sb2o3Mechanical property conservation rate > 90%.
The present invention is to described sb2o3The source of substitute does not have special restriction, can be bought by market and obtain, such as using deep
The product of the lhx-999 model that the prosperous Science and Technology Ltd. of ditch between fields joint provides.
The invention provides a kind of preparation method of heat-resistant polyvinyl chloride material, comprising:
By polyvinyl chloride resin powder, trioctyl trimellitate (TOTM), filler, ca-zn complex stabilizer, ethylene-acrylic acid just
Butyl ester-hydroxyl elastomer and fire retardant mixing, obtain mixture;Described filler includes Calcium Carbonate and Kaolin, described fire-retardant
Agent includes sb2o3And/or sb2o3Succedaneum, described sb2o3Succedaneum is in parts by weight, comprising: 45 parts~46 parts of titanium dioxide
Silicon;30 parts~35 parts of magnesium oxide;8 parts~9 parts of montmorillonite;2 parts~2.5 parts of zinc oxide;5 parts~5.5 parts of three oxidations
Two aluminum;1 part~1.5 parts of copper oxide;
Described mixture is kneaded, is obtained intermediate product;
Described intermediate product is vulcanized, is obtained heat-resistant polyvinyl chloride material.
The present invention is by polyvinyl chloride resin powder, trioctyl trimellitate (TOTM), filler, ca-zn complex stabilizer, ethylene-the third
Olefin(e) acid N-butyl-hydroxyl elastomer and fire retardant mixing, obtain mixture.In the present invention, described polyvinyl chloride resin powder, partially
Benzenetricarboxylic acid three monooctyl ester, filler, ca-zn complex stabilizer, ethylene/n-butyl acrylate-hydroxyl elastomer and the kind of fire retardant
Polyvinyl chloride resin powder described in class, source and parts by weight and technique scheme, trioctyl trimellitate (TOTM), filler, ca-
Zn complex stabilizer, ethylene/n-butyl acrylate-hydroxyl elastomer is consistent with parts by weight with the species of fire retardant, source,
This repeats no more.
In an embodiment of the present invention, can mix under conditions of stirring.In an embodiment of the present invention, can be in glass
Mix in glass mixing ware.
After obtaining mixture, described mixture is kneaded by the present invention, obtains intermediate product.In embodiments of the invention
In, the temperature of described mixing is 150 DEG C~170 DEG C;In other examples, the temperature of described mixing is 165 DEG C~175
℃;In a further embodiment, the temperature of described mixing is 160 DEG C.The present invention does not have special limit to the time of described mixing
System, described mixture plasticizing is good, uniformly can stop mixing.In an embodiment of the present invention, time≤20 of described mixing
Minute.In an embodiment of the present invention, the equipment of described mixing can be opening rubber mixing machine, and such as Shanghai balance level device science and technology has
The rubber mixing machine of the hz-7015 model that limit company provides.
After obtaining intermediate product, described intermediate product is vulcanized by the present invention, obtains heat-resistant polyvinyl chloride material.At this
In inventive embodiment, the temperature of described sulfuration is 160 DEG C~180 DEG C;In other examples, the temperature of described sulfuration is
165 DEG C~175 DEG C;In a further embodiment, the temperature of described sulfuration is 170 DEG C.In an embodiment of the present invention, described sulfur
Preheating time during change is 3 minutes~7 minutes;In other examples, the preheating time in described sulfidation is 4
Minute~6 minutes;In a further embodiment, the preheating time in described sulfidation is 5 minutes.
In an embodiment of the present invention, the pressing time in described sulfidation is 3 minutes~7 minutes;Other real
Apply in example, the pressing time in described sulfidation is 4 minutes~6 minutes;In a further embodiment, in described sulfidation
Pressing time be 5 minutes.In an embodiment of the present invention, the moulding pressure in described sulfidation is 19mpa~22mpa.
In an embodiment of the present invention, the cool time in described sulfidation is 3 minutes~7 minutes;Other real
Apply in example, the cool time in described sulfidation is 4 minutes~6 minutes;In a further embodiment, in described sulfidation
Cool time be 5 minutes.In an embodiment of the present invention, the equipment of described sulfuration can be compression molding instrument, such as Shanghai weighing apparatus
The vulcameter of the hz-7014 model that quasi- instrument Science and Technology Ltd. provides.
In the preparing raw material of the heat-resistant polyvinyl chloride material that the present invention provides and preparation method thereof, elastomer can improve material
The black brittleness of material, but elastomer is relatively costly;The electrical property that Kaolin can improve material simultaneously effective reduces product
The cost of product, but the mechanical performance of material can be reduced, such as tensile property;The present invention adds a small amount of sexual valence in preparing raw material
Relatively higher fire retardant, by the interaction of elastomer, Kaolin and fire retardant, the cooperation with other preparing raw materials simultaneously
Use, cost is relatively low simultaneously finally to make the heat-resistant polyvinyl chloride material that the present invention provides have preferable black brittleness.Additionally, this
The heat-resistant polyvinyl chloride material that invention provides also has preferable mechanical and physical performance and thermostability.
The invention provides a kind of electric wire, the heat-resistant polyvinyl chloride material described in technique scheme prepares, or
The heat-resistant polyvinyl chloride material that method described in technique scheme prepares prepares.
The present invention does not have special restriction to the preparation method of described electric wire, using utilization well known to those skilled in the art
The technical scheme of electric wire prepared by heat-resistant polyvinyl chloride material.In an embodiment of the present invention, can be by technique scheme
Carry out extrusion molding after described heat-resistant polyvinyl chloride material disintegrating, prepare electric wire.
In inventive embodiment, the equipment of described extrusion molding can be extruder.In an embodiment of the present invention, institute
The diameter stating extruder can be 25mm~35mm;In other examples, the diameter of described extruder can for 28mm~
32mm;In a further embodiment, the diameter of described extruder can be 30mm.In an embodiment of the present invention, described extrusion
The screw speed of machine is 1400 revs/min~1500 revs/min;In other examples, the screw speed of described extruder is
1440 revs/min~1480 revs/min.In an embodiment of the present invention, the linear velocity of described extruder is 220m/min~230m/
min;In other examples, the linear velocity of described extruder is 224m/min~226m/min;In a further embodiment,
The linear velocity of described extruder is 225m/min.
In an embodiment of the present invention, the preheating temperature of described extruder is 70 DEG C~80 DEG C;In other examples,
The preheating temperature of described extruder is 74 DEG C~76 DEG C;In a further embodiment, the preheating temperature of described extruder is 75 DEG C.
In an embodiment of the present invention, area's temperature of described extruder is 140 DEG C~160 DEG C;In other examples, described crowded
Go out Ji mono- area's temperature and be 145 DEG C~155 DEG C;In a further embodiment, area's temperature of described extruder is 150 DEG C.
In an embodiment of the present invention, two area's temperature of described extruder are 160 DEG C~180 DEG C;In other embodiments
In, two area's temperature of described extruder are 165 DEG C~175 DEG C;In a further embodiment, two area's temperature of described extruder are
170℃.In an embodiment of the present invention, three area's temperature of described extruder are 170 DEG C~190 DEG C;In other examples,
Three area's temperature of described extruder are 175 DEG C~185 DEG C;In a further embodiment, three area's temperature of described extruder are 180
℃.
In an embodiment of the present invention, four area's temperature of described extruder are 170 DEG C~190 DEG C;In other embodiments
In, four area's temperature of described extruder are 175 DEG C~185 DEG C;In a further embodiment, four area's temperature of described extruder are
180℃.In an embodiment of the present invention, five area's temperature of described extruder are 170 DEG C~190 DEG C;In other examples,
Five area's temperature of described extruder are 175 DEG C~185 DEG C;In a further embodiment, five area's temperature of described extruder are 180
℃.
In an embodiment of the present invention, six area's temperature of described extruder are 170 DEG C~190 DEG C;In other embodiments
In, six area's temperature of described extruder are 175 DEG C~185 DEG C;In a further embodiment, six area's temperature of described extruder are
180℃.In an embodiment of the present invention, seven area's temperature of described extruder are 175 DEG C~195 DEG C;In other examples,
Seven area's temperature of described extruder are 180 DEG C~190 DEG C;In a further embodiment, seven area's temperature of described extruder are 185
℃.
Heat-resistant polyvinyl chloride material described in technique scheme for the electric wire that the present invention provides prepares, therefore this
Electric wire also has preferable black brittleness, and cost is relatively low simultaneously.Additionally, the electric wire that the present invention provides also has preferably mechanical thing
Rationality energy, electrical insulation capability and thermostability.
The heat-resistant polyvinyl chloride material that the present invention is provided is according to gb/t1410-2006 " solid insulating material volume resistance
Rate and surface resistivity test method " standard, test its specific insulation, test result is, the resistance to hot polymerization that the present invention provides
Vinyl chloride material specific insulation at room temperature is 1.9 × 1014ω cm~2.3 × 1014ω cm, the body at 30 DEG C
Long-pending resistivity is 2 × 1013ω cm~8 × 1013ω·cm.
The heat-resisting pvc material that the present invention is provided is surveyed at 200 DEG C according to the method for jis c 30052014 standard
Test, the thermostability of the heat-resisting pvc material that the test present invention provides, test result is, the heat-resisting pvc material that the present invention provides
Hot setting time is 136 minutes~198 minutes.
According to the standard of gb/t 5470-2008 " mensure of plastic impact method brittle temperature ", test the resistance to of present invention offer
The low temperature brittleness performance of hot pvc material, test result is that the low temperature brittleness performance of the heat-resisting pvc material that the present invention provides is -11
DEG C~-21 DEG C.
According to gb/t1033.1-2008 " the mensure part 1 infusion process of the non-foam plastic density of plastics, liquid specific gravity bottle
Method and titrimetry " standard, the density of the heat-resisting pvc material of offer of the test present invention, test result is, the present invention provides
The density of heat-resisting pvc material is 1.34g/cm3~1.35g/cm3.
Mark according to gb/t2406.2-2009 " plastics oxygen index method measures burning behavior part 2: room temperature test "
Standard, the oxygen index (OI) of the heat-resisting pvc material of offer of the test present invention, test result is, the heat-resisting pvc material that the present invention provides
Oxygen index (OI) is 26%~27%.
According to gb/t531.1-2008 " vulcanite or thermoplastic elastomer penetration hardness test method part 1: shore is hard
Degree meter method (Shao Er hardness) " standard, test the present invention provide heat-resisting pvc material hardness, test result is that the present invention carries
For heat-resisting pvc material hardness a be 94~95, d be 60.
The cost of the heat-resisting pvc material that the present invention provides is relatively low, and its cost is 10 yuan/kg~10.2 yuan/kg, with existing skill
Art compare the present invention offer heat-resisting pvc material per ton can 850 yuan~1000 yuan of reduces cost.
Raw material used in following examples of the present invention is commercial goods, and pvc resin-oatmeal used carries for Taiwan Plastic Group
For, totm used provides for Zhejiang Province Jia'aoEnvironmental Science and Technology Co., Ltd, and hp441 used provides for E.I.Du Pont Company
, ground calcium carbonate used provides for Fuyang Xin Chao Calcium Carbonate company limited, and Kaolin used is that Fujian Tao Jinfeng is new
The product of a pvcpfas-5010 model that Materials Co., Ltd provides, ca-zn complex stabilizer used is that Kai meter Sen is (big
Even) the product of the pdk2347m model that chemical products company limited provides, all of sb2o3There is provided for Shanghai Niu Weisi chemical industry
The product of 998 models, sb used2o3The product of the lhx-999 model that substitute provides for the prosperous Science and Technology Ltd. of Shenzhen joint
Product.
Embodiment 1
The proportioning raw materials preparing heat-resisting pvc material are:
The pvc resin-oatmeal of 100g;
The totm of 50g;
The ground calcium carbonate of 20g;
The Kaolin of 5g;
The ca-zn complex stabilizer of 5g;
The sb of 2g2o3;
The sb of 1g2o3Substitute;
The hp441 of 7g.
By above-mentioned raw materials stirring under conditions of mix homogeneously, obtain mixture;By described mixture in Shanghai balance level
Knead 15 minutes at 160 DEG C in the rubber mixing machine of hz-7015 model that device Science and Technology Ltd. provides, obtain intermediate product;By institute
State intermediate product 170 DEG C in the vulcameter of the hz-7014 model that Shanghai balance level device Science and Technology Ltd. provides at carry out sulfur
Change, obtain heat-resisting pvc material, the preheating time in described sulfidation is 5 minutes, pressing time is 5 minutes, moulding pressure is
20mpa, cool time is 5 minutes.
According to the method described in technique scheme, test the close of the heat-resisting pvc material that the embodiment of the present invention 1 prepares
Degree, thermostability, specific insulation, black brittleness, oxygen index (OI) and hardness, as shown in table 1, table 1 is that the present invention is real to test result
Apply example 1~embodiment 3 and the performance test results of heat-resisting pvc material that comparative example 1 prepares.
The cost of the heat-resisting pvc material that the embodiment of the present invention 1 prepares is 10.40 yuan/kg.
Embodiment 2
Prepare heat-resisting pvc material according to the method described in embodiment 1, as different from Example 1, using the hp441 of 5g
The hp441 of 7g in alternative embodiment 1.
According to the method described in technique scheme, test the close of the heat-resisting pvc material that the embodiment of the present invention 2 prepares
Degree, thermostability, specific insulation, black brittleness, oxygen index (OI) and hardness, test result is as shown in table 1.
The cost of the heat-resisting pvc material that the embodiment of the present invention 2 prepares is 10.23 yuan/kg.
Embodiment 3
Prepare heat-resisting pvc material according to the method described in embodiment 1, as different from Example 1, using the totm of 45g
The totm of 50g in alternative embodiment 1, using the sb of 1g2o3The sb of 2g in alternative embodiment 12o3, using the sb of 2g2o3Substitute
The sb of 1g in alternative embodiment 12o3Substitute.
According to the method described in technique scheme, test the close of the heat-resisting pvc material that the embodiment of the present invention 3 prepares
Degree, thermostability, specific insulation, black brittleness, oxygen index (OI) and hardness, test result is as shown in table 1.
Comparative example 1
Prepare heat-resisting pvc material according to the method described in embodiment 1, as different from Example 1, without hp441, adopt
With the Kaolin of 5g in the Kaolin alternative embodiment 1 of 3g, using the sb of 1g2o3The sb of 2g in alternative embodiment 12o3, using 2g
Sb2o3The sb of 1g in substitute alternative embodiment 12o3Substitute.
According to the method described in technique scheme, test the close of the heat-resisting pvc material that comparative example 1 of the present invention prepares
Degree, thermostability, specific insulation, black brittleness, oxygen index (OI) and hardness, test result is as shown in table 1.
The performance test results of the heat-resisting pvc material that table 1 embodiment of the present invention 1~3 and comparative example 1 prepare
Embodiment 4
The proportioning raw materials preparing heat-resisting pvc material are:
The pvc resin-oatmeal of 100g;
The totm of 48g;
The ground calcium carbonate of 22g;
The Kaolin of 5g
The ca-zn complex stabilizer of 5g;
The sb of 2g2o3;
The sb of 1.5g2o3Substitute;
The hp441 of 5.5g.
Prepare heat-resisting pvc material according to the method described in embodiment 1.
According to technique scheme methods described, test the volume of the heat-resisting pvc material that the embodiment of the present invention 4 prepares
Resistivity, thermostability and black brittleness, test result is, at 30 DEG C of the heat-resisting pvc material that the embodiment of the present invention 4 prepares
Specific insulation be 7.9 × 1013ω cm, thermostability is 198min, and black brittleness is -17 DEG C.
The cost of the heat-resisting pvc material that the embodiment of the present invention 4 prepares is 10.14 yuan/kg.
Comparative example 2
The proportioning raw materials preparing heat-resisting pvc material are:
The pvc resin-oatmeal of 100g;
The totm of 60g;
The ground calcium carbonate of 20g;
The ca-zn complex stabilizer of 10g;
The sb of 11g2o3.
Prepare heat-resisting pvc material according to the method described in embodiment 1.
According to technique scheme methods described, test the volume of the heat-resisting pvc material that comparative example 2 of the present invention prepares
Resistivity, thermostability and black brittleness, test result is, at 30 DEG C of the heat-resisting pvc material that comparative example 2 of the present invention prepares
Specific insulation be 2.9 × 1012ω cm, thermostability is 126min, and black brittleness is -8 DEG C.
The cost of the heat-resisting pvc material that comparative example 2 of the present invention prepares is 11.09 yuan/kg.
Embodiment 5
The proportioning raw materials preparing heat-resisting pvc material are:
The pvc resin-oatmeal of 100g;
The totm of 50g;
The ground calcium carbonate of 20g;
The ca-zn complex stabilizer of 10g;
The sb of 10g2o3;
The hp441 of 10g.
Prepare heat-resisting pvc material according to the method described in embodiment 1.
According to the method described in technique scheme, test the low of the heat-resisting pvc material that the embodiment of the present invention 5 prepares
Warm fragility, test result is that the black brittleness of the heat-resisting pvc material that the embodiment of the present invention 5 prepares is -21 DEG C.
Comparative example 3
Prepare heat-resisting pvc material according to the method described in embodiment 5, as different from Example 5, using the tpu of 10g
(thermoplastic polyurethane) replaces the hp441 of 10g.
According to the method described in technique scheme, test the low of the heat-resisting pvc material that comparative example 3 of the present invention prepares
Warm fragility, test result is that the black brittleness of the heat-resisting pvc material that comparative example 3 of the present invention prepares is -8 DEG C.
Comparative example 4
Prepare heat-resisting pvc material according to the method described in embodiment 5, as different from Example 5, using the acr of 10g
(acrylic acid esters co-polymer) replaces the hp441 of 10g.
According to the method described in technique scheme, test the low of the heat-resisting pvc material that comparative example 4 of the present invention prepares
Warm fragility, test result is that the black brittleness of the heat-resisting pvc material that comparative example 4 of the present invention prepares is -10 DEG C.
Comparative example 5
Prepare heat-resisting pvc material according to the method described in embodiment 5, as different from Example 5, without hp441.
According to the method described in technique scheme, test the low of the heat-resisting pvc material that comparative example 5 of the present invention prepares
Warm fragility, test result is that the black brittleness of the heat-resisting pvc material that comparative example 5 of the present invention prepares is -8 DEG C.
Comparative example 6
The proportioning raw materials preparing heat-resisting pvc material are:
The pvc resin-oatmeal of 100g;
The totm of 60g;
The Calcium Carbonate of 20g;
The ca-zn complex stabilizer of 10g;
The sb of 10g2o3.
Prepare heat-resisting pvc material according to the method described in embodiment 1.
According to the method described in technique scheme, test the body of the heat-resisting pvc material that comparative example 6 of the present invention prepares
Long-pending resistivity;According to gb/t2951.32-2008 " cable and optical cable insulating and sheath material GENERAL EXPERIMENTATION the 32nd part: poly-
Vinyl chloride compound Special test method zero-G test heat stabilization test " standard, using ul1581 fourth editio,
dated october 31,2001 reference standard for electrical wire,cables,and
The equipment of flexible cords model, tests the ul heat ageing quality of the heat-resisting pvc material that comparative example 6 of the present invention prepares
Loss, the residual rate of the aging rear tensile strength of ul and the residual rate of the aging rear elongation at break of ul, as shown in table 2, table 2 is this to test result
The performance test results of the heat-resisting pvc material that bright comparative example 6~comparative example 11 prepares.
Comparative example 7
Prepare heat-resisting pvc material according to the method described in comparative example 6, from unlike comparative example 6 adopt 55g totm and
The eso of 5g replaces the totm of 60g in comparative example 6.
According to the method described in comparative example 6, test the volume electricity of the heat-resisting pvc material that comparative example 7 of the present invention prepares
The residual rate of the aging rear elongation at break of the residual rate of the aging rear tensile strength of resistance rate, ul heat ageing mass loss, ul, ul, test result is such as
Shown in table 2.
Comparative example 8
Prepare heat-resisting pvc material according to the method described in comparative example 6, and unlike comparative example 6, using the totm of 52g
Replace the totm of 60g in comparative example 6 with the eso of 8g.
According to the method described in comparative example 6, test the volume electricity of the heat-resisting pvc material that comparative example 8 of the present invention prepares
The residual rate of the aging rear elongation at break of the residual rate of the aging rear tensile strength of resistance rate, ul heat ageing mass loss, ul, ul, test result is such as
Shown in table 2.
Comparative example 9
Prepare heat-resisting pvc material according to the method described in comparative example 6, and unlike comparative example 6, using the totm of 50g
Replace the totm of 60g in comparative example 6.
According to the method described in comparative example 6, test the volume electricity of the heat-resisting pvc material that comparative example 9 of the present invention prepares
The residual rate of the aging rear elongation at break of the residual rate of the aging rear tensile strength of resistance rate, ul heat ageing mass loss, ul, ul, test result is such as
Shown in table 2.
Comparative example 10
Prepare heat-resisting pvc material according to the method described in comparative example 6, and unlike comparative example 6, using the dotp of 50g
(DOTP) replaces the totm of 60g in comparative example 6.
According to the method described in comparative example 6, test the volume electricity of the heat-resisting pvc material that comparative example 10 of the present invention prepares
The residual rate of the aging rear elongation at break of the residual rate of the aging rear tensile strength of resistance rate, ul heat ageing mass loss, ul, ul, test result is such as
Shown in table 2.
Comparative example 11
Prepare heat-resisting pvc material according to the method described in comparative example 6, and unlike comparative example 6, using the polyester of 50g
The totm of 60g in comparative example 6 replaced by plasticizer.
According to the method described in comparative example 6, test the volume electricity of the heat-resisting pvc material that comparative example 11 of the present invention prepares
The residual rate of the aging rear elongation at break of the residual rate of the aging rear tensile strength of resistance rate, ul heat ageing mass loss, ul, ul, test result is such as
Shown in table 2.
The heat-resisting pvc material properties test result that table 2 comparative example 6~comparative example 11 of the present invention prepares
As shown in Table 2, the totm of part is replaced as plasticizer using eso (epoxy soybean oil), prepare is heat-resisting
The resistivity properties of pvc material reduce;Totm is replaced as increasing using dotp (DOTP) or polyester plasticizer
Mould agent, the physical and mechanical propertiess such as tensile property after the heat-resisting pvc material aging preparing is poor.
Embodiment 6
Electric wire is prepared using the heat-resisting pvc material that embodiment 2 prepares, method particularly includes:
By extrusion molding in the extruder of a diameter of 30mm after described heat-resisting pvc material disintegrating, prepare electric wire, institute
The screw speed stating extruder is 1440 revs/min, and linear velocity is 225m/min, and conductor pre-heating temperature degree is 75 DEG C, area's temperature
For 150 DEG C, two area's temperature are 170 DEG C, and three area's temperature are 180 DEG C, and four area's temperature are 180 DEG C, and five area's temperature are 180 DEG C, 6th area
Temperature is 180 DEG C, and seven area's temperature are 185 DEG C.
Using gb/t2951.14-2008 " cable and optical cable insulating and sheath material GENERAL EXPERIMENTATION the 14th part: logical
With test method-low-temperature test " standard, the low-temperature bending performance of electric wire that the test embodiment of the present invention 6 prepares;Using
Jis c 3,005 2014 standard is test at 200 DEG C, and the heat of the electric wire that the test embodiment of the present invention 6 prepares is stabilized
Performance;Test using in jis c 20 DEG C of water of 3,005 2014 standard, the electric wire that the test embodiment of the present invention 6 prepares
Insulation resistance;Test result is that -60 DEG C of the low-temperature bending of the electric wire that the embodiment of the present invention 6 prepares passes through, thermostability
For 140min, it is 8.7 × 10 in insulation resistance (20 DEG C) water2ω, temperature classification is 105 DEG C.
As seen from the above embodiment, the invention provides a kind of heat-resistant polyvinyl chloride material, in parts by weight, described heat-resisting
The preparing raw material of pvc material includes: 100 parts of polyvinyl chloride resin powder;45 parts~52 parts of trioctyl trimellitate (TOTM);
22 parts~31 parts of filler, described filler includes Calcium Carbonate and Kaolin;3 parts~8 parts of ca-zn complex stabilizer;4 parts
~7 parts of ethylene/n-butyl acrylate-hydroxyl elastomer;1.5 parts~5 parts of fire retardant, described fire retardant includes sb2o3With/
Or sb2o3Succedaneum, described sb2o3Succedaneum is in parts by weight, comprising: 45 parts~46 parts of silicon dioxide;30 parts~35 parts
Magnesium oxide;8 parts~9 parts of montmorillonite;2 parts~2.5 parts of zinc oxide;5 parts~5.5 parts of aluminium sesquioxide;1 part~1.5 parts
Copper oxide.The invention provides a kind of preparation method of heat-resistant polyvinyl chloride material, comprising: by polyvinyl chloride resin powder, partially
Benzenetricarboxylic acid three monooctyl ester, filler, ca-zn complex stabilizer, ethylene/n-butyl acrylate-hydroxyl elastomer and fire retardant mixing,
Obtain mixture;Described mixture is kneaded, is obtained intermediate product;Described intermediate product is vulcanized, is obtained heat-resisting
Pvc material.The invention provides a kind of electric wire, the heat-resistant polyvinyl chloride material described in technique scheme is prepared into
Arrive, or the heat-resistant polyvinyl chloride material that the method described in technique scheme prepares prepares.
In the preparing raw material of the heat-resistant polyvinyl chloride material that the present invention provides and preparation method thereof, elastomer can improve material
The black brittleness of material, but elastomer is relatively costly;The electrical property that Kaolin can improve material simultaneously effective reduces product
The cost of product, but the mechanical performance of material can be reduced, such as tensile property;The present invention adds a small amount of sexual valence in preparing raw material
Relatively higher fire retardant, by the interaction of elastomer, Kaolin and fire retardant, the cooperation with other preparing raw materials simultaneously
Use, cost is relatively low simultaneously finally to make the heat-resistant polyvinyl chloride material that the present invention provides have preferable black brittleness.Additionally, this
The heat-resistant polyvinyl chloride material that invention provides also has preferable mechanical and physical performance and thermostability.The electricity that the present invention provides
Heat-resistant polyvinyl chloride material described in technique scheme for the line prepares, and it is crisp that therefore this electric wire also has preferable low temperature
Cost is relatively low simultaneously for property.Additionally, the electric wire that the present invention provides also has preferable mechanical and physical performance, electrical insulation capability and heat
Stability.