CN105733081A - Corrosion-resistant high-flame-retarding thermoplastic low-smoke halogen-free cable material and preparation method thereof - Google Patents
Corrosion-resistant high-flame-retarding thermoplastic low-smoke halogen-free cable material and preparation method thereof Download PDFInfo
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- 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
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- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
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Abstract
The invention discloses a corrosion-resistant high-flame-retarding thermoplastic low-smoke halogen-free cable material including the following components, by weight, 100 parts of polyolefin, 5-20 parts of a compatilizer, 150-200 parts of a flame retardant, 5-40 parts of a high-molecular coating agent, 10-20 parts of an ionic absorber, 1-5 parts of a coupling agent, and 1-5 parts of a lubricant. The invention also provides the preparation method of the corrosion-resistant high-flame-retarding thermoplastic low-smoke halogen-free cable material. Compared with the thermoplastic low-smoke halogen-free cable materials in the prior art, the cable material in the invention effectively solves a problem of poor resistance against acid and alkali of the cable material on the basis of ensuring flame retarding property passes the standard A when the material is used for producing cables. At room temperature, the cable material is less than 20% in change rate on tensile strength and break elongation when being soaked in 10% hydrochloric acid and 10% sodium hydroxide solutions for 30 days respectively.
Description
Technical field
The present invention relates to CABLE MATERIALS and preparation field thereof, be specifically related to a kind of corrosion-resistant high fire-retardance thermoplastic low-smoke halide-free CABLE MATERIALS and preparation method thereof.
Background technology
Along with the quickening of modernization of the country process, as electric power transmission and the data transmission industry in the following main development direction of country, performance more and more important, its range of application and usage quantity also increase year by year.Accordingly, the requirement of CABLE MATERIALS is also being improved by year by year, at present, adopt thermoplastic low-smoke halide-free cable material of polyolefin as the cable of oversheath, in use, often due to the existence of external environment acid-base value, the fire retardant in material is made to create disadvantageous side reaction, so that the performance of cable and life-span reduce rapidly, it is impossible to meet use.Adopting the good silicone rubber of corrosion resistance, finished product is of a relatively high again, and reduces the content of additive, although can reduce the extent of corrosion of cable, but fire-retardant aspect can not reach again corresponding requirements.Therefore a kind of its of invention can meet key property, and thermoplastic cable's material again with good corrosion resistance simultaneously is extremely urgent.
Summary of the invention
One of the technical problem to be solved be in that the deficiency existing for above-mentioned prior art and provide a kind of ensure material make cable after fire-retardant by, while bunchy A, can effectively solve the corrosion-resistant high fire-retardance thermoplastic low-smoke halide-free CABLE MATERIALS of the problem of thermoplastic low-smoke halide-free material not acid and alkali-resistance.
The two of the technical problem to be solved are in that the preparation method providing above-mentioned corrosion-resistant high fire-retardance thermoplastic low-smoke halide-free CABLE MATERIALS.
As the corrosion-resistant high fire-retardance thermoplastic low-smoke halide-free CABLE MATERIALS of one of first aspect present invention, including each component of following parts by weight:
In an excellent embodiment of the present invention, described polyolefin is the mixing of a kind of in ethylene-vinyl acetate copolymer, Low Density Polyethylene, high density polyethylene (HDPE), ethylene methyl acrylate, POE or any two kinds.Polyolefin used by the present invention be with GB/T3682-2000 method measure melt index for 1～20g/10min, the molecular weight vistanex more than 20,000, it is compared with other matrix resin, and price is relatively low, can effectively save cost.
In a preferred embodiment of the invention, described compatilizer is a kind of or arbitrarily two or more mixing in maleic anhydride grafted polyethylene, maleic anhydride inoculated polypropylene, acrylic acid-grafted polyethylene.The addition of compatilizer can improve the compatibility between resin, indirectly increases the macro property of material.
In a preferred embodiment of the invention, described fire retardant is a kind of or arbitrarily two or more mixing in unmodified aluminium hydroxide, magnesium hydroxide, calcium carbonate, red phosphorus.Selected fire retardant particle diameter is all below 2 microns.
In of the present invention is preferable to carry out, described high-molecular coating agent is a kind of or arbitrarily two or more mixing in brucite, water calcium aluminate, metal soap, fatty acid amide, dicarboxylic ester.High-molecular coating agent can be coated on outside fire retardant, it is to avoid fire retardant directly contacts generation side reaction with corrosive reagents.
In of the present invention is preferable to carry out, described ionic absorption agent is the mixing of a kind of in ethoxyquin alkanamine, diethanolamine, ethoxylated alcohol, alkyl carboxylate, alkylphosphonic or any two kinds.Ionic absorption agent can react by the ion preferentially and in corrosive reagents, avoids fire retardant to produce unnecessary side reaction further.
In a preferred embodiment of the invention, described coupling agent is a kind of or arbitrarily two or more mixing in vinyl silanes, amino silane, titanate ester silane.The addition of coupling agent can increase the compatibility between resin and auxiliary agent, make in combination with tightr.
In a preferred embodiment of the invention, described lubricant is end group is a kind of or arbitrarily two or more mixing in the silica gel of vinyl, silicone oil, satisfied fatty acid.The effect of lubricant is the internal pressure reducing and adding screw rod in man-hour, enables material to extrude faster.
As the preparation method of a kind of corrosion-resistant high fire-retardance thermoplastic low-smoke halide-free CABLE MATERIALS of second aspect present invention, comprise the steps:
1) first being put in impregnating by pressure rotary drum by fire retardant and preheat, preheating temperature is 120 DEG C, and preheating time is 15 minutes；Subsequently impregnating by pressure rotary drum is carried out evacuation process, pumpdown time is 15 minutes, pressure≤-0.05Mpa, after evacuation terminates, use the negative pressure within impregnating by pressure rotary drum, again high-molecular coating agent and ionic absorption agent are drawn in impregnating by pressure rotary drum from charge door, and start to rotate impregnating by pressure rotary drum, enable three kinds of materials to be sufficiently mixed, incorporation time is 15 minutes, by vacuum pump, impregnating by pressure rotary drum is pressurizeed subsequently, pressing time is 30 minutes, and pressure >=0.4MPa, after mixing, blowing, obtains semi-finished product A；This step adopts impregnating by pressure rotary drum, additive can be allowed better to enter into inside fire retardant, air in fire retardant internal voids and impurity can be extracted out by evacuation, additive is facilitated to enter, pressurization is that the additive allowing and being attached to flame-retardant skin layer can enter further into inside fire retardant, carries out better being coated with completely.
2) polyolefin, compatilizer being mixed in high-speed mixer, incorporation time is 5 minutes, and speed is 300r/min, is subsequently added coupling agent and lubricant, and incorporation time is 5 minutes, and speed is 300r/min, obtains semi-finished product B；
3) proportionally carry out semi-finished product A and semi-finished product B melting in double screw extruder, mixing, pelletizing, packaging, twin screw design temperature is 130～160 DEG C, and yield is 350kg/h.
In a preferred embodiment of invention, the velocity of rotation of described impregnating by pressure rotary drum is 5～10r/min.
In a preferred embodiment of invention, the volume 2000L of described impregnating by pressure rotary drum, the stainless steel that whole body adopts thickness to be 20mm is prepared from.
Compared with the present invention expects with conventional thermoplastic cable, ensure that on the basis of material high flame resistance, add again the decay resistance of material itself, material of the present invention is individually positioned in the hydrochloric acid of 10% concentration and the sodium hydroxide solution of 10% concentration after 30 days, and the rate of change of its hot strength and elongation at break is respectively less than 20%.The present invention does not adopt silicone rubber that price is higher as main material, can save the production cost of more than 50%；It is better that the present invention does not contain anticorrosive property, but can release the halogen fire retardant of harmful substance during burning, it is ensured that the feature of environmental protection of product itself；The new manufacturing process technology that this product adopts, can make covering and ionic absorption agent better be attached in flame retardant molecule, it is ensured that the decay resistance of product.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.Following example will assist in those skilled in the art and are further appreciated by the present invention, but do not limit the present invention in any form.It should be pointed out that, to those skilled in the art, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement.These broadly fall into protection scope of the present invention.
Because conventional thermoplastic cable expects in use, often due to the existence of external environment acid-base value, the fire retardant in material is made to create disadvantageous side reaction, so that the performance of cable and life-span reduce rapidly, it is impossible to meet and use.Adopting the good silicone rubber of corrosion resistance, finished product is of a relatively high again, and reduces the content of additive, although can reduce the extent of corrosion of cable, but fire-retardant aspect can not reach again corresponding requirements.Therefore a kind of its of invention can meet key property, and thermoplastic cable's material again with good corrosion resistance simultaneously is extremely urgent, and the technical scheme being consequently formed and parts by weight formula composition be:
The material that the present invention obtains is individually positioned in the hydrochloric acid of 10% concentration and the sodium hydroxide solution of 10% concentration after 30 days, and the rate of change of its hot strength and elongation at break is respectively less than 20%.
Concrete corrosion-resistant high fire-retardance thermoplastic low-smoke halide-free CABLE MATERIALS and preparation method thereof is shown in following embodiment, the volume 2000L of the impregnating by pressure rotary drum used in example below, and the stainless steel that whole body adopts thickness to be 20mm is prepared from.The velocity of rotation of impregnating by pressure rotary drum is 5～10r/min.
Embodiment 1
A kind of corrosion-resistant high fire-retardance thermoplastic low-smoke halide-free CABLE MATERIALS, the material composition and the weight portion that comprise are as follows:
The preparation method of this corrosion-resistant high fire-retardance thermoplastic low-smoke halide-free CABLE MATERIALS, comprises the steps:
1) first aluminium hydroxide, calcium carbonate being put in impregnating by pressure rotary drum and preheated, preheating temperature is 120 DEG C, and preheating time is 15 minutes；Subsequently impregnating by pressure rotary drum is carried out evacuation process, pumpdown time is 15 minutes, pressure≤-0.05Mpa, after evacuation terminates, use the negative pressure within impregnating by pressure rotary drum, again by brucite, fatty acid amide, ethoxyquin alkanamine, ethoxylated alcohol is drawn in impregnating by pressure rotary drum from charge door, and start to rotate impregnating by pressure rotary drum, allow them to be sufficiently mixed, incorporation time is 15 minutes, by vacuum pump, impregnating by pressure rotary drum is pressurizeed subsequently, pressing time is 30 minutes, pressure >=0.4MPa, after mixing, blowing, obtain semi-finished product A；
2) ethylene-vinyl acetate copolymer, Low Density Polyethylene, maleic anhydride grafted polyethylene, acrylic acid-grafted polyethylene are mixed in high-speed mixer, incorporation time is 5 minutes, speed is 300r/min, it is subsequently added vinyl silanes, titanate ester silane, satisfied fatty acid, silicone oil, incorporation time is 5 minutes, speed is 300r/min, obtains semi-finished product B；
3) proportionally carry out semi-finished product A and semi-finished product B melting in double screw extruder, mixing, pelletizing, packaging, twin screw design temperature is 130～160 DEG C, and yield is 350kg/h.
Embodiment 2
A kind of corrosion-resistant high fire-retardance thermoplastic low-smoke halide-free CABLE MATERIALS, the material composition and the weight portion that comprise are as follows:
The preparation method of this corrosion-resistant high fire-retardance thermoplastic low-smoke halide-free CABLE MATERIALS, comprises the steps:
1) first magnesium hydroxide, red phosphorus being put in impregnating by pressure rotary drum and preheated, preheating temperature is 120 DEG C, and preheating time is 15 minutes；Subsequently impregnating by pressure rotary drum is carried out evacuation process, pumpdown time is 15 minutes, pressure≤-0.05Mpa, after evacuation terminates, use the negative pressure within impregnating by pressure rotary drum, again by water calcium aluminate, metal soap, diethanolamine, alkylphosphonic is drawn in impregnating by pressure rotary drum from charge door, and start to rotate impregnating by pressure rotary drum, allow them to be sufficiently mixed, incorporation time is 15 minutes, by vacuum pump, impregnating by pressure rotary drum is pressurizeed subsequently, pressing time is 30 minutes, pressure >=0.4MPa, after mixing, blowing, obtain semi-finished product A；
2) high density polyethylene (HDPE), ethylene methyl acrylate, acrylic acid-grafted polyethylene being mixed in high-speed mixer, incorporation time is 5 minutes, and speed is 300r/min, it is subsequently added amino silane, silica gel, silicone oil, incorporation time is 5 minutes, and speed is 300r/min, obtains semi-finished product B；
3) proportionally carry out semi-finished product A and semi-finished product B melting in double screw extruder, mixing, pelletizing, packaging, twin screw design temperature is 130～160 DEG C, and yield is 350kg/h.
Embodiment 3
A kind of corrosion-resistant high fire-retardance thermoplastic low-smoke halide-free CABLE MATERIALS, the material composition and the weight portion that comprise are as follows:
The preparation method of this corrosion-resistant high fire-retardance thermoplastic low-smoke halide-free CABLE MATERIALS, comprises the steps:
1) first aluminium hydroxide, magnesium hydroxide being put in impregnating by pressure rotary drum and preheated, preheating temperature is 120 DEG C, and preheating time is 15 minutes；Subsequently impregnating by pressure rotary drum is carried out evacuation process, pumpdown time is 15 minutes, pressure≤-0.05Mpa, after evacuation terminates, use the negative pressure within impregnating by pressure rotary drum, again dicarboxylic ester, alkyl carboxylate are drawn in impregnating by pressure rotary drum from charge door, and start to rotate impregnating by pressure rotary drum, allowing them to be sufficiently mixed, incorporation time is 15 minutes, by vacuum pump, impregnating by pressure rotary drum is pressurizeed subsequently, pressing time is 30 minutes, and pressure >=0.4MPa, after mixing, blowing, obtains semi-finished product A；
2) POE, ethylene-vinyl acetate copolymer, maleic anhydride grafted polyethylene are mixed in high-speed mixer, incorporation time is 5 minutes, speed is 300r/min, it is subsequently added vinyl silanes, satisfied fatty acid, silica gel, incorporation time is 5 minutes, speed is 300r/min, obtains semi-finished product B；
3) proportionally carry out semi-finished product A and semi-finished product B melting in double screw extruder, mixing, pelletizing, packaging, twin screw design temperature is 130～160 DEG C, and yield is 350kg/h.
Comparative example
This comparative example is not corrosion resistant high fire-retardance thermoplastic low-smoke halide-free polyolefin products.
After above example 1～3 and comparative example detect, result is shown in table 1 below.
Table 1 embodiment, comparative example the performance test results
As shown in Table 1, the data of embodiment significantly better than the data of comparative example, to illustrate that the technique in the employing present invention and auxiliary agent can effectively improve the decay resistance of material.
Above specific embodiments of the invention are described.It is to be appreciated that the invention is not limited in above-mentioned particular implementation, those skilled in the art can make various deformation or amendment within the scope of the claims, and this has no effect on the flesh and blood of the present invention.
Claims (12)
1. a corrosion-resistant high fire-retardance thermoplastic low-smoke halide-free CABLE MATERIALS, it is characterised in that described CABLE MATERIALS includes each component of following parts by weight:
2. corrosion-resistant high fire-retardance thermoplastic low-smoke halide-free CABLE MATERIALS as claimed in claim 1, it is characterised in that polyolefin used be with GB/T3682-2000 method measure melt index for 1～20g/10min, the molecular weight vistanex more than 20,000.
3. corrosion-resistant high fire-retardance thermoplastic low-smoke halide-free CABLE MATERIALS as claimed in claim 1, it is characterized in that, described polyolefin is a kind of or arbitrarily two or more mixing in ethylene-vinyl acetate copolymer, Low Density Polyethylene, high density polyethylene (HDPE), ethylene methyl acrylate, POE.
4. corrosion-resistant high fire-retardance thermoplastic low-smoke halide-free CABLE MATERIALS as claimed in claim 1, it is characterised in that described compatilizer is a kind of or arbitrarily two or more mixing in maleic anhydride grafted polyethylene, maleic anhydride inoculated polypropylene, acrylic acid-grafted polyethylene.
5. corrosion-resistant high fire-retardance thermoplastic low-smoke halide-free CABLE MATERIALS as claimed in claim 1, it is characterised in that described fire retardant is a kind of or arbitrarily two or more mixing in unmodified aluminium hydroxide, magnesium hydroxide, calcium carbonate, red phosphorus.
6. corrosion-resistant high fire-retardance thermoplastic low-smoke halide-free CABLE MATERIALS as claimed in claim 1, it is characterised in that described high-molecular coating agent is a kind of arbitrarily two or more mixing in brucite, water calcium aluminate, metal soap, fatty acid amide, dicarboxylic ester.
7. corrosion-resistant high fire-retardance thermoplastic low-smoke halide-free CABLE MATERIALS as claimed in claim 1 and manufacturing process thereof, it is characterized in that, described ionic absorption agent is a kind of or arbitrarily two or more mixing in ethoxyquin alkanamine, diethanolamine, ethoxylated alcohol, alkyl carboxylate, alkylphosphonic.
8. corrosion-resistant high fire-retardance thermoplastic low-smoke halide-free CABLE MATERIALS as claimed in claim 1 and manufacturing process thereof, it is characterised in that described coupling agent is a kind of or arbitrarily two or more mixing in vinyl silanes, amino silane, titanate ester silane.
9. corrosion-resistant high fire-retardance thermoplastic low-smoke halide-free CABLE MATERIALS as claimed in claim 1 and manufacturing process thereof, it is characterised in that described lubricant is end group is a kind of or arbitrarily two or more mixing in the silica gel of vinyl, silicone oil, satisfied fatty acid.
10. the preparation method of the corrosion-resistant high fire-retardance thermoplastic low-smoke halide-free CABLE MATERIALS described in claim 1 to a 9 any one claim, it is characterised in that comprise the steps:
1) being put in impregnating by pressure rotary drum by fire retardant and preheat, preheating temperature is 120 DEG C, and preheating time is 15 minutes；Subsequently impregnating by pressure rotary drum is carried out evacuation process, pumpdown time is 15 minutes, pressure≤-0.05Mpa, after evacuation terminates, use the negative pressure within impregnating by pressure rotary drum, high-molecular coating agent and ionic absorption agent are drawn in impregnating by pressure from charge door, and start to rotate impregnating by pressure rotary drum, enable three kinds of materials to be sufficiently mixed, incorporation time is 15 minutes, by vacuum pump, impregnating by pressure rotary drum is pressurizeed subsequently, pressing time is 30 minutes, and pressure >=0.4MPa, after mixing, blowing, obtains semi-finished product A；
2) polyolefin, compatilizer being mixed in high-speed mixer, incorporation time is 5 minutes, and speed is 300r/min, is subsequently added coupling agent and lubricant, and incorporation time is 5 minutes, and speed is 300r/min, obtains semi-finished product B；
3) proportionally carry out semi-finished product A and semi-finished product B melting in double screw extruder, mixing, pelletizing, packaging, twin screw design temperature is 130～160 DEG C, and yield is 350kg/h.
11. preparation method as claimed in claim 10, it is characterised in that the velocity of rotation of described impregnating by pressure rotary drum is 5～10r/min.
12. preparation method as claimed in claim 10, it is characterised in that at the volume 2000L of the impregnating by pressure rotary drum described in a preferred reality of invention, the stainless steel that whole body adopts thickness to be 20mm is prepared from.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108752746A (en) * | 2018-06-25 | 2018-11-06 | 合肥安力电力工程有限公司 | A kind of high-strength cable protection pipe and preparation method thereof |
| CN108864558A (en) * | 2018-06-01 | 2018-11-23 | 安徽电信器材贸易工业有限责任公司 | A kind of fiber optic cable flame retardant sheath and preparation method thereof |
| CN111499954A (en) * | 2020-05-25 | 2020-08-07 | 上海方之德新材料有限公司 | Corrosion-resistant low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262772A (en) * | 2010-03-08 | 2015-01-07 | 旭化成化学株式会社 | Foam Composition, Method For Producing Same, And Foam |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104262772A (en) * | 2010-03-08 | 2015-01-07 | 旭化成化学株式会社 | Foam Composition, Method For Producing Same, And Foam |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108864558A (en) * | 2018-06-01 | 2018-11-23 | 安徽电信器材贸易工业有限责任公司 | A kind of fiber optic cable flame retardant sheath and preparation method thereof |
| CN108752746A (en) * | 2018-06-25 | 2018-11-06 | 合肥安力电力工程有限公司 | A kind of high-strength cable protection pipe and preparation method thereof |
| CN111499954A (en) * | 2020-05-25 | 2020-08-07 | 上海方之德新材料有限公司 | Corrosion-resistant low-smoke halogen-free flame-retardant polyolefin cable material and preparation method thereof |
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Effective date of registration: 20210707 Address after: 201100 Building 5, 268 beihengshahe Road, Minhang District, Shanghai Patentee after: Shanghai Zhizheng New Material Co., Ltd Address before: 5050 Yuanjiang Road, Xinzhuang Industrial Zone, Minhang District, Shanghai 201108 Patentee before: SHANGHAI ORIGINALDOW ADVANCED COMPOUNDS Co.,Ltd. |