CN105153528B - A kind of soft, wear-resisting cross-linking radiation environment-friendly polyolefin CABLE MATERIALS and preparation method thereof - Google Patents
A kind of soft, wear-resisting cross-linking radiation environment-friendly polyolefin CABLE MATERIALS and preparation method thereof Download PDFInfo
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- CN105153528B CN105153528B CN201510503801.4A CN201510503801A CN105153528B CN 105153528 B CN105153528 B CN 105153528B CN 201510503801 A CN201510503801 A CN 201510503801A CN 105153528 B CN105153528 B CN 105153528B
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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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention belongs to the preparation of CABLE MATERIALS, particularly a kind of soft, wear-resisting cross-linking radiation environment-friendly polyolefin CABLE MATERIALS and preparation method thereof.The present invention uses the ethylene-vinyl acetate copolymer of effective quantity, haloflex, POE, compatilizer, fire retardant, fire retarding synergist, plasticizer, antioxidant, lubricant, crosslinking agent, reinforcing agent, releasing agent, stabilizer, surface modifier is through fire retardant and the surface activation process of fire retarding synergist, it is plasticized the preparation of haloflex, banburying, the steps such as granulation are prepared from, the present invention solves the reduction of existing product anti-wear performance, the problem of flexibility difference, it is good with soft and anti-wear performance, finish and intensity are high, the advantages of good flame resistance.
Description
Technical field
The invention belongs to the preparation of CABLE MATERIALS, particularly a kind of soft, wear-resisting cross-linking radiation environment-friendly polyolefin CABLE MATERIALS and
Its preparation method.
Background technology
Cross-linking radiation cable material of polyolefin on domestic market is most with polymer such as EVA, PE as matrix resin, hydrogen
The hydroxide such as aluminum oxide, magnesium hydroxide are fire retardant, add a certain amount of antioxidant, lubricant, crosslinking agent and function
Auxiliary agent is prepared from.To meet CABLE MATERIALS flame-retardancy requirements, the loading of fire retardant need to reach more than 50%.A large amount of fire retardants are filled out
Fill and not only make CABLE MATERIALS hardness and reach more than 97A, and make the reduction of its anti-wear performance, easily because friction produces scratch.In addition spoke
Hardness according to rear CABLE MATERIALS can further increase.Therefore such CABLE MATERIALS cannot be met to pliability and antifriction performance higher wanting
The particular cable industry asked is used, such as welding gun line, portable power source dragging line field.Domestic patent discloses some cross-linking radiations electricity
The preparation method of cable material, but not to irradiation material pliability, antifriction performance make requirement higher, such as just mould macromolecule material
Expect a kind of " weatherability cross-linking radiation CABLE MATERIALS " of (Shanghai) Co., Ltd., ZhiZhengDaoHua macromolecule Materials Co., Ltd., ShangHai
" a kind of 150 DEG C of low-smoke zero-halogen cable materials ", " the photovoltaic cable irradiation of Shanghai Sirui PolymerTechnology Co., Ltd.
The patent documents such as crosslinking type low-smoke halogen-free flame-retardant polyolefin CABLE MATERIALS ".
The content of the invention
It is an object of the invention to provide soft, the wear-resisting cross-linking radiation environment-friendly polyolefin CABLE MATERIALS of one kind and its preparation side
Method, soft, wear-resisting index request is met using its cross-linking radiation environment-friendly polyolefin CABLE MATERIALS for producing.
Overall technology solution of the invention is：
A kind of soft, wear-resisting cross-linking radiation environment-friendly polyolefin CABLE MATERIALS, it by following mass fraction (similarly hereinafter) component system
Into：Ethylene-vinyl acetate copolymer 20-30 parts, haloflex 10-20 parts, ethylene-octene copolymer 5-15 parts, compatilizer
5-10 parts, fire retardant 40-60 parts, fire retarding synergist 5-10 parts, plasticizer 2-6 parts, antioxidant 1-2 parts, lubricant 1-2 parts, friendship
1-2 parts, reinforcing agent 0.5-1.5 parts, releasing agent 0.3-1.0 parts, stabilizer 0.1-0.5 parts, surface modifier 0.5-1 parts of agent of connection.
A kind of method for preparing soft, wear-resisting cross-linking radiation environment-friendly polyolefin CABLE MATERIALS, comprises the following steps：
A, fire retardant, the surface activation process of fire retarding synergist：Fire retardant, fire retarding synergist are poured into spraying respectively
The homogenizer high speed stirring 10-15min of device, surface modifier is sprayed while stirring to powder, is made modified resistance
Combustion agent；
The preparation of b, plasticising haloflex：Haloflex is poured into the homogenizer high speed with sprayer unit
Stirring 5-10min, sprays plasticizer while stirring, be made plasticising haloflex；
C, banburying：Rest materials are weighed by formula, pouring into after being stirred 3 minutes in banbury carries out banburying, is in material temperature
100-111 DEG C, 110-120 DEG C, 120-130 DEG C when material is respectively turned over once, blowing when material temperature reaches 140-150 DEG C；
D, granulation：Treat to send into extruding pelletization in twin-screw Dual inoculation after the completion of material banburying, each area's temperature of screw rod is
100-160℃。
Concrete technology condition of the invention also has：
Vinyl acetate content in described ethylene-vinyl acetate copolymer is 28%, and melt index is 3-10g/
10min。
Content of Cl element is 30%-40%, shore hardness≤50A, Mooney viscosity 70- in described haloflex
80ML。
Described ethylene-octene copolymer melt index under the conditions of 190 DEG C, 2.16Kg is 3-5g/10min, and shore is hard
Degree≤85A.
Described compatilizer is maleic anhydride grafted ethene-acetate ethylene copolymer, and its grafting rate is 0.5%-1.0%.
Described fire retardant is from a kind of in aluminium hydroxide, magnesium hydroxide, hydrotalcite or its combination, its particle diameter≤1.5 μm.
Described fire retarding synergist is made up of TDE and antimony oxide, and the two mass ratio is decabrominated dipheny second
Alkane：Antimony oxide=1-3：1.
Described plasticizer is from the one kind in DOS, DOP, DOA.
Described antioxidant by etc. quality primary antioxidant 1010 and auxiliary antioxidant 168 constitute.
Described lubricant is made up of silicone master batch and Tissuemat E, and wherein the content of siloxane in silicone master batch is more than
50%.
Described crosslinking agent is made up of iso-cyanuric acid triallyl ester and cumyl peroxide.
Described reinforcing agent selects white carbon, its dioxide-containing silica >=97%, fineness >=2000 mesh.
Described releasing agent is EBS, and its fusing point is 140-147 DEG C.
Described stabilizer is calcium-zinc composite stabilizing agent.
Described surface modifier is the one kind in silane coupler, titanate esters, stearic acid.
The substantive distinguishing features having of the invention and the notable technological progress for obtaining are：
1st, novelty of the present invention haloflex and ethylene-vinyl acetate copolymer are arranged in pairs or groups uses, because chlorination is poly-
The characteristics of ethene has soft, wear-resisting, -30 DEG C still have fabulous pliability, and weatherability, resistance to ozone, chemical-resistant resistance,
Ageing-resistant, fire resistance and anti-drip can be splendid.Therefore, CABLE MATERIALS of the present invention has fabulous softness (shore is hard after irradiation
Degree≤90A), anti-wear performance.
2nd, ethylene-octene copolymer (＜ -70 DEG C of brittle temperature) is added in matrix resin, this can be not only improved
The resistance to low temperature of the prepared CABLE MATERIALS of invention, and its flexibility and finish can be improved.
3rd, due to haloflex have it is highly polar, it is compatible with ethylene-vinyl acetate copolymer, ethylene-octene copolymer
Property is poor, it is therefore desirable to carry out reinforcement to matrix resin to improve its tensile strength.The present invention carries out reinforcement by three aspects：
First adds the compatilizer with polar group maleic anhydride, to improve the compatibility of matrix resin；Second adds reinforcing agent white
Carbon black, to improve the intensity of CABLE MATERIALS；3rd adds crosslinking agent in matrix resin so that matrix resin is cross-linked to form certain
Network structure, and then improve CABLE MATERIALS intensity.
4th, from TDE and antimony oxide as fire retarding synergist.Bromide fire retardant self-extinguishment ability and height
Effect, environmental protection；Antimony oxide has cooperative flame retardant effect higher to TDE and haloflex, can significantly improve
The fire resistance of CABLE MATERIALS.Cable prepared by CABLE MATERIALS of the present invention can be by bunchy burning A class hierarchies.
Specific embodiment
The invention will be further described with reference to embodiments, but not as a limitation of the invention, guarantor of the invention
Shield scope is defined by the content that claim is recorded, and any equivalent technical elements made according to this specification are replaced, not
Depart from protection scope of the present invention.
Each raw material proportioning in embodiment 1-5 is as follows：
The preparation method of embodiment 1-5 is as follows：
A, fire retardant, fire retarding synergist are poured into homogenizer high speed with sprayer unit respectively by formula stir
10-15min, surface modifier is sprayed while stirring to powder, obtains modified flame-retardant agent；
B, haloflex is poured into homogenizer high speed with sprayer unit by formula stir 5-10min, stir
Plasticizer is sprayed while mixing, obtains being plasticized haloflex；
C and then rest materials are weighed by formula, pouring into after being stirred 3-5 minutes in banbury carries out banburying；It is in material temperature
100-111 DEG C, 110-120 DEG C, 120-130 DEG C when material is respectively turned over once, blowing when material temperature reaches 140-150 DEG C；
D, when material temperature reaches 145-160 DEG C send into KS75-180 twin-screw Dual inoculations in carry out extruding pelletization, spiral shell
Gan Ge areas temperature is 100-160 DEG C.
Ethylene-vinyl acetate copolymer selects EVA1055 in embodiment 1, and haloflex is from Hangzhou section profit Chemical Manufacture
CM135B, ethylene-octene copolymer selects DF810, fire retardant to select aluminium hydroxide, and fire retarding synergist is by 3 parts of decabrominated diphenies
Ethane, 2 parts of antimony oxide compositions, plasticizer select DOP, and lubricant is by 0.8 part of silicone master batch and 0.2 part of Tissuemat E group
Into crosslinking agent is made up of 0.9 part of iso-cyanuric acid triallyl ester and 0.1 part of cumyl peroxide, and surface modifier is selected
Silane coupler.
Ethylene-vinyl acetate copolymer selects EVA1828 in embodiment 2, and haloflex is from Hangzhou section profit Chemical Manufacture
CM135B, ethylene-octene copolymer selects DF810, fire retardant to select hydrotalcite, and fire retarding synergist is by 4 parts of decabrominated dipheny second
Alkane, 3 parts of antimony oxide compositions, plasticizer select DOP, and lubricant agent is by 0.9 part of silicone master batch and 0.3 part of Tissuemat E group
Into crosslinking agent is made up of 1.3 parts of iso-cyanuric acid triallyl esters and 0.1 part of cumyl peroxide, and surface modifier is selected
Silane coupler.
Ethylene-vinyl acetate copolymer selects EVA2803, haloflex to be produced from LG-DOW company in embodiment 3
CPE702P, ethylene-octene copolymer selects DF840, fire retardant to select aluminium hydroxide, and fire retarding synergist is by 5 parts of decabrominated diphenies
Ethane and 3 parts of antimony oxide compositions, plasticizer select DOS, and lubricant agent is by 1 part of silicone master batch and 0.4 part of Tissuemat E group
Into crosslinking agent is made up of 1.5 parts of iso-cyanuric acid triallyl esters and 0.2 part of cumyl peroxide, and surface modifier is selected
Titanate coupling agent.
Ethylene-vinyl acetate copolymer selects EVA28005, haloflex to be produced for LG-DOW company in embodiment 4
CPE702P, ethylene-octene copolymer selects DF840, fire retardant to be made up of 45 parts of aluminium hydroxides and 10 parts of magnesium hydroxides, hinders
Combustion synergist is made up of 7 parts of TDEs and 3 parts of antimony oxides, and plasticizer selects DOS, and lubricant agent is by 1.4 parts of silicon
Ketone master batch and 0.4 part of Tissuemat E composition, crosslinking agent are different by 1.6 parts of iso-cyanuric acid triallyl esters and 0.2 part of peroxidating two
Propyl benzene is constituted, and surface modifier selects titanate coupling agent.
Ethylene-vinyl acetate copolymer selects EVA265 in embodiment 5, and haloflex is from Hangzhou section profit Chemical Manufacture
CPE702P, ethylene-octene copolymer selects DF840, and fire retardant is made up of 50 parts of hydrotalcites and 10 parts of magnesium hydroxides, fire-retardant
Synergist is made up of 7 parts of TDEs and 3 parts of antimony oxides, and plasticizer selects DOA, and lubricant is by 1.5 parts of silicone mothers
Grain and 0.5 part of Tissuemat E composition, crosslinking agent is by 1.8 parts of iso-cyanuric acid triallyl esters and 0.2 part of cumyl peroxide
Composition, surface modifier is stearic acid surface activating agent.
Remaining content is for example foregoing in embodiment 1-5.
Applicant is to foundation People's Republic of China (PRC) machinery industry standard after the CABLE MATERIALS irradiation prepared by embodiment 1-5
GB/T10436-2004 is detected that specific testing result is shown in Table 2, and wherein embodiment 1,2 irradiation doses are 15 Megarads, real
A 3-5 irradiation dose is applied for 12 Megarads.
Claims (8)
1. a kind of soft, wear-resisting cross-linking radiation environment-friendly polyolefin CABLE MATERIALS, it is characterised in that it by following mass fraction component
It is made：Ethylene-vinyl acetate copolymer 20-30 parts, haloflex 10-20 parts, ethylene-octene copolymer 5-15 parts, it is compatible
Agent 5-10 parts, fire retardant 40-60 parts, fire retarding synergist 5-10 parts, plasticizer 2-6 parts, antioxidant 1-2 parts, lubricant 1-2 parts,
Crosslinking agent 1-2 parts, reinforcing agent 0.5-1.5 parts, releasing agent 0.3-1.0 parts, stabilizer 0.1-0.5 parts, surface modifier 0.5-1
Part；Content of Cl element is 30%-40%, shore hardness≤50A, Mooney viscosity 70-80ML in described haloflex；It is described
Compatilizer be maleic anhydride grafted ethene-acetate ethylene copolymer, its grafting rate is 0.5%-1.0%, and fire retardant selects hydrogen
A kind of or its combination, its particle diameter≤1.5 μm in aluminum oxide, magnesium hydroxide, hydrotalcite；Fire retarding synergist by TDE and
Antimony oxide is constituted, and the two mass ratio is TDE：Antimony oxide=1-3：1；Crosslinking agent is different by triallyl
Cyanurate and cumyl peroxide are constituted；Reinforcing agent selects white carbon, its dioxide-containing silica >=97%, and fineness >=
2000 mesh；Vinyl acetate content in described ethylene-vinyl acetate copolymer is 28%, and melt index is 3-10g/10min；
Described ethylene-octene copolymer melt index under the conditions of 190 DEG C, 2.16Kg is 3-5g/10min, shore hardness≤85A.
2. one kind according to claim 1 is soft, wear-resisting cross-linking radiation environment-friendly polyolefin CABLE MATERIALS, it is characterised in that described
Plasticizer from the one kind in DOS, DOP, DOA.
3. one kind according to claim 1 is soft, wear-resisting cross-linking radiation environment-friendly polyolefin CABLE MATERIALS, it is characterised in that described
Antioxidant by etc. quality primary antioxidant 1010 and auxiliary antioxidant 168 constitute.
4. one kind according to claim 1 is soft, wear-resisting cross-linking radiation environment-friendly polyolefin CABLE MATERIALS, it is characterised in that described
Lubricant be made up of silicone master batch and Tissuemat E, wherein the content of siloxane in silicone master batch be more than 50%.
5. one kind according to claim 1 is soft, wear-resisting cross-linking radiation environment-friendly polyolefin CABLE MATERIALS, it is characterised in that described
Releasing agent be EBS, its fusing point be 140-147 DEG C.
6. one kind according to claim 1 is soft, wear-resisting cross-linking radiation environment-friendly polyolefin CABLE MATERIALS, it is characterised in that described
Stabilizer be calcium-zinc composite stabilizing agent.
7. one kind according to claim 1 is soft, wear-resisting cross-linking radiation environment-friendly polyolefin CABLE MATERIALS, it is characterised in that described
Surface modifier be the one kind in silane coupler, titanate esters, stearic acid.
8. a kind of method of soft, the wear-resisting cross-linking radiation environment-friendly polyolefin CABLE MATERIALS prepared described in claim 1, its feature exists
In comprising the following steps：
A, fire retardant, the surface activation process of fire retarding synergist：Fire retardant, fire retarding synergist are poured into sprayer unit respectively
Homogenizer high speed stirring 10-15min, while stirring to powder spray surface modifier, be made modified flame-retardant agent；
The preparation of b, plasticising haloflex：Haloflex is poured into the homogenizer high speed stirring with sprayer unit
5-10min, sprays plasticizer while stirring, be made plasticising haloflex；
C, banburying：Rest materials are weighed by formula, pouring into after being stirred 3 minutes in banbury carries out banburying, be 100-111 in material temperature
DEG C, 110-120 DEG C, 120-130 DEG C when material is respectively turned over once, blowing when material temperature reaches 140-150 DEG C；
D, granulation：Treat to send into extruding pelletization in twin-screw Dual inoculation after the completion of material banburying, each area's temperature of screw rod is 100-
160℃。
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| CN106349539A (en) * | 2016-08-29 | 2017-01-25 | 湖北祥源新材科技股份有限公司 | Blister sheets of flame-retardant and heat insulation and preparing method thereof |
| CN106590006A (en) * | 2016-12-07 | 2017-04-26 | 安徽合聚阻燃新材料股份有限公司 | Class-B flame-retarding irradiation crosslinking halogen-free low-smoke insulated cable material |
| CN107200917B (en) * | 2017-06-30 | 2020-03-24 | 江苏德威新材料股份有限公司 | High-flame-retardant composite material for new energy high-voltage wire and preparation method thereof |
| CN109306108A (en) * | 2018-09-12 | 2019-02-05 | 苏州希普拉斯新材料有限公司 | XLPE low smoke and low halogen cable material of polyolefin |
| CN109553845A (en) * | 2018-11-13 | 2019-04-02 | 苏州亨利通信材料有限公司 | Prevent adhesion the preparation method of cable material of polyolefin |
| CN109438825A (en) * | 2018-11-13 | 2019-03-08 | 苏州亨利通信材料有限公司 | High working property energy cross-linking radiation cable material of polyolefin |
| CN112574518B (en) * | 2020-12-14 | 2022-08-05 | 上海凯波电缆特材股份有限公司 | Ultraviolet irradiation crosslinked chlorinated polyethylene cable material and preparation method thereof |
| CN114605749A (en) * | 2022-02-21 | 2022-06-10 | 镇江市华银仪表电器有限公司 | Flame-retardant heat-resistant irradiation cross-linked chlorinated polyethylene cable material and preparation method thereof |
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| JPS60252646A (en) * | 1984-05-30 | 1985-12-13 | Showa Electric Wire & Cable Co Ltd | Flame-retardant composition |
| CN102070821B (en) * | 2010-12-14 | 2013-02-13 | 江苏德威新材料股份有限公司 | Irradiation cross-linking oil resistance type soft low smoke zero halogen flame-retardant cable material |
| CN102276928B (en) * | 2011-06-17 | 2013-03-20 | 湖北祥源新材科技有限公司 | Olefin rubber high-flame-retardant oil-resistant heat-shrinkable bush and preparation method thereof |
| CN102585322B (en) * | 2012-02-27 | 2014-06-25 | 广州凯恒科塑有限公司 | Easily-processed low-smoke halogen-free flame-retardant heat shrinkable label sleeve as well as preparation and application thereof |
| CN103709539B (en) * | 2013-12-19 | 2016-04-27 | 广州凯恒科塑有限公司 | A kind of oil resistant fire-retardant chlorinated polyethylene heat-shrinkable T bush and preparation method and application |
| CN103694551A (en) * | 2013-12-21 | 2014-04-02 | 深圳市沃尔核材股份有限公司 | Irradiation crosslinking environment-friendly fire-retardant material for non-foaming pipe wall in heat shrinkage and application thereof |
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Effective date of registration: 20201215 Address after: No.29 Xingfu Road, tianshenggang street, Chongchuan District, Nantong City, Jiangsu Province, 226000 Patentee after: Jiangsu duoshang New Material Technology Co.,Ltd. Address before: 465450 Chengang formation, Guoxiang village, Suntiepu Town, Guangshan County, Xinyang City, Henan Province Patentee before: Li Bing |
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Effective date of registration: 20211229 Address after: 7 / F, Chenqiao hi tech Pioneer Park, 188 Jimei Road, Chenqiao street, Gangzha District, Nantong City, Jiangsu Province, 226000 Patentee after: Jiangsu Xushu New Material Co.,Ltd. Address before: No.29 Xingfu Road, tianshenggang street, Chongchuan District, Nantong City, Jiangsu Province, 226000 Patentee before: Jiangsu duoshang New Material Technology Co.,Ltd. |