CN107141631A - A kind of ethylene propylene diene rubber polyvinyl chloride composite jacket pipe of carbon black toughening modifying and preparation method thereof - Google Patents

A kind of ethylene propylene diene rubber polyvinyl chloride composite jacket pipe of carbon black toughening modifying and preparation method thereof Download PDF

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Publication number
CN107141631A
CN107141631A CN201710276760.9A CN201710276760A CN107141631A CN 107141631 A CN107141631 A CN 107141631A CN 201710276760 A CN201710276760 A CN 201710276760A CN 107141631 A CN107141631 A CN 107141631A
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pipe
carbon black
ethylene propylene
diene rubber
propylene diene
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许义彬
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JING FENG GROUP
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JING FENG GROUP
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00Compositions 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
    • C08L27/02Compositions 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
    • C08L27/04Compositions 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
    • C08L27/06Homopolymers or copolymers of vinyl chloride
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C08F283/124Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F285/00Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/045Polysiloxanes containing less than 25 silicon atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/18Applications used for pipes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The ethylene propylene diene rubber polyvinyl chloride composite jacket pipe of a kind of carbon black toughening modifying, it is characterised in that eight vinyl polyhedral silsesquioxanes are obtained with vinyl trichlorosilane hydrolytic condensation first;The vinyl of eight vinyl polyhedral silsesquioxanes and the pi-allyl catalytic polymerization of allyl glycidyl ether, obtain epoxy radicals polyhedral silsesquioxane;Then with vinyl chloride and epoxy radicals polyhedral silsesquioxane graft polymerization coating modification carbon black, then by modified carbon black, ethylene propylene diene rubber, polyvinyl chloride and other auxiliary agents by premix, melting, plasticizing, mixing extrusion obtain tubing material;Last extruded shaping and biaxial tension, obtain the ethylene propylene diene rubber polyvinyl chloride composite jacket pipe of carbon black toughening modifying.The protecting pipe of the present invention, the characteristics of laying equal stress on high intensity and high tenacity, strong shock resistance.

Description

A kind of ethylene propylene diene rubber of carbon black toughening modifying-polyvinyl chloride composite jacket pipe and Its preparation method
Technical field
The invention belongs to tubing field, and in particular to a kind of ethylene propylene diene rubber-polyvinyl chloride of carbon black toughening modifying is multiple Close protecting pipe and preparation method thereof.
Background technology
Polyhedral oligomeric silsesquioxane (polyhedral oligomeric silsesquioxane, POSS) is a class Special silsesquioxane, molecule is (RSiO1.5)n, its structure is generally by the inorganic kernels of Si-O-Si of hexahedron cage type and top 8 organic substituent R compositions of point, wherein R can be one or more organo-functional groups, be a kind of molecule truly Nano hybridization compound.This new hybrid material not only possesses that the toughness of high polymer material, cost be low and well processed Property, while multiple advantages such as intensity is high, not oxidizable, high temperature resistant, mechanical property are good with inorganic material again.At present, utilize POSS prepares the focus that novel organic-inorganic hybrid material has become research as nanostructures, and material can be improved by introducing POSS The heat endurance of material, improves mechanical performance and other physical properties.
Author Tang Wei et al. exists《The synthesis of Epoxy-silsesquioxanes and sign》In one text, passed through with vinyl trichlorosilane Hydrolytic condensation, first prepares eight vinyl polyhedral silsesquioxanes, is then made with Peracetic acid direct oxidation ethene functional group Epoxy radicals polyhedral silsesquioxane.The epoxy radicals polyhedral silsesquioxane prepared is adopted this method, it is average each Polyhedral silsesquioxane can only carry 3-4 epoxy radicals, and the relative position of epoxy radicals is not fixed, and what is obtained is with difference The polyhedral silsesquioxane of number and diverse location epoxy radicals.And the epoxy radicals that such a method is obtained directly publishes in instalments polyhedron On the skeleton Si of silsesquioxane, because steric hindrance is larger, reactivity is substantially reduced, and influences its performance.
The content of the invention
A kind of ethylene-propylene-diene monomer for the carbon black toughening modifying laid equal stress on it is an object of the invention to provide high intensity and high tenacity Glue-polyvinyl chloride composite jacket pipe and preparation method thereof.
To achieve these goals, present invention employs following technical scheme:
A kind of ethylene propylene diene rubber of carbon black toughening modifying-polyvinyl chloride composite jacket pipe, it is characterised in that first with vinyl Trichlorosilane hydrolytic condensation obtains eight vinyl polyhedral silsesquioxanes;The vinyl of eight vinyl polyhedral silsesquioxanes With the pi-allyl catalytic polymerization of allyl glycidyl ether, epoxy radicals polyhedral silsesquioxane is obtained;Then with chloroethene Alkene and epoxy radicals polyhedral silsesquioxane graft polymerization coating modification carbon black, then by modified carbon black, ethylene propylene diene rubber, polychlorostyrene Ethene and other auxiliary agents obtain tubing material by premix, melting, plasticizing, mixing extrusion;Last extruded shaping and two-way drawing Stretch, obtain ethylene propylene diene rubber-polyvinyl chloride composite jacket pipe of carbon black toughening modifying.
The ethylene propylene diene rubber of described carbon black toughening modifying-polyvinyl chloride composite jacket pipe, it is characterised in that it is by such as Lower step is prepared from:
(1)It is 1 in mass ratio by vinyl trichlorosilane and acetone:10-12 ratio is added in reaction vessel, mechanical agitation It is well mixed, the deionized water equivalent to acetone parts by weight 35-45%, 40- are slowly added dropwise with 30-40 drops/min speed 45 DEG C of constant-temperature condensations backflow 60-72h, suction filtration, acetone is washed 3-4 times, then uses tetrahydrofuran with methanol volume ratio for 1:2-3 matches somebody with somebody The mixed solution recrystallization put, 60-65 DEG C of vacuum drying 20-24h, obtains eight vinyl polyhedral silsesquioxanes;
(2)By step(1)Product, allyl glycidyl ether and toluene in mass ratio 1:1.2-1.3:8-10, which adds reaction, to be held In device, logical nitrogen 30-40min excludes oxygen and is mixed evenly, and adds catalyst 2,2 '-azodiisobutyronitrile and co-catalysis Agent pentanedione acid chromium, continues to be mixed evenly, and is warming up to 60-70 DEG C, temperature constant magnetic stirring condensing reflux 12-15h, rotation Turn to be concentrated by evaporation, 60-65 DEG C of vacuum drying obtains epoxy radicals polyhedral silsesquioxane;
(3)In mass ratio 1 in polymeric kettle:6-8:0.2-0.3:0.6-0.8 adds vinyl chloride, petroleum ether and step(2)Production Thing and carbon black, add premixing tank and are premixed, and are heated to 40-45 DEG C, constant temperature stirring 3-5h, while stirring addition peroxidating two Benzoyl, rise temperature starts to polymerize 5-8h to 70-80 DEG C;Wherein the mass ratio of benzoyl peroxide and vinyl chloride is 0.01- 0.02:1;
(4)By Corvic, step(3)Product, ethylene propylene diene rubber and zinc stearate in mass ratio be 1:0.08- 0.15:0.18-0.25:0.06-0.08 is added to be mixed in mixer, is then heated to 75-85 DEG C, is stirred 1-2h;Continue Material in mixer is stirred, and raises temperature to 100-110 DEG C, Tissuemat E, disulfide group acetic acid is sequentially added different Monooctyl ester stannous methide and octadecylimidazoline, continue constant temperature stirring 3-4h, are cooled to 55 DEG C of dischargings;Pre- mixed material is added Pass through the processes such as melting, plasticizing, mixing into extruder from the continuous extruded material of head, as tubing material;Wherein polychlorostyrene second Olefine resin, Tissuemat E, the mass ratio of disulfide group 2-ethyl hexyl ethanoate stannous methide and octadecylimidazoline are 1:0.08-0.1: 0.01-0.02:0.01-0.02.
(5)By the conical double screw extruder extrusion molding of tubing material, pipe, conical double screw extruder die head temperature are obtained 180-195℃;Enter the outside dimension that water cooling sizing tank is determined tubing by calibration sleeve, cooling water after pipe extrusion after air cooling 15-20 DEG C of temperature;Through being cut into pieces after pipe cooling and shaping, pipe to be orientated is obtained;
(6)Pipe to be orientated is immersed in 95-98 DEG C of water bath, heating water bath 4-6min makes to be passed through 95-98 DEG C in tube chamber Hot water, axial tension, rate of extension 25-30mm/s are carried out with stretching device by pipe;To tube cavity heat while pipe is stretched Water applies pressure, pipe is radially dilated by the pressure of pipe inner chamber hot water, while dilating, with sizing sleeve pipe come to swollen Big pipe external diameter pipe is placed in the water-bath that temperature is 10-15 DEG C after sizing, sizing and cooled down, and cool time is 5- 7min, shaping, obtains ethylene propylene diene rubber-polyvinyl chloride composite jacket pipe of carbon black toughening modifying.
It is 80-100nm that described carbon black is ground to average grain diameter in advance.
Described step(6)Middle to apply pressure to tube cavity hot water, its heat hydraulic pressure is 1.6-3.0MPa.
Using above-mentioned technical scheme, beneficial effects of the present invention are:
The present invention obtains eight vinyl polyhedral silsesquioxanes with vinyl trichlorosilane hydrolytic condensation;Eight ethene polyhedrals The vinyl of silsesquioxane and the pi-allyl catalytic polymerization of allyl glycidyl ether, obtain epoxy polyhedral sesquialter Siloxanes;Such a method obtains being whole epoxy radicals polyhedral silsesquioxanes, and epoxy radicals and polyhedral silsesquioxane Skeleton Si between be connected by the flexible chain of certain length, steric hindrance is smaller, and the reactivity of epoxy radicals is higher.The present invention is with chlorine Ethene and epoxy radicals polyhedral silsesquioxane graft polymerization coating modification carbon black, with this filling polyvinyl chloride;Not only incrementss The compatibility of carbon black and polyvinyl chloride, and by the larger Si-O keys of bond energy and Si-C keys and epoxy radicals polyhedral silsesquioxane Huge polyhedron rigid structure is introduced into polyvinyl chloride in molecule, hinders the motion of strand and the effusion of small molecule, its is comprehensive The cooperation heat endurance and shock resistance for improving protecting pipe.A kind of high polymer of saturation of ethylene propylene diene rubber, with excellent Different ageing-resistant performance, weather resistance, electrical insulation capability, chemical resistance, impact elasticity;The present invention is with ethylene propylene diene rubber It is compound as base material with polyvinyl chloride, improve that polyvinyl chloride material is hard, plasticity is poor, impact resistance and weatherability is poor asks Topic.The protecting pipe of the present invention, the characteristics of laying equal stress on high intensity and high tenacity, strong shock resistance.
Embodiment
The ethylene propylene diene rubber of the carbon black toughening modifying of the present embodiment-polyvinyl chloride composite jacket pipe, it is by following steps It is prepared from:
(1)It is 1 in mass ratio by vinyl trichlorosilane and acetone:12 ratio is added in reaction vessel, and mechanical agitation makes It is well mixed, and the deionized water equivalent to acetone parts by weight 35%, 45 DEG C of constant-temperature condensations is slowly added dropwise with 40 drops/min speed Flowed back 72h, and suction filtration, acetone is washed 3 times, then uses tetrahydrofuran with methanol volume ratio for 1:The mixed solution recrystallization of 3 configurations, 65 DEG C of vacuum drying 24h, obtain eight vinyl polyhedral silsesquioxanes;
(2)By step(1)Product, allyl glycidyl ether and toluene in mass ratio 1:1.3:10 add in reaction vessel, Logical nitrogen 40min excludes oxygen and is mixed evenly, and adds catalyst 2,2 '-azodiisobutyronitrile and co-catalyst acetyl group Pyruvic acid chromium, continues to be mixed evenly, and is warming up to 70 DEG C, temperature constant magnetic stirring condensing reflux 15h, rotary evaporation concentration, 65 DEG C vacuum drying, obtain epoxy radicals polyhedral silsesquioxane;
(3)In mass ratio 1 in polymeric kettle:8:0.3:0.8 adds vinyl chloride, petroleum ether and step(2)Product and carbon black, plus Enter premixing tank to be premixed, and be heated to 45 DEG C, constant temperature stirring 5h adds dibenzoyl peroxide, raises temperature while stirring Start to polymerize 8h to 80 DEG C;Wherein the mass ratio of benzoyl peroxide and vinyl chloride is 0.02:1;
(4)By Corvic, step(3)Product, ethylene propylene diene rubber and zinc stearate in mass ratio be 1:0.1: 0.2:Mixed in 0.08 addition mixer, be then heated to 85 DEG C, stir 2h;Continuation is stirred the material in mixer Mix, and raise temperature to 110 DEG C, sequentially add Tissuemat E, disulfide group 2-ethyl hexyl ethanoate stannous methide and octadecyl imidazoles Quinoline, continues constant temperature stirring 4h, is cooled to 55 DEG C of dischargings;Pre- mixed material is added in extruder by melting, plasticizing, mixing Etc. process from the continuous extruded material of head, as tubing material;Wherein Corvic, Tissuemat E, disulfide group acetic acid are different The mass ratio of monooctyl ester stannous methide and octadecylimidazoline is 1:0.1:0.02:0.02.
(5)By the conical double screw extruder extrusion molding of tubing material, pipe, conical double screw extruder die head temperature are obtained 195℃;Enter the outside dimension that water cooling sizing tank is determined tubing by calibration sleeve, the temperature of cooling water after pipe extrusion after air cooling 20 DEG C of degree;Through being cut into pieces after pipe cooling and shaping, pipe to be orientated is obtained;
(6)Pipe to be orientated is immersed in 95 DEG C of water baths, heating water bath 6min makes to be passed through 95 DEG C of hot water in tube chamber, used Pipe is carried out axial tension, rate of extension 30mm/s by stretching device;Apply pressure to tube cavity hot water while pipe is stretched, Pipe is set radially to dilate by the pressure of pipe inner chamber hot water, while dilating, with sizing sleeve pipe come outside to the pipe swollen Footpath pipe is placed in the water-bath that temperature is 15 DEG C after sizing, sizing and cooled down, and cool time is 7min, shaping, obtains charcoal The ethylene propylene diene rubber of black toughening modifying-polyvinyl chloride composite jacket pipe.
It is 100nm that the carbon black of the present embodiment is ground to average grain diameter in advance.
The step of the present embodiment(6)Middle to apply pressure to tube cavity hot water, its heat hydraulic pressure is 3.0MPa.

Claims (4)

1. a kind of ethylene propylene diene rubber of carbon black toughening modifying-polyvinyl chloride composite jacket pipe, it is characterised in that first with ethene Base trichlorosilane hydrolytic condensation obtains eight vinyl polyhedral silsesquioxanes;The ethene of eight vinyl polyhedral silsesquioxanes The pi-allyl catalytic polymerization of base and allyl glycidyl ether, obtains epoxy radicals polyhedral silsesquioxane;Then with chlorine Ethene and epoxy radicals polyhedral silsesquioxane graft polymerization coating modification carbon black, then by modified carbon black, ethylene propylene diene rubber, poly- Vinyl chloride and other auxiliary agents obtain tubing material by premix, melting, plasticizing, mixing extrusion;It is finally extruded to be molded and two-way Stretching, obtains ethylene propylene diene rubber-polyvinyl chloride composite jacket pipe of carbon black toughening modifying.
2. the ethylene propylene diene rubber of the carbon black toughening modifying according to claims 1-polyvinyl chloride composite jacket pipe, it is special Levy and be, it is prepared from by following steps:
(1)It is 1 in mass ratio by vinyl trichlorosilane and acetone:10-12 ratio is added in reaction vessel, mechanical agitation It is well mixed, the deionized water equivalent to acetone parts by weight 35-45%, 40- are slowly added dropwise with 30-40 drops/min speed 45 DEG C of constant-temperature condensations backflow 60-72h, suction filtration, acetone is washed 3-4 times, then uses tetrahydrofuran with methanol volume ratio for 1:2-3 matches somebody with somebody The mixed solution recrystallization put, 60-65 DEG C of vacuum drying 20-24h, obtains eight vinyl polyhedral silsesquioxanes;
(2)By step(1)Product, allyl glycidyl ether and toluene in mass ratio 1:1.2-1.3:8-10, which adds reaction, to be held In device, logical nitrogen 30-40min excludes oxygen and is mixed evenly, and adds catalyst 2,2 '-azodiisobutyronitrile and co-catalysis Agent pentanedione acid chromium, continues to be mixed evenly, and is warming up to 60-70 DEG C, temperature constant magnetic stirring condensing reflux 12-15h, rotation Turn to be concentrated by evaporation, 60-65 DEG C of vacuum drying obtains epoxy radicals polyhedral silsesquioxane;
(3)In mass ratio 1 in polymeric kettle:6-8:0.2-0.3:0.6-0.8 adds vinyl chloride, petroleum ether and step(2)Production Thing and carbon black, add premixing tank and are premixed, and are heated to 40-45 DEG C, constant temperature stirring 3-5h, while stirring addition peroxidating two Benzoyl, rise temperature starts to polymerize 5-8h to 70-80 DEG C;Wherein the mass ratio of benzoyl peroxide and vinyl chloride is 0.01- 0.02:1;
(4)By Corvic, step(3)Product, ethylene propylene diene rubber and zinc stearate in mass ratio be 1:0.08- 0.15:0.18-0.25:0.06-0.08 is added to be mixed in mixer, is then heated to 75-85 DEG C, is stirred 1-2h;Continue Material in mixer is stirred, and raises temperature to 100-110 DEG C, Tissuemat E, disulfide group acetic acid is sequentially added different Monooctyl ester stannous methide and octadecylimidazoline, continue constant temperature stirring 3-4h, are cooled to 55 DEG C of dischargings;Pre- mixed material is added Pass through the processes such as melting, plasticizing, mixing into extruder from the continuous extruded material of head, as tubing material;Wherein polychlorostyrene second Olefine resin, Tissuemat E, the mass ratio of disulfide group 2-ethyl hexyl ethanoate stannous methide and octadecylimidazoline are 1:0.08-0.1: 0.01-0.02:0.01-0.02.
(5)By the conical double screw extruder extrusion molding of tubing material, pipe, conical double screw extruder die head temperature are obtained 180-195℃;Enter the outside dimension that water cooling sizing tank is determined tubing by calibration sleeve, cooling water after pipe extrusion after air cooling 15-20 DEG C of temperature;Through being cut into pieces after pipe cooling and shaping, pipe to be orientated is obtained;
(6)Pipe to be orientated is immersed in 95-98 DEG C of water bath, heating water bath 4-6min makes to be passed through 95-98 DEG C in tube chamber Hot water, axial tension, rate of extension 25-30mm/s are carried out with stretching device by pipe;To tube cavity heat while pipe is stretched Water applies pressure, pipe is radially dilated by the pressure of pipe inner chamber hot water, while dilating, with sizing sleeve pipe come to swollen Big pipe external diameter pipe is placed in the water-bath that temperature is 10-15 DEG C after sizing, sizing and cooled down, and cool time is 5- 7min, shaping, obtains ethylene propylene diene rubber-polyvinyl chloride composite jacket pipe of carbon black toughening modifying.
3. the system of the ethylene propylene diene rubber of the carbon black toughening modifying according to claims 2-polyvinyl chloride composite jacket pipe Preparation Method, it is characterised in that it is 80-100nm that described carbon black is ground to average grain diameter in advance.
4. the system of the ethylene propylene diene rubber of the carbon black toughening modifying according to claims 2-polyvinyl chloride composite jacket pipe Preparation Method, it is characterised in that described step(6)Middle to apply pressure to tube cavity hot water, its heat hydraulic pressure is 1.6-3.0MPa.
CN201710276760.9A 2017-04-25 2017-04-25 A kind of ethylene propylene diene rubber polyvinyl chloride composite jacket pipe of carbon black toughening modifying and preparation method thereof Pending CN107141631A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110776750A (en) * 2019-09-24 2020-02-11 宁波泰意德过滤技术有限公司 Heat-resistant ozone-resistant pressure-variable rubber sealing element and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1644494A (en) * 2004-12-22 2005-07-27 华东师范大学 Method for preparing carbon nanometer tube composites by sol and gel method
CN101942130A (en) * 2009-07-06 2011-01-12 北京华通博奥科贸有限责任公司 Thermoplastic composite material and preparation method thereof as well as cable channel and preparation method thereof
CN103113812A (en) * 2013-02-20 2013-05-22 合肥杰事杰新材料股份有限公司 POSS (Polyhedral oligomeric silsesquioxane)-based nano material modified polyester powder coating and preparation method thereof
CN104356284A (en) * 2014-11-04 2015-02-18 江南大学 Epoxy functional group containing nano-reinforcer for hybrid polymer epoxy resin
CN106046624A (en) * 2016-08-05 2016-10-26 安徽蓝通科技股份有限公司 Carbon black toughened modified PVC pipe and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1644494A (en) * 2004-12-22 2005-07-27 华东师范大学 Method for preparing carbon nanometer tube composites by sol and gel method
CN101942130A (en) * 2009-07-06 2011-01-12 北京华通博奥科贸有限责任公司 Thermoplastic composite material and preparation method thereof as well as cable channel and preparation method thereof
CN103113812A (en) * 2013-02-20 2013-05-22 合肥杰事杰新材料股份有限公司 POSS (Polyhedral oligomeric silsesquioxane)-based nano material modified polyester powder coating and preparation method thereof
CN104356284A (en) * 2014-11-04 2015-02-18 江南大学 Epoxy functional group containing nano-reinforcer for hybrid polymer epoxy resin
CN106046624A (en) * 2016-08-05 2016-10-26 安徽蓝通科技股份有限公司 Carbon black toughened modified PVC pipe and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110776750A (en) * 2019-09-24 2020-02-11 宁波泰意德过滤技术有限公司 Heat-resistant ozone-resistant pressure-variable rubber sealing element and preparation method thereof

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Application publication date: 20170908