CN103724812A - Modified cable protection pipe material and preparation method thereof - Google Patents

Modified cable protection pipe material and preparation method thereof Download PDF

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Publication number
CN103724812A
CN103724812A CN201410014018.7A CN201410014018A CN103724812A CN 103724812 A CN103724812 A CN 103724812A CN 201410014018 A CN201410014018 A CN 201410014018A CN 103724812 A CN103724812 A CN 103724812A
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Prior art keywords
cable protection
protection tube
tube material
propylene
maleic anhydride
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严曾评
刘志光
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SHANGHAI SHENHE PLASTIC INDUSTRY Co Ltd
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SHANGHAI SHENHE PLASTIC INDUSTRY Co Ltd
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Publication of CN103724812A publication Critical patent/CN103724812A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/24—Crystallisation aids

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Organic Insulating Materials (AREA)
  • Insulated Conductors (AREA)

Abstract

The invention discloses a modified cable protection pipe material which comprises the following components in percentage by mass: 80-95% of polypropylene, 1-18% of a flexibilizer, 0.01-0.3% of a beta nucleating agent, 0.01-1% of an antioxidant, 0.5-3% of a lubricant and 0.05-2.5% of a modifying assistant. The invention further provides a preparation method of the modified cable protection pipe material. Through mechanical performance tests, the impact strength, the elongation at break and the yield stress of the material obtained by a modifying method of beta crystal synergetic enhancement and toughening are remarkably enhanced, and particularly, the low-temperature impact strength of the material is improved by 5-6 times.

Description

A kind of modification cable protection tube material and preparation method thereof
Technical field:
The present invention relates to polymeric material field, relate in particular to the material of processing cable protective tube, particularly a kind of modification cable protection tube material and preparation method thereof.
Background technology:
Since 20th century, the system of laying of high voltage power cable and telecommunication cable from built on stilts enter buried.In prior art, for the protective casing of buried cable, be widely used pvc material processing, wherein dosed leaded and stablizer chromium.So tubing is long-term when buried, has heavy metal ion releasing, causes soil lead tolerance to exceed standard.By contrast, polypropylene pipe itself is nontoxic, and also the compound of heavy metal free ion, is a kind of power cable and telecommunication cable protective casing material of environmental protection.But the shortcomings such as impelling strength is low, low temperature brittleness that polypropylene exists.Polyacrylic toughness modification conventionally adopts and adds elastomeric method, and elastomerics is obvious to improving toughness effect, but also can reduce the intensity of material thereupon.
Summary of the invention:
The object of the present invention is to provide a kind of modification cable protection tube material, described this modification cable protection tube material will solve that polypropylene pipe impelling strength of the prior art is low, the technical problem of low temperature brittleness.
This modification cable protection tube material of the present invention, is comprised of polypropylene, toughner, beta nucleater, oxidation inhibitor, lubricant and modified additive, and in described cable protection tube material, the mass percent of each composition is:
Figure BDA0000456208000000011
Figure BDA0000456208000000021
Further, described polyacrylic melt flow rate (MFR) (MFR) is 0.2～0.4g/10min(230 ℃, 2.16kg).
Further, described toughner is maleic anhydride grafted ethene-propylene-octene terpolymer (EPO-g-MAH), and in described ethylene-propylene-octene terpolymer, ethylene content is 1～10%, and octene content is 0.1～10%.Maleic anhydride graft toughner, by introducing strong polar reaction group, makes material have high polarity and reactivity, greatly improves the consistency of matrix material.
Further, described beta nucleater is aromatic amides compounds or rare-earth compounds.
Further, described aromatic amides compounds is selected from dicyclohexyl terephthalamide (DCHT) or 2,6 one phthalic acid Cyclohexamides.
Further, to be selected from ordination number be 57 to 71 lanthanide oxide to described rare-earth compounds.
Further, described oxidation inhibitor is the combination of a kind of in antioxidant 1010 (four [β (3,5-di-tert-butyl-phenyl-4-hydroxy phenyl) propionic acid] pentaerythritol ester) or irgasfos 168 (three [2,4-di-tert-butyl-phenyl] phosphorous acid ester) or two kinds.The effect of described oxidation inhibitor is to protect polymkeric substance, avoids and oxygen generation Degradation, improves the heat-resisting oxidation stability of goods.
Further, when antioxidant 1010 and person's irgasfos 168 are used in combination, its mass ratio is 1～3:1～3.
Further, described lubricant is diffusant ethylene bis stearamide (EBS).
Further, described modified additive is organosilicon polymer (PSI), and its molecular formula is:
Figure BDA0000456208000000022
Wherein, R and R ' are respectively
Figure BDA0000456208000000023
or
Figure BDA0000456208000000024
or-CH=CH-or-CH 3, or-NH 2.Organosilicon polymer (PSI) has lubrication, to processing, brings convenience, and can also change material crystalline state, reduces the contraction of material.
The present invention also provides a kind of method of preparing above-mentioned modification cable protection tube material, described method comprises a step that takes ethylene-propylene-octene terpolymer, also comprise a step that takes maleic anhydride (MAH) and superoxide, described maleic anhydride (MAH) is 1:0.01～1 with the mass ratio of superoxide, maleic anhydride (MAH) is mixed with superoxide, with acetone solution, solution is added in load weighted ethylene-propylene-octene terpolymer, with high-speed mixer heated and stirred 3～15min, mixture is joined to twin-screw extrusion unit, when melt extruding, produce graft reaction, obtain maleic anhydride grafted ethene-propylene-octene terpolymer (EPO-g-MAH), then proportionally take maleic anhydride grafted ethene-propylene-octene terpolymer (EPO-g-MAH) and polypropylene, beta nucleater, oxidation inhibitor, lubricant, the quality of modified additive, by mentioned component at high speed mixer high speed blend 5～10min, then join in twin screw extruder and extrude and granulation, make modification cable protection tube material.
Further, described superoxide is dicumyl peroxide (DCP).
Principle of work of the present invention is: polyacrylic crystal formation is that α is brilliant, only has under given conditions and could form β crystalline substance.β Jingjing sheet and macromole folded chain link together, and the crystalline substance bundle of phase vincial faces and other one brilliant bundle intersect to form IPN, therefore there is no obvious interface, thereby have improved polypropylene material toughness and intensity.Maleic anhydride graft reaction is in melting process, and MAH is monomer-grafted in polymer molecular chain, makes material have high polarity and reactivity, can have good consistency with each component compound, improves the mechanical property of matrix material.
The present invention be take polypropylene as base material, usings maleic anhydride grafted ethene-propylene-octene terpolymer as toughner, improves material compatibility, toughness.Add beta nucleater, induction beta-crystalline form becomes, and keeps and improves the strength of materials.By formula of the present invention, make matrix material, significantly improved toughness and intensity, improved low temperature brittleness, use more safety and reliable.
The present invention and prior art are compared, and its effect is actively with obvious.Adopt that β brilliantly collaboratively strengthens, toughness reinforcing method of modifying, the material according to said method obtaining, by Mechanics Performance Testing, the resistance to impact shock of material, elongation at break, yielding stress significantly promote, and particularly in the low temperature impact strength of material, have improved 5～6 times.
Embodiment:
Below in conjunction with example, content of the present invention is further set forth to explanation, but the content of invention is not only confined to listed experiment below:
Embodiment 1
Take formula material (mass percent %):
Figure BDA0000456208000000041
The preparation process of maleic anhydride grafted ethene-propylene-octene terpolymer is as follows:
First take ethylene-propylene-octene terpolymer, then maleic anhydride (MAH) is mixed in 1:0.01～1 ratio with dicumyl peroxide (DCP), use acetone solution.Solution is added to load weighted ethylene-propylene-octene terpolymer, with high-speed mixer heated and stirred 5min, mixture is joined to twin-screw extrusion unit.Prepare maleic anhydride grafted ethene-propylene-octene terpolymer (EPO-g-MAH).
Then by said components, by proportion speed, take material, by maleic anhydride grafted ethene-propylene-octene terpolymer (EPO-g-MAH) and the polypropylene of preparation, aromatic amides beta nucleater, antioxidant 1010, irgasfos 168, EBS, methyl vinyl silicone rubber at high speed mixer high speed blend 5～10min, then join in twin screw extruder and extrude and granulation, make matrix material.Its performance is in Table 1.
Embodiment 2
Take formula material (mass percent %):
The preparation process of maleic anhydride grafted ethene-propylene-octene terpolymer is as follows:
First take ethylene-propylene-octene terpolymer, then maleic anhydride (MAH) is mixed in 1:0.01～1 ratio with dicumyl peroxide (DCP), use acetone solution.Solution is added to load weighted ethylene-propylene-octene terpolymer, with high-speed mixer heated and stirred 5min, mixture is joined to twin-screw extrusion unit.Prepare maleic anhydride grafted ethene-propylene-octene terpolymer (EPO-g-MAH).
Then by said components, by proportion speed, take material, by maleic anhydride grafted ethene-propylene-octene terpolymer (EPO-g-MAH) and the polypropylene of preparation, aromatic amides beta nucleater, antioxidant 1010, irgasfos 168, EBS, dimethyl silicone rubber at high speed mixer high speed blend 5～10min, then join in twin screw extruder and extrude and granulation, make matrix material.Its performance is in Table 1.
Embodiment 3
Take formula material: (mass percent %):
Figure BDA0000456208000000052
Prepare maleic anhydride grafted ethene-propylene-octene terpolymer:
First take ethylene-propylene-octene terpolymer, maleic anhydride (MAH) and dicumyl peroxide (DCP) are mixed in proportion, use acetone solution.Solution is added to load weighted ethylene-propylene-octene terpolymer, with high-speed mixer heated and stirred 5min, mixture is joined to twin-screw extrusion unit.Prepare maleic anhydride grafted ethene-propylene-octene terpolymer (EPO-g-MAH).
Then by said components, by proportion speed, take material, by maleic anhydride grafted ethene-propylene-octene terpolymer (EPO-g-MAH) and the polypropylene of preparation, aromatic amides beta nucleater, antioxidant 1010, irgasfos 168, EBS, dimethyl silicone rubber at high speed mixer high speed blend 5～10min, then join in twin screw extruder and extrude and granulation, make matrix material.Its performance is in Table 1.
Embodiment 4
Take formula material (mass percent %):
Figure BDA0000456208000000061
The preparation process of maleic anhydride grafted ethene-propylene-octene terpolymer is as follows:
First take ethylene-propylene-octene terpolymer, then maleic anhydride (MAH) is mixed in 1:0.01～1 ratio with dicumyl peroxide (DCP), use acetone solution.Solution is added to load weighted ethylene-propylene-octene terpolymer, with high-speed mixer heated and stirred 5min, mixture is joined to twin-screw extrusion unit.Prepare maleic anhydride grafted ethene-propylene-octene terpolymer (EPO-g-MAH).
Then by said components, by proportion speed, take material, by maleic anhydride grafted ethene-propylene-octene terpolymer (EPO-g-MAH) and the polypropylene of preparation, rare earth class beta nucleater, antioxidant 1010, irgasfos 168, EB-FF, methyl vinyl silicone rubber at high speed mixer high speed blend 5～10min, then join in twin screw extruder and extrude and granulation, make matrix material.Its performance is in Table 1.
The made cable protection tube material over-all properties of the present invention is good, strengthens toughening effect obvious.
Table 1 cable protection tube material over-all properties
? Pure PP Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Flexural strength, MPa 25.2 24.5 26.7 27.3 25.3
Bending elastic modulus, MPa 1220 940 1065 1030 1190
Notched Izod impact strength, KJ/m 2(normal temperature) 36.7 37.2 54.8 75.1 38.5
Notched Izod impact strength, KJ/m 2（-20℃） 9.4 12.4 15.2 37.7 11.6
Elongation at break, % 372 542 988 879 430
Yielding stress, MPa 23.5 22.7 35.7 38.4 24.9
Vicat softening temperature, ℃ 135 149 152 151 153
As can be seen from Table 1, through the polypropylene composite material of method modification of the present invention, its shock strength, elongation at break, yielding stress, vicat softening temperature are improved.Its shock strength is brought up to 75.1KJ/ ㎡ by the resistance to impact shock of pure PP by 36.7KJ/ ㎡, particularly the low temperature impact strength of material is brought up to 37.7KJ/ ㎡ by 9.4KJ/ ㎡, greatly overcome the deficiency of polypropylene low temperature fragility, avoided the problem of easy embrittlement in cold district and winter construction.Adopt the brilliant collaborative enhancing of β, toughening modifying cable protection tube material, effect is remarkable.

Claims (12)

1. a modification cable protection tube material, is characterized in that: polypropylene, toughner, beta nucleater, oxidation inhibitor, lubricant and modified additive, consist of, in described cable protection tube material, the mass percent of each composition is:
Figure FDA0000456207990000011
2. modification cable protection tube material as claimed in claim 1, is characterized in that: described polyacrylic melt flow rate (MFR) is 0.2～0.4g/10min.
3. modification cable protection tube material as claimed in claim 1; it is characterized in that: described toughner is maleic anhydride grafted ethene-propylene-octene terpolymer; in described ethylene-propylene-octene terpolymer, ethylene content is 1～10%, and octene content is 0.1～10%.
4. modification cable protection tube material as claimed in claim 1, is characterized in that: described beta nucleater is aromatic amides compounds or rare-earth compounds.
5. modification cable protection tube material as claimed in claim 4, is characterized in that: described aromatic amides compounds is selected from dicyclohexyl terephthalamide or 2,6 one phthalic acid Cyclohexamides.
6. modification cable protection tube material as claimed in claim 4, is characterized in that: it is 57 to 71 lanthanide oxide that described rare-earth compounds is selected from ordination number.
7. modification cable protection tube material as claimed in claim 1; it is characterized in that: described oxidation inhibitor is selected from four, and [β (3; 5-di-tert-butyl-phenyl-4-hydroxy phenyl) propionic acid] combination of a kind of in pentaerythritol ester, three [2,4-di-tert-butyl-phenyl] phosphorous acid ester or two kinds.
8. modification cable protection tube material as claimed in claim 7; it is characterized in that: described four [β (3; 5-di-tert-butyl-phenyl-4-hydroxy phenyl) propionic acid] pentaerythritol ester and three [2,4-di-tert-butyl-phenyl] phosphorous acid ester is when be used in combination, and its mass ratio is 1～3:1～3.
9. modification cable protection tube material as claimed in claim 1, is characterized in that: described lubricant is ethylene bis stearamide, and its molecular formula is C 17h 35(CO) NHCH 2cH 2hN (CO) C 17h 35.
10. modification cable protection tube material as claimed in claim 1, is characterized in that: described modified additive is organosilicon polymer (PSI), and its molecular formula is:
Figure FDA0000456207990000021
Wherein, R and R ' are respectively
Figure FDA0000456207990000022
or
Figure FDA0000456207990000023
or-CH=CH-or-CH 3, or-NH 2.
11. 1 kinds of methods of preparing modification cable protection tube material as claimed in claim 1, it is characterized in that: comprise a step that takes ethylene-propylene-octene terpolymer, also comprise a step that takes maleic anhydride and superoxide, described maleic anhydride (MAH) is 1:0.01～1 with the mass ratio of superoxide, maleic anhydride is mixed with superoxide, with acetone solution, solution is added in load weighted ethylene-propylene-octene terpolymer, with high-speed mixer heated and stirred 3～15min, mixture is joined to twin-screw extrusion unit, when melt extruding, produce graft reaction, obtain maleic anhydride grafted ethene-propylene-octene terpolymer (EPO-g-MAH), then proportionally take maleic anhydride grafted ethene-propylene-octene terpolymer and polypropylene, beta nucleater, oxidation inhibitor, the quality of lubricant modified auxiliary agent, by mentioned component at high speed mixer high speed blend 5～10min, then join in twin screw extruder and extrude and granulation, make modification cable protection tube material.
The preparation method of 12. modification cable protection tube materials as claimed in claim 11, is characterized in that: described superoxide is dicumyl peroxide, and molecular formula is: C 18h 22o 2.
CN201410014018.7A 2014-01-13 2014-01-13 Modified cable protection pipe material and preparation method thereof Pending CN103724812A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104299711A (en) * 2014-09-26 2015-01-21 安徽华峰电缆集团有限公司 High-heat-dissipation cable protection pipe
CN104927185A (en) * 2015-05-08 2015-09-23 镇江荣诚管业有限公司 Anti-aging antioxidant PP pipe and processing method thereof
CN106589610A (en) * 2017-02-16 2017-04-26 深圳市博富隆新材料科技有限公司 MPP electric power pipe polymer and preparation method thereof
CN109233087A (en) * 2018-06-20 2019-01-18 安徽瑞鑫自动化仪表有限公司 A kind of preparation method of impact resistance electric submersible pump polypropylene cable Insulation Material
CN110498970A (en) * 2019-09-04 2019-11-26 安徽上造智能设备科技有限公司 A kind of high-strength ageing power cable protection sleeve

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CN101067032A (en) * 2007-06-11 2007-11-07 浙江大学 Compositely modified polypropylene and its prepn process
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104299711A (en) * 2014-09-26 2015-01-21 安徽华峰电缆集团有限公司 High-heat-dissipation cable protection pipe
CN104927185A (en) * 2015-05-08 2015-09-23 镇江荣诚管业有限公司 Anti-aging antioxidant PP pipe and processing method thereof
CN106589610A (en) * 2017-02-16 2017-04-26 深圳市博富隆新材料科技有限公司 MPP electric power pipe polymer and preparation method thereof
CN109233087A (en) * 2018-06-20 2019-01-18 安徽瑞鑫自动化仪表有限公司 A kind of preparation method of impact resistance electric submersible pump polypropylene cable Insulation Material
CN110498970A (en) * 2019-09-04 2019-11-26 安徽上造智能设备科技有限公司 A kind of high-strength ageing power cable protection sleeve

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Application publication date: 20140416