CN117820756A - Outdoor high-flame-retardance cable material and preparation process thereof - Google Patents
Outdoor high-flame-retardance cable material and preparation process thereof Download PDFInfo
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- CN117820756A CN117820756A CN202410012802.8A CN202410012802A CN117820756A CN 117820756 A CN117820756 A CN 117820756A CN 202410012802 A CN202410012802 A CN 202410012802A CN 117820756 A CN117820756 A CN 117820756A
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- 239000000463 material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 65
- 239000003063 flame retardant Substances 0.000 claims abstract description 46
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 39
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 39
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001125 extrusion Methods 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract 7
- 239000000178 monomer Substances 0.000 claims description 66
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 63
- 238000002156 mixing Methods 0.000 claims description 38
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 36
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 36
- 239000007822 coupling agent Substances 0.000 claims description 35
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 34
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 27
- 239000000314 lubricant Substances 0.000 claims description 26
- RIEUDAULTPEOAB-UHFFFAOYSA-N 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyl chloride Chemical compound CC=1C=C(C=C(C1O)C(C)(C)C)CCC(=O)Cl RIEUDAULTPEOAB-UHFFFAOYSA-N 0.000 claims description 25
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 24
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 21
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 21
- 239000011574 phosphorus Substances 0.000 claims description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 19
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 18
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 18
- 229920001903 high density polyethylene Polymers 0.000 claims description 18
- 239000004700 high-density polyethylene Substances 0.000 claims description 18
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 18
- 229920003225 polyurethane elastomer Polymers 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 17
- 150000004645 aluminates Chemical class 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 125000003277 amino group Chemical group 0.000 claims description 12
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 9
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical group [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000005457 ice water Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 abstract description 9
- -1 polyethylene Polymers 0.000 abstract description 9
- 229920000573 polyethylene Polymers 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 6
- 230000003078 antioxidant effect Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 10
- 230000032683 aging Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical group CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of cable materials, in particular to an outdoor high-flame-retardance cable material and a preparation process thereof. The cable material is prepared by melt extrusion, and has excellent flame retardant property, excellent antioxidant property of the product, improved tensile strength and mechanical property, and can be widely applied to the production and processing of outdoor cables. The invention discloses a preparation process of an outdoor high-flame-retardance cable material, which adjusts the formula and the processing process of the polyethylene cable material, and dispersedly flame-retardant modifies magnesium hydroxide, so that the prepared product has excellent mechanical property, improved flame retardance, low cost and higher practicability.
Description
Technical Field
The invention relates to the technical field of cable materials, in particular to an outdoor high-flame-retardance cable material and a preparation process thereof.
Background
The electric wires and cables are indispensable basic products in our daily life, the main functions of the electric wires are to transmit electric energy, and the complete electric wire network building is the basis for realizing the electric energy transmission in China. With the intensive research of research personnel on electric wires and cables, the requirements on the flame retardant property and the ageing resistance of the cable material are higher and higher, magnesium hydroxide or aluminum hydroxide is generally adopted as a flame retardant in the conventional cable material, but the addition amount of the magnesium hydroxide or the aluminum hydroxide is larger, and the comprehensive performance of the cable material is influenced.
Therefore, based on the situation, the application discloses an outdoor high-flame-retardance cable material and a preparation process thereof, and the cable material is improved in flame retardance and excellent in comprehensive mechanical property, so that the technical problem to be solved is urgent.
Disclosure of Invention
The invention aims to provide an outdoor high-flame-retardance cable material and a preparation process thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation process of an outdoor high-flame-retardance cable material comprises the following steps:
(1) Mixing vinyl trimethoxy silane, DOPO and chloroform, heating to 70-75 ℃, stirring until the mixture is dissolved, adding azodiisobutyronitrile, continuing to react for 8-10 h, cooling to 25-30 ℃, and removing the solvent by rotary evaporation to obtain a phosphorus-containing monomer;
mixing a phosphorus-containing monomer, an aminosilane coupling agent and vinyl trimethoxy silane, adding methyl ethyl ketone and 12mL of absolute methanol, adjusting the temperature to 0 ℃, adding a sodium hydroxide aqueous solution, continuously reacting for 1-1.5 h, heating to 75-80 ℃, preserving heat and reacting for 25-30 h, collecting a product after the reaction is finished, washing and drying to obtain an amino-containing POSS monomer;
(2) Mixing an amino-containing POSS monomer, potassium carbonate and deionized water, uniformly stirring, adding a benzene solution of beta- (3-methyl-5-tertiary butyl-4-hydroxyphenyl) propionyl chloride in an ice water bath at 0 ℃, heating to 25 ℃, carrying out heat preservation reaction for 20-24 hours, and carrying out suction filtration, washing and drying after the reaction is finished to obtain a double-bond-containing flame-retardant monomer;
(3) Mixing deionized water, absolute ethyl alcohol and an aluminate coupling agent, stirring for 10-20 min, adding magnesium hydroxide at 60-65 ℃, stirring for 20-30 min under a nitrogen environment, adding butyl acrylate, a double bond-containing flame-retardant monomer and azodiisobutyronitrile, carrying out heat preservation reaction for 1-2 h, collecting a product after the reaction is finished, washing and drying to obtain modified magnesium hydroxide;
(4) And (3) taking high-density polyethylene, EVA, polyurethane elastomer, modified magnesium hydroxide, lubricant and calcium carbonate powder, putting into a high-speed mixer, mixing for 10-15 min, and carrying out melt extrusion to obtain the cable material.
In the more optimized scheme, in the step (4), the cable material comprises the following components in parts by mass: 25-35 parts of high-density polyethylene, 65-75 parts of EVA, 6-8 parts of polyurethane elastomer, 40-50 parts of modified magnesium hydroxide, 1-1.5 parts of lubricant and 10-15 parts of calcium carbonate powder; the lubricant is zinc stearate.
In a more optimized scheme, in the step (1), the mol ratio of the vinyl trimethoxy silane to the DOPO is 1:1, wherein the dosage of the azodiisobutyronitrile is 2 to 2.5 weight percent of the vinyl trimethoxy silane.
In a more optimized scheme, in the step (1), the mole ratio of the phosphorus-containing monomer, the aminosilane coupling agent and the vinyl trimethoxy silane is 7:1.2:2, the concentration of the sodium hydroxide aqueous solution is 0.1-0.2 mol/L; the molar ratio of the aminosilane coupling agent to the sodium hydroxide aqueous solution is 1.2: (70-80).
In a more optimized scheme, in the step (2), the molar ratio of amino groups and beta- (3-methyl-5-tertiary butyl-4-hydroxyphenyl) propionyl chloride of the POSS monomer containing amino groups is 1:1, a step of; the molar ratio of the beta- (3-methyl-5-tertiary butyl-4-hydroxyphenyl) propionyl chloride to the potassium carbonate is 1:1, a step of; the concentration of the benzene solution of the beta- (3-methyl-5-tertiary butyl-4-hydroxyphenyl) propionyl chloride is 0.4mol/L.
In the more optimized scheme, in the step (3), the mass ratio of the deionized water, the absolute ethyl alcohol, the aluminate coupling agent and the magnesium hydroxide is (28-30): (2-3): 1:14; the mass ratio of the magnesium hydroxide, the butyl acrylate and the flame-retardant monomer containing double bonds is (4-5): 1:1, a step of; the amount of the azodiisobutyronitrile is 3-4wt% of the butyl acrylate.
In a more optimized scheme, the mixing temperature is 60-65 ℃ and the extrusion temperature is 130-140 ℃.
According to the optimized scheme, the high-flame-retardant cable material is prepared by the preparation process of the outdoor high-flame-retardant cable material.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation process of an outdoor high-flame-retardance cable material, which comprises the steps of taking high-density polyethylene, EVA, polyurethane elastomer and other components as main resin materials in a blending manner, adding modified magnesium hydroxide as a flame retardant, adding other auxiliary agents such as a lubricant and the like, and carrying out melt extrusion to obtain the cable material.
In the conventional scheme, magnesium hydroxide is generally used as a flame retardant, but magnesium hydroxide is used as a flame retardant, the addition amount of the magnesium hydroxide is very large, and the magnesium hydroxide has the characteristics of large specific surface area and easy agglomeration of particles, so that the compatibility and interface bonding property with a polyethylene matrix are poor, and therefore, the processing performance of the polyethylene can be influenced by a large amount of magnesium hydroxide filled, and the appearance of a product is rough. The flame-retardant monomer not only can improve the flame-retardant property of the product, but also can replace an antioxidant, so that the oxidation resistance of the polyethylene cable material is improved, and an antioxidant is not required to be additionally added in the subsequent processing process of the polyethylene cable material, so that the cost is effectively reduced; and because of the existence of POSS monomer, it has also overcome the problem that the conventional antioxidant is easy to migrate, the practicability is higher.
On the basis, the magnesium hydroxide is grafted by the aluminate coupling agent, and then the grafted acrylate monomer and the flame-retardant monomer containing double bonds are initiated by the initiator, so that the magnesium hydroxide is modified, on one hand, the dispersibility of the modified magnesium hydroxide is improved, and the modified magnesium hydroxide can participate in the reaction of a polyethylene system because the flame-retardant monomer containing double bonds contains more C=C, so that the interface compatibility of the modified magnesium hydroxide and the polyethylene is higher; on the other hand, the grafting of the flame-retardant monomer containing double bonds can improve the flame retardant property of the magnesium hydroxide, greatly reduce the addition amount of the magnesium hydroxide, and still maintain the excellent flame retardant property.
The invention discloses a preparation process of an outdoor high-flame-retardance cable material, which adjusts the formula and the processing process of the polyethylene cable material, and dispersedly flame-retardant modifies magnesium hydroxide, so that the prepared product has excellent mechanical property, improved flame retardance, low cost and higher practicability.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In this example, the aluminate coupling agent is ethyl acetoacetate diisopropylaluminate; the aminosilane coupling agent is KH-550; magnesium hydroxide has a specification of 5000 mesh and is provided by sea city essence mineral products limited company; the high-density polyethylene model is 5000S, which is provided by Yangzi petrochemical company; the VA mass fraction in EVA is 18%, which is provided by Korean Sanxingzhu company; the polyurethane elastomer is TPU58887, which is provided by Dongguan City technical engineering plastics Co., ltd; the lubricant is zinc stearate. The grain size of the calcium carbonate powder is 30-40 nm, which is provided by Shandong Haizze nano calcium carbonate Co.
Example 1: a preparation process of an outdoor high-flame-retardance cable material comprises the following steps:
(1) Mixing 0.5mol of vinyl trimethoxy silane, 0.5mol of DOPO and 100mL of chloroform, heating to 70 ℃, stirring until the mixture is dissolved, adding azo-bis-isobutyronitrile, continuously reacting for 10 hours, cooling to 25 ℃, and removing the solvent by rotary evaporation to obtain a phosphorus-containing monomer; the mol ratio of the vinyl trimethoxy silane to DOPO is 1:1, wherein the content of the azodiisobutyronitrile is 2.5 weight percent of the vinyl trimethoxy silane.
Mixing 0.07mol of phosphorus-containing monomer, 0.012mol of aminosilane coupling agent and 0.02mol of vinyltrimethoxysilane, adding 75mL of methyl ethyl ketone and 12mL of absolute methanol, adjusting the temperature to 0 ℃, adding sodium hydroxide aqueous solution, continuing to react for 1h, heating to 75 ℃, preserving heat for 30h, collecting a product after the reaction is finished, washing and drying to obtain an amino-containing POSS monomer; the mole ratio of the phosphorus-containing monomer to the aminosilane coupling agent to the vinyltrimethoxysilane is 7:1.2:2, the concentration of the sodium hydroxide aqueous solution is 0.1mol/L; the molar ratio of the aminosilane coupling agent to the sodium hydroxide aqueous solution is 1.2:75.
(2) Mixing an amino-containing POSS monomer, potassium carbonate and deionized water, uniformly stirring, adding a benzene solution of beta- (3-methyl-5-tertiary butyl-4-hydroxyphenyl) propionyl chloride in an ice water bath at 0 ℃, heating to 25 ℃, preserving heat, reacting for 20 hours, filtering after the reaction is finished, washing and drying to obtain a double bond-containing flame-retardant monomer; the molar ratio of amino groups to beta- (3-methyl-5-tert-butyl-4-hydroxyphenyl) propionyl chloride of the POSS monomer containing amino groups is 1:1, a step of; the molar ratio of the beta- (3-methyl-5-tertiary butyl-4-hydroxyphenyl) propionyl chloride to the potassium carbonate is 1:1, a step of; the concentration of the benzene solution of the beta- (3-methyl-5-tertiary butyl-4-hydroxyphenyl) propionyl chloride is 0.4mol/L.
(3) Mixing 600g of deionized water, 50g of absolute ethyl alcohol and 20g of aluminate coupling agent, stirring for 10min, adding 280g of magnesium hydroxide at 60 ℃, stirring for 30min under a nitrogen environment, adding butyl acrylate, a double bond-containing flame-retardant monomer and azodiisobutyronitrile, carrying out heat preservation reaction for 1h, collecting a product after the reaction is finished, and washing and drying to obtain modified magnesium hydroxide; the mass ratio of deionized water to absolute ethyl alcohol to aluminate coupling agent to magnesium hydroxide is 30:2.5:1:14; the mass ratio of the magnesium hydroxide to the butyl acrylate to the double bond-containing flame-retardant monomer is 4:1:1, a step of; the azodiisobutyronitrile is used in an amount of 3% by weight of butyl acrylate.
(4) And (3) taking high-density polyethylene, EVA, polyurethane elastomer, modified magnesium hydroxide, lubricant and calcium carbonate powder, putting into a high-speed mixer, mixing for 10min, and carrying out melt extrusion at 65 ℃ and 135 ℃ to obtain the cable material.
The cable material comprises the following components in parts by mass: 35 parts of high-density polyethylene, 75 parts of EVA, 8 parts of polyurethane elastomer, 45 parts of modified magnesium hydroxide, 1.5 parts of lubricant and 15 parts of calcium carbonate powder; the lubricant is zinc stearate.
Example 2: a preparation process of an outdoor high-flame-retardance cable material comprises the following steps:
(1) Mixing 0.5mol of vinyl trimethoxy silane, 0.5mol of DOPO and 100mL of chloroform, heating to 75 ℃, stirring until the mixture is dissolved, adding azo-bis-isobutyronitrile, continuously reacting for 9 hours, cooling to 28 ℃, and removing the solvent by rotary evaporation to obtain a phosphorus-containing monomer; the mol ratio of the vinyl trimethoxy silane to DOPO is 1:1, wherein the content of the azodiisobutyronitrile is 2.5 weight percent of the vinyl trimethoxy silane.
Mixing 0.07mol of phosphorus-containing monomer, 0.012mol of aminosilane coupling agent and 0.02mol of vinyltrimethoxysilane, adding 75mL of methyl ethyl ketone and 12mL of absolute methanol, adjusting the temperature to 0 ℃, adding sodium hydroxide aqueous solution, continuing to react for 1.5h, heating to 80 ℃, preserving heat for 28h, collecting a product after the reaction is finished, washing and drying to obtain an amino-containing POSS monomer; the mole ratio of the phosphorus-containing monomer to the aminosilane coupling agent to the vinyltrimethoxysilane is 7:1.2:2, the concentration of the sodium hydroxide aqueous solution is 0.1mol/L; the molar ratio of the aminosilane coupling agent to the sodium hydroxide aqueous solution is 1.2:75.
(2) Mixing an amino-containing POSS monomer, potassium carbonate and deionized water, uniformly stirring, adding a benzene solution of beta- (3-methyl-5-tertiary butyl-4-hydroxyphenyl) propionyl chloride in an ice water bath at 0 ℃, heating to 25 ℃, preserving heat, reacting for 22 hours, filtering after the reaction is finished, washing and drying to obtain a double bond-containing flame-retardant monomer; the molar ratio of amino groups to beta- (3-methyl-5-tert-butyl-4-hydroxyphenyl) propionyl chloride of the POSS monomer containing amino groups is 1:1, a step of; the molar ratio of the beta- (3-methyl-5-tertiary butyl-4-hydroxyphenyl) propionyl chloride to the potassium carbonate is 1:1, a step of; the concentration of the benzene solution of the beta- (3-methyl-5-tertiary butyl-4-hydroxyphenyl) propionyl chloride is 0.4mol/L.
(3) Mixing 600g of deionized water, 50g of absolute ethyl alcohol and 20g of aluminate coupling agent, stirring for 15min, adding 280g of magnesium hydroxide at 65 ℃, stirring for 25min under a nitrogen environment, adding butyl acrylate, a double bond-containing flame-retardant monomer and azodiisobutyronitrile, carrying out heat preservation reaction for 1.5h, collecting a product after the reaction is finished, washing and drying to obtain modified magnesium hydroxide; the mass ratio of deionized water to absolute ethyl alcohol to aluminate coupling agent to magnesium hydroxide is 30:2.5:1:14; the mass ratio of the magnesium hydroxide to the butyl acrylate to the double bond-containing flame-retardant monomer is 4:1:1, a step of; the azodiisobutyronitrile is used in an amount of 3% by weight of butyl acrylate.
(4) And (3) taking high-density polyethylene, EVA, polyurethane elastomer, modified magnesium hydroxide, lubricant and calcium carbonate powder, putting into a high-speed mixer, mixing for 15min, and carrying out melt extrusion at 65 ℃ and 135 ℃ to obtain the cable material.
The cable material comprises the following components in parts by mass: 35 parts of high-density polyethylene, 75 parts of EVA, 8 parts of polyurethane elastomer, 48 parts of modified magnesium hydroxide, 1.5 parts of lubricant and 15 parts of calcium carbonate powder; the lubricant is zinc stearate.
Example 3: a preparation process of an outdoor high-flame-retardance cable material comprises the following steps:
(1) Mixing 0.5mol of vinyl trimethoxy silane, 0.5mol of DOPO and 100mL of chloroform, heating to 75 ℃, stirring until the mixture is dissolved, adding azo-bis-isobutyronitrile, continuously reacting for 8 hours, cooling to 30 ℃, and removing the solvent by rotary evaporation to obtain a phosphorus-containing monomer; the mol ratio of the vinyl trimethoxy silane to DOPO is 1:1, wherein the content of the azodiisobutyronitrile is 2.5 weight percent of the vinyl trimethoxy silane.
Mixing 0.07mol of phosphorus-containing monomer, 0.012mol of aminosilane coupling agent and 0.02mol of vinyltrimethoxysilane, adding 75mL of methyl ethyl ketone and 12mL of absolute methanol, adjusting the temperature to 0 ℃, adding sodium hydroxide aqueous solution, continuing to react for 1.5h, heating to 75 ℃, preserving heat and reacting for 30h, collecting a product after the reaction is finished, washing and drying to obtain an amino-containing POSS monomer; the mole ratio of the phosphorus-containing monomer to the aminosilane coupling agent to the vinyltrimethoxysilane is 7:1.2:2, the concentration of the sodium hydroxide aqueous solution is 0.1mol/L; the molar ratio of the aminosilane coupling agent to the sodium hydroxide aqueous solution is 1.2:75.
(2) Mixing an amino-containing POSS monomer, potassium carbonate and deionized water, uniformly stirring, adding a benzene solution of beta- (3-methyl-5-tertiary butyl-4-hydroxyphenyl) propionyl chloride in an ice water bath at 0 ℃, heating to 25 ℃, preserving heat, reacting for 24 hours, filtering after the reaction is finished, washing and drying to obtain a double bond-containing flame-retardant monomer; the molar ratio of amino groups to beta- (3-methyl-5-tert-butyl-4-hydroxyphenyl) propionyl chloride of the POSS monomer containing amino groups is 1:1, a step of; the molar ratio of the beta- (3-methyl-5-tertiary butyl-4-hydroxyphenyl) propionyl chloride to the potassium carbonate is 1:1, a step of; the concentration of the benzene solution of the beta- (3-methyl-5-tertiary butyl-4-hydroxyphenyl) propionyl chloride is 0.4mol/L.
(3) Mixing 600g of deionized water, 50g of absolute ethyl alcohol and 20g of aluminate coupling agent, stirring for 20min, adding 280g of magnesium hydroxide at 65 ℃, stirring for 20min under a nitrogen environment, adding butyl acrylate, a double bond-containing flame-retardant monomer and azodiisobutyronitrile, carrying out heat preservation reaction for 2h, collecting a product after the reaction is finished, washing and drying to obtain modified magnesium hydroxide; the mass ratio of deionized water to absolute ethyl alcohol to aluminate coupling agent to magnesium hydroxide is 30:2.5:1:14; the mass ratio of the magnesium hydroxide to the butyl acrylate to the double bond-containing flame-retardant monomer is 4:1:1, a step of; the azodiisobutyronitrile is used in an amount of 3% by weight of butyl acrylate.
(4) And (3) taking high-density polyethylene, EVA, polyurethane elastomer, modified magnesium hydroxide, lubricant and calcium carbonate powder, putting into a high-speed mixer, mixing for 15min, and carrying out melt extrusion at 65 ℃ and 135 ℃ to obtain the cable material.
The cable material comprises the following components in parts by mass: 35 parts of high-density polyethylene, 75 parts of EVA, 8 parts of polyurethane elastomer, 50 parts of modified magnesium hydroxide, 1.5 parts of lubricant and 15 parts of calcium carbonate powder; the lubricant is zinc stearate.
Comparative example 1: using example 3 as a control, comparative example 1 was not reacted with beta- (3-methyl-5-tert-butyl-4-hydroxyphenyl) propionyl chloride, the remaining steps being unchanged.
A preparation process of an outdoor high-flame-retardance cable material comprises the following steps:
(1) Mixing 0.5mol of vinyl trimethoxy silane, 0.5mol of DOPO and 100mL of chloroform, heating to 75 ℃, stirring until the mixture is dissolved, adding azo-bis-isobutyronitrile, continuously reacting for 8 hours, cooling to 30 ℃, and removing the solvent by rotary evaporation to obtain a phosphorus-containing monomer; the mol ratio of the vinyl trimethoxy silane to DOPO is 1:1, wherein the content of the azodiisobutyronitrile is 2.5 weight percent of the vinyl trimethoxy silane.
Mixing 0.07mol of phosphorus-containing monomer and 0.32mol of vinyl trimethoxy silane, adding 75mL of methyl ethyl ketone and 12mL of absolute methanol, adjusting the temperature to 0 ℃, adding sodium hydroxide aqueous solution, continuing to react for 1.5h, heating to 75 ℃, preserving heat for 30h, collecting a product after the reaction is finished, washing and drying to obtain a flame-retardant monomer containing double bonds; the mole ratio of the phosphorus-containing monomer to the vinyl trimethoxy silane is 7:3.2, the concentration of the sodium hydroxide aqueous solution is 0.1mol/L; the mol ratio of the vinyl trimethoxy silane to the sodium hydroxide aqueous solution is 1.2:75.
(2) Mixing 600g of deionized water, 50g of absolute ethyl alcohol and 20g of aluminate coupling agent, stirring for 20min, adding 280g of magnesium hydroxide at 65 ℃, stirring for 20min under a nitrogen environment, adding butyl acrylate, a double bond-containing flame-retardant monomer and azodiisobutyronitrile, carrying out heat preservation reaction for 2h, collecting a product after the reaction is finished, washing and drying to obtain modified magnesium hydroxide; the mass ratio of deionized water to absolute ethyl alcohol to aluminate coupling agent to magnesium hydroxide is 30:2.5:1:14; the mass ratio of the magnesium hydroxide to the butyl acrylate to the double bond-containing flame-retardant monomer is 4:1:1, a step of; the azodiisobutyronitrile is used in an amount of 3% by weight of butyl acrylate.
(3) And (3) taking high-density polyethylene, EVA, polyurethane elastomer, modified magnesium hydroxide, lubricant and calcium carbonate powder, putting into a high-speed mixer, mixing for 15min, and carrying out melt extrusion at 65 ℃ and 135 ℃ to obtain the cable material.
The cable material comprises the following components in parts by mass: 35 parts of high-density polyethylene, 75 parts of EVA, 8 parts of polyurethane elastomer, 50 parts of modified magnesium hydroxide, 1.5 parts of lubricant and 15 parts of calcium carbonate powder; the lubricant is zinc stearate.
Comparative example 2: with example 3 as a control, only magnesium hydroxide was introduced in comparative example 2, and the rest of the steps were unchanged.
A preparation process of an outdoor high-flame-retardance cable material comprises the following steps:
and (3) taking high-density polyethylene, EVA, polyurethane elastomer, magnesium hydroxide, lubricant and calcium carbonate powder, putting into a high-speed mixer, mixing for 15min, and carrying out melt extrusion at 65 ℃ and 135 ℃ to obtain the cable material.
The cable material comprises the following components in parts by mass: 35 parts of high-density polyethylene, 75 parts of EVA, 8 parts of polyurethane elastomer, 50 parts of magnesium hydroxide, 1.5 parts of lubricant and 15 parts of calcium carbonate powder; the lubricant is zinc stearate.
Comparative example 3: based on example 3, comparative example 3 was prepared by adjusting the amount of modified magnesium hydroxide to 38 parts, and the remaining steps were unchanged.
A preparation process of an outdoor high-flame-retardance cable material comprises the following steps:
(1) Mixing 0.5mol of vinyl trimethoxy silane, 0.5mol of DOPO and 100mL of chloroform, heating to 75 ℃, stirring until the mixture is dissolved, adding azo-bis-isobutyronitrile, continuously reacting for 8 hours, cooling to 30 ℃, and removing the solvent by rotary evaporation to obtain a phosphorus-containing monomer; the mol ratio of the vinyl trimethoxy silane to DOPO is 1:1, wherein the content of the azodiisobutyronitrile is 2.5 weight percent of the vinyl trimethoxy silane.
Mixing 0.07mol of phosphorus-containing monomer, 0.012mol of aminosilane coupling agent and 0.02mol of vinyltrimethoxysilane, adding 75mL of methyl ethyl ketone and 12mL of absolute methanol, adjusting the temperature to 0 ℃, adding sodium hydroxide aqueous solution, continuing to react for 1.5h, heating to 75 ℃, preserving heat and reacting for 30h, collecting a product after the reaction is finished, washing and drying to obtain an amino-containing POSS monomer; the mole ratio of the phosphorus-containing monomer to the aminosilane coupling agent to the vinyltrimethoxysilane is 7:1.2:2, the concentration of the sodium hydroxide aqueous solution is 0.1mol/L; the molar ratio of the aminosilane coupling agent to the sodium hydroxide aqueous solution is 1.2:75.
(2) Mixing an amino-containing POSS monomer, potassium carbonate and deionized water, uniformly stirring, adding a benzene solution of beta- (3-methyl-5-tertiary butyl-4-hydroxyphenyl) propionyl chloride in an ice water bath at 0 ℃, heating to 25 ℃, preserving heat, reacting for 24 hours, filtering after the reaction is finished, washing and drying to obtain a double bond-containing flame-retardant monomer; the molar ratio of amino groups to beta- (3-methyl-5-tert-butyl-4-hydroxyphenyl) propionyl chloride of the POSS monomer containing amino groups is 1:1, a step of; the molar ratio of the beta- (3-methyl-5-tertiary butyl-4-hydroxyphenyl) propionyl chloride to the potassium carbonate is 1:1, a step of; the concentration of the benzene solution of the beta- (3-methyl-5-tertiary butyl-4-hydroxyphenyl) propionyl chloride is 0.4mol/L.
(3) Mixing 600g of deionized water, 50g of absolute ethyl alcohol and 20g of aluminate coupling agent, stirring for 20min, adding 280g of magnesium hydroxide at 65 ℃, stirring for 20min under a nitrogen environment, adding butyl acrylate, a double bond-containing flame-retardant monomer and azodiisobutyronitrile, carrying out heat preservation reaction for 2h, collecting a product after the reaction is finished, washing and drying to obtain modified magnesium hydroxide; the mass ratio of deionized water to absolute ethyl alcohol to aluminate coupling agent to magnesium hydroxide is 30:2.5:1:14; the mass ratio of the magnesium hydroxide to the butyl acrylate to the double bond-containing flame-retardant monomer is 4:1:1, a step of; the azodiisobutyronitrile is used in an amount of 3% by weight of butyl acrylate.
(4) And (3) taking high-density polyethylene, EVA, polyurethane elastomer, modified magnesium hydroxide, lubricant and calcium carbonate powder, putting into a high-speed mixer, mixing for 15min, and carrying out melt extrusion at 65 ℃ and 135 ℃ to obtain the cable material.
The cable material comprises the following components in parts by mass: 35 parts of high-density polyethylene, 75 parts of EVA, 8 parts of polyurethane elastomer, 38 parts of modified magnesium hydroxide, 1.5 parts of lubricant and 15 parts of calcium carbonate powder; the lubricant is zinc stearate.
Detection experiment:
1. taking the cable materials prepared in examples 1-3 and comparative examples 1-3, performing press molding by a flat vulcanizing machine under the conditions of 15MPa, 160 ℃ and hot pressing for 10min, and cooling to obtain a sample; referring to the method disclosed in GB/T1040, a dumbbell-shaped sample with a thickness of 1mm was produced, and tensile strength was measured at a tensile speed of 200mm/min; the limiting oxygen index of the test specimens was tested with reference to the method disclosed in GB/T2046.
2. The dumbbell-shaped test sample is placed in an aging box, air in the box is replaced by oxygen for three times, an aging experiment is carried out at 90 ℃ for 75 days, and the tensile strength of the product is retested.
| Project | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Tensile strength MPa | 13.6 | 13.9 | 14.1 | 13.8 | 11.7 | 12.5 |
| Limiting oxygen index | 29.4 | 30.3 | 30.9 | 31.2 | 21.4 | 27.9 |
| Tensile Strength after aging MPa | 11.6 | 12.1 | 12.4 | 6.2 | 5.8 | 11.1 |
Conclusion: the invention discloses a preparation process of an outdoor high-flame-retardance cable material, which adjusts the formula and the processing process of the polyethylene cable material, and dispersedly flame-retardant modifies magnesium hydroxide, so that the prepared product has excellent mechanical property, improved flame retardance, low cost and higher practicability.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation process of an outdoor high-flame-retardance cable material is characterized by comprising the following steps of: the method comprises the following steps:
(1) Mixing vinyl trimethoxy silane, DOPO and chloroform, heating to 70-75 ℃, stirring until the mixture is dissolved, adding azodiisobutyronitrile, continuing to react for 8-10 h, cooling to 25-30 ℃, and removing the solvent by rotary evaporation to obtain a phosphorus-containing monomer;
mixing a phosphorus-containing monomer, an aminosilane coupling agent and vinyl trimethoxy silane, adding methyl ethyl ketone and absolute methanol, adjusting the temperature to 0 ℃, adding a sodium hydroxide aqueous solution, continuously reacting for 1-1.5 h, heating to 75-80 ℃, preserving heat, reacting for 25-30 h, collecting a product after the reaction is finished, washing and drying to obtain an amino-containing POSS monomer;
(2) Mixing an amino-containing POSS monomer, potassium carbonate and deionized water, uniformly stirring, adding a benzene solution of beta- (3-methyl-5-tertiary butyl-4-hydroxyphenyl) propionyl chloride in an ice water bath at 0 ℃, heating to 25 ℃, carrying out heat preservation reaction for 20-24 hours, and carrying out suction filtration, washing and drying after the reaction is finished to obtain a double-bond-containing flame-retardant monomer;
(3) Mixing deionized water, absolute ethyl alcohol and an aluminate coupling agent, stirring for 10-20 min, adding magnesium hydroxide at 60-65 ℃, stirring for 20-30 min under a nitrogen environment, adding butyl acrylate, a double bond-containing flame-retardant monomer and azodiisobutyronitrile, carrying out heat preservation reaction for 1-2 h, collecting a product after the reaction is finished, washing and drying to obtain modified magnesium hydroxide;
(4) And (3) taking high-density polyethylene, EVA, polyurethane elastomer, modified magnesium hydroxide, lubricant and calcium carbonate powder, putting into a high-speed mixer, mixing for 10-15 min, and carrying out melt extrusion to obtain the cable material.
2. The process for preparing the outdoor high-flame-retardant cable material according to claim 1, wherein the process comprises the following steps of: in the step (4), the cable material comprises the following components in parts by mass: 25-35 parts of high-density polyethylene, 65-75 parts of EVA, 6-8 parts of polyurethane elastomer, 40-50 parts of modified magnesium hydroxide, 1-1.5 parts of lubricant and 10-15 parts of calcium carbonate powder; the lubricant is zinc stearate.
3. The process for preparing the outdoor high-flame-retardant cable material according to claim 1, wherein the process comprises the following steps of: in the step (1), the mol ratio of the vinyl trimethoxy silane to the DOPO is 1:1, wherein the dosage of the azodiisobutyronitrile is 2 to 2.5 weight percent of the vinyl trimethoxy silane.
4. The process for preparing the outdoor high-flame-retardant cable material according to claim 1, wherein the process comprises the following steps of: in the step (1), the mole ratio of the phosphorus-containing monomer, the aminosilane coupling agent and the vinyl trimethoxy silane is 7:1.2:2, the concentration of the sodium hydroxide aqueous solution is 0.1-0.2 mol/L; the molar ratio of the aminosilane coupling agent to the sodium hydroxide aqueous solution is 1.2: (70-80).
5. The process for preparing the outdoor high-flame-retardant cable material according to claim 1, wherein the process comprises the following steps of: in the step (2), the molar ratio of amino groups and beta- (3-methyl-5-tertiary butyl-4-hydroxyphenyl) propionyl chloride of the POSS monomer containing amino groups is 1:1, a step of; the molar ratio of the beta- (3-methyl-5-tertiary butyl-4-hydroxyphenyl) propionyl chloride to the potassium carbonate is 1:1, a step of; the concentration of the benzene solution of the beta- (3-methyl-5-tertiary butyl-4-hydroxyphenyl) propionyl chloride is 0.4mol/L.
6. The process for preparing the outdoor high-flame-retardant cable material according to claim 1, wherein the process comprises the following steps of: in the step (3), the mass ratio of the deionized water to the absolute ethyl alcohol to the aluminate coupling agent to the magnesium hydroxide is (28-30): (2-3): 1:14; the mass ratio of the magnesium hydroxide, the butyl acrylate and the flame-retardant monomer containing double bonds is (4-5): 1:1, a step of; the amount of the azodiisobutyronitrile is 3-4wt% of the butyl acrylate.
7. The process for preparing the outdoor high-flame-retardant cable material according to claim 1, wherein the process comprises the following steps of: the mixing temperature is 60-65 ℃, and the extrusion temperature is 130-140 ℃.
8. The high flame retardant cable material for outdoor use according to any one of claims 1 to 7.
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| Title |
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| B.M.WALKER著: "《热塑性弹性体手册》", 31 August 1984, 化学工业出版社, pages: 251 * |
| 孙绍灿等: "《中外工程塑料牌号大全》", 31 March 2003, 浙江科学技术出版社, pages: 1228 * |
| 谢荣化: "《塑料购销手册》", 31 May 1994, 中国物资出版社, pages: 26 * |
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