CN106188942B - A kind of polyvinyl chloride high-low temperature resistant hose and preparation method thereof - Google Patents
A kind of polyvinyl chloride high-low temperature resistant hose and preparation method thereof Download PDFInfo
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- CN106188942B CN106188942B CN201610559109.8A CN201610559109A CN106188942B CN 106188942 B CN106188942 B CN 106188942B CN 201610559109 A CN201610559109 A CN 201610559109A CN 106188942 B CN106188942 B CN 106188942B
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
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- C08J2327/00—Characterised by the use 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; Derivatives of such polymers
- C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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- C08J2427/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/04—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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Abstract
A kind of polyvinyl chloride high-low temperature resistant hose, raw material composition and weight part ratio are：Corvic SH 200 30~50, Corvic WS 1,300 30~50, powder nbr P83 8~10, ethylene-vinyl acetate carbonyl copolymer E/VA/CO 8~10, plasticizer 50~65, stabilizer 6~8, crosslinking coagent 8~10, antioxidant 0.8~1, anti-aging agent 0.3~0.5, lubricant 1~2, filler 9~12, when preparation, first by above-mentioned raw materials melt blending, then it is crosslinked successively via extrusion process, electron accelerator irradiation.The design has good high and low temperature resistance.
Description
Technical field
The invention belongs to novel high polymer material fields, and in particular to a kind of polyvinyl chloride high-low temperature resistant hose and preparation side
Method.
Background technology
Currently, polyvinyl chloride hose purposes is very extensive, such as automobile-used casing, electric wire protection hose, industrial acid and alkali-resistance
The fields such as hose, high temperature resistant delivery hose.Although polyvinyl chloride hose has the following advantages that：(1) light-weight, only with size steel
/ 6th of weight；(2) corrosion resistance and good；(3) electrical insulation capability is good；(4) frictional resistance is small；(5) thermal coefficient is small；(6) colour
It is convenient；(7) energy consumption is low, but its there is also following defects in use：(1) easily it is hardened under low temperature, embrittlement；(2) under high temperature
It is easy to aging, it is hardened；(3) use temperature range is narrow, generally between -15~70 DEG C；(4) thermal deformation is larger.
Invention content
The purpose of the present invention is overcoming the problems, such as that the performance of the existing technology under high and low temperature is poor, providing one kind can
Polyvinyl chloride hose of high-low temperature resistant and preparation method thereof.
In order to achieve the above object, the present invention provides following technical schemes：
A kind of polyvinyl chloride high-low temperature resistant hose, the raw material composition and its weight part ratio of the hose are：Corvic
SH-20030~50, Corvic WS-130030~50, powder nbr P838~10, the copolymerization of ethene-vinyl acetate carbonyl
Object E/VA/CO 8~10, plasticizer 50~65, stabilizer 6~8, crosslinking coagent 8~10, antioxidant 0.8~1, anti-aging agent 0.3
~0.5, lubricant 1~2, filler 9~12；
The hose is made in required ratio by radiation crosslinking modified by above-mentioned raw materials.
The plasticizer presses 10~15 by dioctyl sebacate DOS, dioctyl phthalate DOP:40~50 weight
Than mixing, the stabilizer is calcium-zinc composite stabilizing agent 8890, and the crosslinking coagent is trimethylol propane trimethyl third
Olefin(e) acid ester TMPTMA, the antioxidant are bisphenol-A, and the anti-aging agent is 4010NA, and the lubricant is polyethylene wax, described to fill out
Material presses 8~10 by nano-calcium carbonate, color masterbatch:1~2 weight ratio mixes.
A kind of preparation method of polyvinyl chloride high-low temperature resistant hose, includes the following steps successively：
Raw material melt blending：First by Corvic SH-200, Corvic WS-1300, powder nbr P83,
Ethene-vinyl acetate carbonyl copolymer E/VA/CO, it plasticizer, stabilizer, crosslinking coagent, antioxidant, anti-aging agent, lubricant, fills out
Material, which is added in required ratio in high-speed mixer, to be uniformly mixed to obtain mixed material, then mixed material is discharged into two steps type and is squeezed out
Melting extrusion, air-cooled blank are to obtain tubing particle in granulation unit；
The preparation of hose：First the tubing particle is extruded to obtain the smooth pipe of inside and outside wall in single screw extrusion machine
Material, then cross-linking radiation is carried out to get to polyvinyl chloride high-low temperature resistant hose to the tubing extruded with electron accelerator.
In the raw material melt blending step, mixing temperature is 70~90 DEG C, and incorporation time is 7~8min,
The technological temperature of two steps type extruding granulator is：
Parallel double-screw：One 125~135 DEG C of area, two 135~145 DEG C of areas, three 145~155 DEG C of areas, four areas 155~165
DEG C, five 160~170 DEG C of areas, six 165~175 DEG C of areas, 155~165 DEG C of head,
Single screw rod：One 135~145 DEG C of area, two 140~150 DEG C of areas, three 145~155 DEG C of areas, four 155~165 DEG C of areas, five
160~170 DEG C of area, 155~165 DEG C of head；
In the preparation process of the hose, irradiation dose is 15~18 Megarads,
The operating temperature of single screw extrusion machine is：One 130~140 DEG C of area, two 140~150 DEG C of areas, three areas 150~160
DEG C, four 160~170 DEG C of areas, five 165~175 DEG C of areas, 160~170 DEG C of head.
The plasticizer presses 10~15 by dioctyl sebacate DOS, dioctyl phthalate DOP:40~50 weight
Than mixing, the stabilizer is calcium-zinc composite stabilizing agent 8890, and the crosslinking coagent is trimethylol propane trimethyl third
Olefin(e) acid ester TMPTMA, the antioxidant are bisphenol-A, and the anti-aging agent is 4010NA, and the lubricant is polyethylene wax, described to fill out
Material presses 8~10 by nano-calcium carbonate, color masterbatch:1~2 weight ratio mixes.
Compared with prior art, beneficial effects of the present invention are：
A kind of raw material composition of polyvinyl chloride high-low temperature resistant hose of the present invention includes the Corvic SH- of high polymerization degree
200, powder nbr P83 and ethene-vinyl acetate carbonyl copolymer E/VA/CO, the low temperature of Corvic SH-200 are tough
Property it is good, powder nbr P83 not only can effectively reduce the brittle temperature of product, and have the effect of plasticising, ethylene-vinegar
Sour ethenecarbonyl copolymer E/VA/CO can also play the role of plasticising, three while improving the low-temperature flexibility of polyvinyl chloride
It is used in combination and ensure that product normal use and can keep higher pliability under conditions of subzero 50 DEG C, by above-mentioned raw materials
It is cross-linking modified by electron beam irradiation, polyvinyl chloride can be made to be cross-linked to form network molecular structure, heat is transformed by thermoplastic material
Thermoset material ensure that product can be used for a long time in the environment of 105 DEG C.Therefore, the present invention has good high-low temperature resistant
Performance.
Specific implementation mode
The invention will be further described With reference to embodiment.
A kind of polyvinyl chloride high-low temperature resistant hose, the raw material composition and its weight part ratio of the hose are：Corvic
SH-20030~50, Corvic WS-130030~50, powder nbr P838~10, the copolymerization of ethene-vinyl acetate carbonyl
Object E/VA/CO 8~10, plasticizer 50~65, stabilizer 6~8, crosslinking coagent 8~10, antioxidant 0.8~1, anti-aging agent 0.3
~0.5, lubricant 1~2, filler 9~12；
The hose is made in required ratio by radiation crosslinking modified by above-mentioned raw materials.
The plasticizer presses 10~15 by dioctyl sebacate DOS, dioctyl phthalate DOP:40~50 weight
Than mixing, the stabilizer is calcium-zinc composite stabilizing agent 8890, and the crosslinking coagent is trimethylol propane trimethyl third
Olefin(e) acid ester TMPTMA, the antioxidant are bisphenol-A, and the anti-aging agent is 4010NA, and the lubricant is polyethylene wax, described to fill out
Material presses 8~10 by nano-calcium carbonate, color masterbatch:1~2 weight ratio mixes.
A kind of preparation method of polyvinyl chloride high-low temperature resistant hose, includes the following steps successively：
Raw material melt blending：First by Corvic SH-200, Corvic WS-1300, powder nbr P83,
Ethene-vinyl acetate carbonyl copolymer E/VA/CO, it plasticizer, stabilizer, crosslinking coagent, antioxidant, anti-aging agent, lubricant, fills out
Material, which is added in required ratio in high-speed mixer, to be uniformly mixed to obtain mixed material, then mixed material is discharged into two steps type and is squeezed out
Melting extrusion, air-cooled blank are to obtain tubing particle in granulation unit；
The preparation of hose：First the tubing particle is extruded to obtain the smooth pipe of inside and outside wall in single screw extrusion machine
Material, then cross-linking radiation is carried out to get to polyvinyl chloride high-low temperature resistant hose to the tubing extruded with electron accelerator.
In the raw material melt blending step, mixing temperature is 70~90 DEG C, and incorporation time is 7~8min,
The technological temperature of two steps type extruding granulator is：
Parallel double-screw：One 125~135 DEG C of area, two 135~145 DEG C of areas, three 145~155 DEG C of areas, four areas 155~165
DEG C, five 160~170 DEG C of areas, six 165~175 DEG C of areas, 155~165 DEG C of head,
Single screw rod：One 135~145 DEG C of area, two 140~150 DEG C of areas, three 145~155 DEG C of areas, four 155~165 DEG C of areas, five
160~170 DEG C of area, 155~165 DEG C of head；
In the preparation process of the hose, irradiation dose is 15~18 Megarads,
The operating temperature of single screw extrusion machine is：One 130~140 DEG C of area, two 140~150 DEG C of areas, three areas 150~160
DEG C, four 160~170 DEG C of areas, five 165~175 DEG C of areas, 160~170 DEG C of head.
The plasticizer presses 10~15 by dioctyl sebacate DOS, dioctyl phthalate DOP:40~50 weight
Than mixing, the stabilizer is calcium-zinc composite stabilizing agent 8890, and the crosslinking coagent is trimethylol propane trimethyl third
Olefin(e) acid ester TMPTMA, the antioxidant are bisphenol-A, and the anti-aging agent is 4010NA, and the lubricant is polyethylene wax, described to fill out
Material presses 8~10 by nano-calcium carbonate, color masterbatch:1~2 weight ratio mixes.
The principle of the present invention is described as follows：
Corvic：
Although the Corvic SH-200 of high polymerization degree has preferable heat-resisting and resistance to low temperature, its elasticity
Greatly, processing performance is poor, therefore the present invention adds the Corvic WS-1300 of low polymerization degree on its basis, to protect
Card can also meet the requirement of expressing technique while meeting properties of product.
Powder nbr P83：
For modified butadiene acrylonitrile rubber, when P83 elastomers are scattered in PVC base system, P83 elastomers can be polychlorostyrene second
Alkene is coated on centre, forms continuous reticular structure.When material is impacted, continuous reticular structure can absorb a large amount of punching
Energy is hit, to protection materials, material is made to avoid being destroyed；Even if the continuous reticular structure is not enough to absorb whole
Impact energy, polyvinyl chloride primary particle can also absorb many energy with protection materials, to significantly improve material in rupture
Low-temperature flexibility.In addition, P83 elastomers are alternatively arranged as polymeric solid plasticizer, and especially when material is in low temperature, the high score
Sub- solid plasticizer will not be easy migration precipitation as small molecule liquid plasticizer, this ensure that the low temperature of polyvinyl chloride is soft
Toughness improves low temperature impact strength, reduces brittle temperature.
Ethene-vinyl acetate carbonyl copolymer E/VA/CO：
The copolymer introduces ketone carbonyl, the compatibility pole with polyvinyl chloride as flexible plasticizer in system
Good, network structure can be formed by being dispersed in PVC base system as modifying agent, and polyvinyl chloride primary particle is located in network.When
When material is by external impacts, which can absorb a large amount of impact energy, improve the low temperature impact strength of material；Separately
Outside, ethene-vinyl acetate carbonyl copolymer E/VA/CO equally can be used as polymeric solid plasticizer, make material in consecutive low temperature
Good performance is kept in environment.
Cold resistant plasticizer dioctyl sebacate DOS：
The cold resistance of cold resistant plasticizer has close relationship with its structure.The good plasticizer cold resistance of general intermiscibility
All poor, especially when containing cyclic structure, cold resistance significantly reduces.Dioctyl sebacate DOS is used as with straight chain methylene
Aliphatic ester based on (- CH2-) has good cold resistance, introduces the glass transition temperature that can reduce polyvinyl chloride
Degree, to reduce the brittle temperature of polyvinyl chloride, improves the cold tolerance of material.
Raw material melt blending step：
The step controls mixing temperature at 70~90 DEG C, is easy to absorption of the Corvic to liquid plasticizer,
The temperature range mixes 7~8min, it is ensured that plasticizer is absorbed by Corvic completely.
Embodiment 1：
A kind of polyvinyl chloride high-low temperature resistant hose, the raw material composition and its weight part ratio of the hose are：Corvic
SH-200 30, Corvic WS-1300 30, powder nbr P83 8, ethene-vinyl acetate carbonyl copolymer E/VA/CO
8, dioctyl sebacate DOS 10, dioctyl phthalate DOP 40, calcium-zinc composite stabilizing agent 8,890 6, trimethylolpropane
Trimethyl acrylic ester TMPTMA 8, antioxidant bisphenol-A 0.8, antioxidant 4010NA 0.3, polyethylene wax 1, nano-calcium carbonate
8, color masterbatch 1.
The polyvinyl chloride high-low temperature resistant hose is adopted successively to be prepared by the following steps：
Raw material melt blending：First by Corvic SH-200, Corvic WS-1300, powder nbr P83,
Ethene-vinyl acetate carbonyl copolymer E/VA/CO, it plasticizer, stabilizer, crosslinking coagent, antioxidant, anti-aging agent, lubricant, fills out
Material is added in high-speed mixer and mixes 7min at 70 DEG C to obtain mixed material according to the above ratio, then mixed material is discharged into double
Melting extrusion, air-cooled blank are to obtain tubing particle in stepwise extruding pelletization unit, wherein the two steps type extruding granulator
Technological temperature is：
Parallel double-screw：One 125~135 DEG C of area, two 135~145 DEG C of areas, three 145~155 DEG C of areas, four areas 155~165
DEG C, five 160~170 DEG C of areas, six 165~175 DEG C of areas, 155~165 DEG C of head,
Single screw rod：One 135~145 DEG C of area, two 140~150 DEG C of areas, three 145~155 DEG C of areas, four 155~165 DEG C of areas, five
160~170 DEG C of area, 155~165 DEG C of head；
The preparation of hose：First the tubing particle is extruded to obtain the smooth pipe of inside and outside wall in single screw extrusion machine
Material, then cross-linking radiation is carried out to get to polyvinyl chloride high-low temperature resistant hose to the tubing extruded with electron accelerator, wherein institute
The operating temperature for stating single screw extrusion machine is：One 130~140 DEG C of area, two 140~150 DEG C of areas, three 150~160 DEG C of areas, 4th area
160~170 DEG C, five 165~175 DEG C of areas, 160~170 DEG C of head, the irradiation dose is 16 Megarads.
Embodiment 2：
Step with embodiment 1, the difference is that：
The raw material of the polyvinyl chloride high-low temperature resistant hose forms and its weight part ratio is：Corvic SH-200
50, Corvic WS-130050, powder nbr P8310, ethene-vinyl acetate carbonyl copolymer E/VA/CO 10, the last of the ten Heavenly stems two
Dioctyl phthalate DOS 15, dioctyl phthalate DOP 50, calcium-zinc composite stabilizing agent 88908, trimethylol propane trimethyl
Acrylate TMPTMA 10, antioxidant bisphenol-A 1, antioxidant 4010NA 0.5, polyethylene wax 2, nano-calcium carbonate 10, color masterbatch
Material 2.
In the raw material melt blending step, mixing temperature is 90 DEG C, incorporation time 8min；
In the preparation process of the hose, irradiation dose is 18 Megarads.
Embodiment 3：
Step with embodiment 1, the difference is that：
The raw material of the polyvinyl chloride high-low temperature resistant hose forms and its weight part ratio is：Corvic SH-200
40, Corvic WS-130040, powder nbr P839, ethene-vinyl acetate carbonyl copolymer E/VA/CO 9, decanedioic acid
Dioctyl ester DOS 12.5, dioctyl phthalate DOP 45, calcium-zinc composite stabilizing agent 8,890 7, trimethylol propane trimethyl
Acrylate TMPTMA 9, antioxidant bisphenol-A 0.9, antioxidant 4010NA 0.4, polyethylene wax 1.5, nano-calcium carbonate 9, color
Masterbatch 1.5.
In the raw material melt blending step, mixing temperature is 75 DEG C, incorporation time 8min；
In the preparation process of the hose, irradiation dose is 15 Megarads.
The polyvinyl chloride high-low temperature resistant hose prepared using above-described embodiment has been subjected to performance detection, it is as a result as follows：
Tensile strength >=16.3MPa；
Elongation at break >=389%；
Low-temperature impact brittle temperature reaches subzero 56 DEG C；
Heat-stable time at 200 DEG C：186 minutes；
Thermal ageing test (135 DEG C × 240h)：Aging post-tensioning intensity >=16.1MPa, elongation at break after aging >=
376%；
Heat ageing mass loss (115 DEG C × 240h)≤9.8g/m2；
Volume resistivity at 20 DEG C：3.8×1010Ω·m；
Thermal deformation≤22.7%.
Claims (5)
1. a kind of polyvinyl chloride high-low temperature resistant hose, it is characterised in that：
The raw material of the hose forms and its weight part ratio is：Corvic SH-20030~50, Corvic WS-
130030~50, powder nbr P838~10, ethene-vinyl acetate carbonyl copolymer E/VA/CO 8~10, plasticizer 50~
65, stabilizer 6~8, crosslinking coagent 8~10, antioxidant 0.8~1, anti-aging agent 0.3~0.5, lubricant 1~2, filler 9~12；
The hose is made in required ratio by radiation crosslinking modified by above-mentioned raw materials.
2. a kind of polyvinyl chloride high-low temperature resistant hose according to claim 1, it is characterised in that：The plasticizer is by the last of the ten Heavenly stems two
Dioctyl phthalate DOS, dioctyl phthalate DOP press 10~15:40~50 weight ratio mixes, and the stabilizer is calcium
Zinc composite stabilizer 8890, the crosslinking coagent are trimethylol-propane trimethacrylate TMPTMA, and the antioxidant is
Bisphenol-A, the anti-aging agent are 4010NA, and the lubricant is polyethylene wax, and the filler presses 8 by nano-calcium carbonate, color masterbatch
~10:1~2 weight ratio mixes.
3. a kind of preparation method of polyvinyl chloride high-low temperature resistant hose described in claim 1, it is characterised in that：
The preparation method includes the following steps successively：
Raw material melt blending：First by Corvic SH-200, Corvic WS-1300, powder nbr P83, ethylene-
Vinyl acetate carbonyl copolymer E/VA/CO, plasticizer, stabilizer, crosslinking coagent, antioxidant, anti-aging agent, lubricant, filler are pressed
Required ratio is added in high-speed mixer and is uniformly mixed to obtain mixed material, then mixed material is discharged into two steps type extruding pelletization
Melting extrusion, air-cooled blank are to obtain tubing particle in unit；
The preparation of hose：First the tubing particle is extruded to obtain the smooth tubing of inside and outside wall in single screw extrusion machine, then
Cross-linking radiation is carried out to get to polyvinyl chloride high-low temperature resistant hose to the tubing extruded with electron accelerator.
4. a kind of preparation method of polyvinyl chloride high-low temperature resistant hose according to claim 3, it is characterised in that：
In the raw material melt blending step, mixing temperature is 70~90 DEG C, and incorporation time is 7~8min,
The technological temperature of two steps type extruding granulator is：
Parallel double-screw：One 125~135 DEG C of area, two 135~145 DEG C of areas, three 145~155 DEG C of areas, four 155~165 DEG C of areas, five
160~170 DEG C of area, six 165~175 DEG C of areas, 155~165 DEG C of head,
Single screw rod：One 135~145 DEG C of area, two 140~150 DEG C of areas, three 145~155 DEG C of areas, four 155~165 DEG C of areas, 5th area
160~170 DEG C, 155~165 DEG C of head；
In the preparation process of the hose, irradiation dose is 15~18 Megarads,
The operating temperature of single screw extrusion machine is：One 130~140 DEG C of area, two 140~150 DEG C of areas, three 150~160 DEG C of areas, four
160~170 DEG C of area, five 165~175 DEG C of areas, 160~170 DEG C of head.
5. a kind of preparation method of polyvinyl chloride high-low temperature resistant hose according to claim 3 or 4, it is characterised in that：Institute
Plasticizer is stated by dioctyl sebacate DOS, dioctyl phthalate DOP by 10~15:40~50 weight ratio mixes,
The stabilizer is calcium-zinc composite stabilizing agent 8890, and the crosslinking coagent is trimethylol-propane trimethacrylate
TMPTMA, the antioxidant are bisphenol-A, and the anti-aging agent is 4010NA, and the lubricant is polyethylene wax, and the filler is by receiving
Rice calcium carbonate, color masterbatch press 8~10:1~2 weight ratio mixes.
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| CN108359172A (en) * | 2018-03-20 | 2018-08-03 | 湖南金龙电缆有限公司 | Insulating layer and sheath material of a kind of charging pile connecting cable and preparation method thereof |
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| CN103450598A (en) * | 2013-09-10 | 2013-12-18 | 天津雅园科技有限公司 | Modified polyvinyl chloride cable material |
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