CN103013021A - Preparation method of silane crosslinked halogen-free flame-retardant polyolefin cable material - Google Patents
Preparation method of silane crosslinked halogen-free flame-retardant polyolefin cable material Download PDFInfo
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Abstract
The invention provides a silane crosslinked halogen-free flame-retardant polyolefin cable material composition. The polyolefin cable material composition comprises a material A and a material B, wherein the material A comprises the following components in parts by weight: 100 parts of silane grafted polyolefin and 50-150 parts of modified flame retardant, 0.1-0.5 part of material A antioxidant and 0.5-2 parts of material A processing assistant; the modified flame retardant is aluminate coupling agent modified flame retardant; the material B comprises the following components in parts by weight: 100 parts of polyolefin, 0.5-5 parts of catalyst, 0.01-5 parts of copper ion inhibitor, 0.1-0.5 part of material B antioxidant and 5-10 parts of material B processing assistant; and the material A is subjected to reciprocating single-screw mixing and extrusion.
Description
Technical field
The invention belongs to technical field of polymer composite materials, be specifically related to a kind of preparation method of cable material of polyolefin of halogen-free flameproof of crosslinked with silicane, be fit to produce the flexible cable series products such as electric wire and transmission line, belong to CABLE MATERIALS preparation method's production technique field.
Background technology
Flame-proof polyolefine cable material is used for electric wire in a large number, because excellent mechanical property and the processing characteristics of polyethylene itself, flame-proof polyolefine cable material is used widely in the production of power cable.
The polyethylene crosslinking main method has three kinds: irradiation crosslinking, peroxide crosslinking method and silane grafting and crosslinking method.The crosslinked polyethylene purity that cross-linking radiation is produced is high, and production technique is simple, but apparatus expensive, radiation pollution is arranged, the difficult control of production technique; The peroxide crosslinking method is accurate, accurate to processing temperature control requirement, and manufacturing process slightly has the performance change of deviation product larger, and the loss that causes is huge.
The polyolefin electric wire and cable material that the halogen-free flameproof of CN101245169B water cooking preventing low-smoke non-halogen flame-proof silicone hydride crosslinked polyolefin composition and preparation method and CN102304254A crosslinked with silicane is arranged about the patent of crosslinked with silicane fireproofing cable material without halide.Traditional preparation method, the first step at first adopt twin screw extruder with Silane Grafted on the sub polyethylene subchain, form the A material, secondly catalyzer and polyethylene are expected at the mixing formation of twin screw extruder B.Second step is extruded A material and B material by a certain percentage after the mixing, the product of moulding is hydrolyzed crosslinked under hot water bath or water vapour.Existing silane crosslinked halogen-free flame-retardant A material is produced and is adopted twin screw extruder, the twin screw extruder internal thread is continuous, can only radial motion, and do not have axial motion, its poly mixing occurs in again radially, so a large amount of fire retardants disperses, the shear effect of melt is all not ideal, simultaneously, because its screw thread is continuous, it is very large that it acts on polyolefinic pressure, and the relevant device energy consumption also strengthens.
Traditional two-step approach is made the crosslinked with silicane fireproofing cable material without halide following shortcoming: 1, the Silane Grafted process has the side reaction of peroxide crosslinking, and grafting A expects poor fluidity, is difficult for processing; 2, the A of silane cross-linked polyolefin material is produced and is adopted double-screw extruding pelletizing, and the dispersion effect of silane crosslinker, initiator is poor, screw thread is continuous, and it is very large that it acts on poly pressure, and the relevant device energy consumption also strengthens.In addition, the crosslinked with silicane fireproofing cable material without halide of prior art also has fire retardant dispersing property and the not good shortcoming of environmental stress cracking resistance, and is not good from angle flame retardant properties and the feel of commodity.
In sum, this area lacks a kind of environmental stress cracking resistance of improving the polyolefin cable preparation method for material, dispersed, the suitable phosphorus flame retardant etc. of producing the crosslinked with silicane of the flexible cable series products such as electric wire and transmission line of fire retardant.
Summary of the invention
The first purpose of the present invention is to obtain a kind of environmental stress cracking resistance of improving the polyolefin cable preparation method for material, dispersed, the suitable phosphorus flame retardant etc. composition of producing the crosslinked with silicane of the flexible cable series products such as electric wire and transmission line of fire retardant.
The second purpose of the present invention is to obtain a kind of environmental stress cracking resistance of improving the polyolefin cable preparation method for material, dispersed, the suitable phosphorus flame retardant etc. of producing the crosslinked with silicane of the flexible cable series products such as electric wire and transmission line of fire retardant.
The 3rd purpose of the present invention is to obtain a kind of environmental stress cracking resistance of improving the polyolefin cable preparation method for material, the preparation method of the phosphorus flame retardant etc. of the crosslinked with silicane of the flexible cable series products such as dispersed, the suitable production electric wire of fire retardant and transmission line.
The 4th purpose of the present invention is to obtain a kind of environmental stress cracking resistance of improving the polyolefin cable preparation method for material, dispersed, the suitable halogen-free anti-flaming polyolefin cable of producing the crosslinked with silicane of the flexible cable series products such as electric wire and transmission line of fire retardant.
A first aspect of the present invention provides a kind of polyolefin cable feed composition of halogen-free flameproof of crosslinked with silicane, and described polyolefin cable feed composition comprises A material and B material,
Composition and the parts by weight of described A material are:
Polyolefine 100 weight parts of Silane Grafted;
Modified flame-retardant agent 50～150 weight parts; Described modified flame-retardant agent is the fire retardant of aluminate coupling agent modification;
A material oxidation inhibitor 0.1～0.5 weight part;
A material processing aid 0.5～2 weight part;
Composition and the parts by weight of described B material are:
Polyolefine 100 weight parts;
Catalyzer 0.5～5 weight part;
Anti copper agent 0.01～5 weight part;
B material oxidation inhibitor 0.1～0.5 weight part;
B material processing aid 5～10 weight parts;
Wherein said A material adopts reciprocating type single screw mixing to extrude.
In a specific embodiment of the present invention, one or more the composition in aluminium hydroxide, magnesium hydroxide or the zinc borate of aluminate coupling agent surface modification treatment is selected in described modified flame-retardant agent.
In a specific embodiment of the present invention, in the described modified flame-retardant agent, the modification consumption of described aluminate coupling agent is the 1%-3% of fire retardant quality.
In a specific embodiment of the present invention, described preparation method through the aluminate coupling agent surface modification treatment: fire retardant is joined in the homogenizer, and evenly adding quality under high-speed stirring is the aluminate coupling agent solution of the 1%-3% of fire retardant quality.
In a specific embodiment of the present invention, the polyolefine of described Silane Grafted makes by the following method: the polyolefine of described Silane Grafted carries out grafting by the component of following parts by weight and obtains:
Polyolefin resin 100 weight parts,
Silane crosslinker 0.2～5 weight part,
Initiator 0.01～1 weight part,
Grafting oxidation inhibitor 0.1～0.5 weight part.
A second aspect of the present invention provides the cable material of polyolefin of the halogen-free flameproof of the crosslinked with silicane that a kind of composition of the present invention makes.
A third aspect of the present invention provides a kind of preparation method of phosphorus flame retardant etc. of crosslinked with silicane of the present invention, and it comprises the steps:
Each component of A material and B material is provided;
Described A expects that each component carries out reciprocating type single Screw Extrusion granulation under 100～150 ℃, obtains the A material particulate material of fire-retardant grafting;
Described B expects that each component carries out mixing granulator under 140～190 ℃, obtains B material particulate material;
A material particulate material and the B of described fire-retardant grafting expect the particulate material dispersing and mixing, obtain the phosphorus flame retardant etc. of crosslinked with silicane.
In an embodiment, comprise the steps:
(1) the polyolefinic preparation of Silane Grafted: Silane Grafted is made the Silane Grafted polyolefine to polyolefin resin;
(2) take the Silane Grafted polyolefine as raw material; mix by proportioning with modified flame-retardant agent, processing aid etc.; through the weightless system of high-precision K-TRON feeding; enter reciprocating type single screw extruder pelletizer group; under 100-150 ℃, carry out mixing, shear, extrude; then carry out granulation with the spraying pelletizing, through overcooling, centrifuge dehydration, fluidized drying, realize fully-automatic packaging by automatic weighing and packing system.
(3) add the processing aid mixing such as catalyzer, oxidation inhibitor take polyolefine as main raw material after 3-5 minute, be delivered to twin screw, mixing granulator in 140-190 ℃ obtains B material particulate material;
(4) the fire-retardant grafting A material that the B material that step (3) is obtained and step (2) obtain obtains product in the mixing machine dispersing and mixing.
Silane Grafted polyolefine preparation process is in the described step (1): polyolefin resin, silane, initiator, oxidation inhibitor make silane grafted polyethylene through batch mixing, extruding pelletization, drying process.
In the described step (1), the extruding and pelletizing process temperature is 130-200 ℃, 60-70 ℃ of drying process temperature.
Silane Grafted polyolefine preparation process is in the described step (2): take the Silane Grafted polyolefine as raw material; mix by proportioning with modified flame-retardant agent, processing aid etc.; through the weightless system of high-precision feeding; enter reciprocating type single screw extruder pelletizer group; under 100-140 ℃, carry out mixing, shear, extrude; then carry out granulation with the spraying pelletizing, through overcooling, centrifuge dehydration, fluidized drying, realize fully-automatic packaging by automatic weighing and packing system.
Described reciprocating type single screw extruder pelletizer group technological temperature is 100-150 ℃, 50-65 ℃ of drying process temperature.
Catalysis master batch preparation process is in the described step (3): polyolefine is that main raw material added the processing aid mixing such as catalyzer, oxidation inhibitor after 3-5 minute, is delivered to twin screw, and mixing granulator in 140-190 ℃ obtains B material particulate material;
Described step (4) with the catalysis mother particle B material of step (3) acquisition and the fire-retardant grafting A material of step (2) acquisition, obtains product in the mixing machine dispersing and mixing.
(90-95) of fire-retardant grafting A material and catalysis mother particle B material: send into again mixing machine after the ratio extraction (5-10) and fully be mixed to get compound, and send into single screw extrusion machine and extrude at 140-190 ℃ and obtain finished product.
In a specific embodiment of the present invention, the A of described fire-retardant grafting material particulate material and B material particulate material are according to (90-95): part by weight dispersing and mixing (5-10), extrude the phosphorus flame retardant etc. that obtains crosslinked with silicane in 140-190 ℃.
In an embodiment, (90-95) of fire-retardant grafting A material particulate material and B material particulate material (catalysis masterbatch): send into again mixing machine after ratio (5-10) is extracted and fully be mixed to get compound, and send into single screw extrusion machine and extrude at 140-190 ℃ and obtain finished product.
A fourth aspect of the present invention provides a kind of prepared cable of cable material of polyolefin of halogen-free flameproof of crosslinked with silicane of the present invention.
Description of drawings
The polyolefinic production technological process of Fig. 1 Silane Grafted;
Fig. 2 Silane Grafted fire retardant polyolefin A material manufacturing technique schema; Adopt reciprocating type single screw mixing to extrude (also being " two steps type is extruded ");
The production technological process of Fig. 3 catalysis mother particle B material.
Embodiment
The inventor is through extensive and deep research, by improving preparation technology, obtained a kind of environmental stress cracking resistance of improving the polyolefin cable preparation method for material, dispersed, the suitable phosphorus flame retardant etc. of producing the crosslinked with silicane of the flexible cable series products such as electric wire and transmission line of fire retardant.Finished on this basis the present invention.
Technical conceive of the present invention is as follows:
The preparation method who relates to a kind of phosphorus flame retardant etc. of crosslinked with silicane, the polyolefin cable preparation method for material of this halogen-free flameproof adopts the preparation of two-step approach crosslinked with silicane technology, and the polyolefin cable preparation method for material of the halogen-free flameproof of this crosslinked with silicane is comprised of fire-retardant grafting A material and catalysis masterbatch B material.Most preferably, the preparation of fire-retardant grafting A material may further comprise the steps: prepare first silane grafted polyolefin resin; Take silane grafted polyolefin resin as raw material; mix by proportioning with modified flame-retardant agent, processing aid etc.; through the weightless system of high-precision feeding; enter reciprocating type single screw extruder pelletizer group; under 100-150 ℃, carry out mixing, shear, extrude; then carry out granulation with the spraying pelletizing, through overcooling, centrifuge dehydration, fluidized drying, realize fully-automatic packaging by automatic weighing and packing system.Catalysis mother particle B material: add the processing aid mixing such as catalyzer, oxidation inhibitor after 3-5 minute take polyolefine as main raw material, be delivered to twin screw, mixing granulator in 140-190 ℃ obtains B material particulate material.The fire-retardant grafting A material of the present invention improves the environmental stress cracking resistance of polyolefin cable preparation method for material, fire retardant is dispersed, and the phosphorus flame retardant etc. of the crosslinked with silicane that provides has soft feel, good flame retardant resistance is fit to produce the flexible cable series products such as electric wire and transmission line.
Among the present invention, term " contains " or the various compositions of " comprising " expression can be applied in mixture of the present invention or the composition together.Therefore, term " mainly by ... form " and " by ... composition " be included in that term " contains " or in " comprising ".
Below describe in detail to various aspects of the present invention:
The polyolefin cable feed composition of the halogen-free flameproof of crosslinked with silicane
A first aspect of the present invention provides a kind of polyolefin cable feed composition of halogen-free flameproof of crosslinked with silicane, and described polyolefin cable feed composition comprises A material and B material,
Composition and the parts by weight of described A material are:
Polyolefine 100 weight parts of Silane Grafted;
Modified flame-retardant agent 50～150 weight parts; Described modified flame-retardant agent is the fire retardant of aluminate coupling agent modification;
A material oxidation inhibitor 0.1～0.5 weight part;
A material processing aid 0.5～2 weight part;
Composition and the parts by weight of described B material are:
Polyolefine 100 weight parts;
Catalyzer 0.5～5 weight part;
Anti copper agent 0.01～5 weight part;
B material oxidation inhibitor 0.1～0.5 weight part;
B material processing aid 5～10 weight parts;
Wherein said A material adopts reciprocating type single screw mixing to extrude.
The polyolefine of Silane Grafted
In a specific embodiment of the present invention, the polyolefine of described Silane Grafted makes by the following method: the polyolefine of described Silane Grafted carries out grafting by the component of following parts by weight and obtains:
Polyolefin resin 100 weight parts,
Silane crosslinker 0.2～5 weight part,
Initiator 0.01～1 weight part,
Oxidation inhibitor 0.1～0.5 weight part.
Among the present invention, described " polyolefin resin " includes but not limited to: Low Density Polyethylene, ultra-low density polyethylene, linear low density polyethylene, metallocene linear-low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-octene copolymer.
Among the present invention, the polyolefine of " polyolefine " in " polyolefine of Silane Grafted " in the A material and B material can be identical, also can difference.
Among the present invention, described " silane crosslinker " includes but not limited to: vinyltrimethoxy silane or vinyltriethoxysilane.
Among the present invention, described " initiator " includes but not limited to: described initiator is selected a kind of in dicumyl peroxide, di-tert-butyl peroxide, the benzoyl peroxide.
1010,1135, one or more the composition among 300#, 168, the DLTP, 1076 among the present invention, described " oxidation inhibitor " includes but not limited to:.Described " oxidation inhibitor " can be identical with " B expects oxidation inhibitor ", also can be different.
Among the present invention, the step of described " grafting " (or crosslinked) comprising: polyolefin resin, silane, initiator, oxidation inhibitor are made through batch mixing, extruding pelletization, drying process.Described " batch mixing, extruding pelletization, drying process " is the ordinary skill in the art.
The modified flame-retardant agent
In a specific embodiment of the present invention, one or more the composition in aluminium hydroxide, magnesium hydroxide or the zinc borate of aluminate coupling agent surface modification treatment is selected in described modified flame-retardant agent.
Among the present invention, described " Aluminate " is this area routine, includes but not limited to aluminic acid trimethyl, aluminic acid three isopropyl esters, aluminic acid three benzyl esters.
In an embodiment, in the described modified flame-retardant agent, the modification consumption of described aluminate coupling agent is the 1%-3% of fire retardant quality.
In an embodiment, described preparation method through the aluminate coupling agent surface modification treatment: fire retardant is joined in the homogenizer, and evenly adding quality under high-speed stirring is the aluminate coupling agent solution of the 1%-3% of fire retardant quality.
Other components
Among the present invention, described " A expects processing aid " includes but not limited to one or more composition of amine hydroxybenzene, polyethylene wax, Poly Propylene Wax.
Among the present invention, described " B expects processing aid " includes but not limited to one or more the composition among the fluorine-containing PPA of amine hydroxybenzene, polyethylene wax, Poly Propylene Wax or rheological agent.
Among the present invention, described " A expects processing aid " can be identical with described " B expects processing aid ", also can be different.Described processing aid can be selected the with lubricator composition of one or more among the fluorine-containing PPA of amine hydroxybenzene, polyethylene wax, Poly Propylene Wax, organosilicon or rheological agent of polyethylene.
Among the present invention, described " anti copper agent " includes but not limited to MDA-5, MDA-1024.
Among the present invention, described " A expects oxidation inhibitor " includes but not limited to four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (1010), β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid isooctyl alcohol ester (1135), three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid esters (168), 4,4 '-thiobis (6-tertiary butyl meta-cresol (300#), the two dodecane esters (DLTP) of thio-2 acid, the composition of one or more in β-(3,5-di-tert-butyl-hydroxy phenyl) positive octadecanol ester of propionic acid (1076).
Among the present invention, described " B expects oxidation inhibitor " includes but not limited to four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (1010), β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid isooctyl alcohol ester (1135), three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid esters (168), 4,4 '-thiobis (6-tertiary butyl meta-cresol (300#), the two dodecane esters (DLTP) of thio-2 acid, the composition of one or more in β-(3,5-di-tert-butyl-hydroxy phenyl) positive octadecanol ester of propionic acid (1076).
Among the present invention, described " A expects oxidation inhibitor " can be identical with described " B expects oxidation inhibitor ", also can be different.
Among the present invention, described " catalyzer " for B material includes but not limited to one or more of positive tetrabutyl zirconate, dioctyl dibutyl tin, dibutyltin diacetate, dibutyl tin laurate.
Reciprocating type single screw mixing is extruded (also being " two steps type is extruded ")
Among the present invention, described " reciprocating type single screw mixing is extruded " refers to adopt and can do radial motion, can make again the reciprocating type machine of extruding of axial motion and produce the A material.Described " the reciprocating type machine of extruding " is that this area is existing, for example the commercially available reciprocating type machine of extruding of SJW-70/SJ-120 unit model.
The inventor finds that described A material adopts reciprocating type single-screw intermixing extruder can greatly improve the performance of cross-linked polyolefin of the present invention.Compare with existing twin screw extruder, reciprocating screw is made the discontinuous screw structure, makes screw rod also do according to certain rules simultaneously axial motion at continuous rotation, and its polyolefinic mixture is subject to uniform shearing stress; Reciprocating type single-screw intermixing extruder self-cleaning is good, when the close spiral shell rib of pin, can play scraping the effect that accumulates in spiral shell rib side-walls material, has guaranteed that reciprocating type single spiral shell reed pin forcing machine has good self-cleaning property; Each shearing and the shunting of the little pin of the length-to-diameter ratio of screw rod and material impel the rapid melting of material; Temperature control accurate pin the stirring action homogenizing distribution of material temperature; So silane crosslinker, DCP initiator are uniformly dispersed, the shear effect of the polyethylene material of melt is good, and simultaneously, because screw rod has interrupted screw thread, its pressure that acts on the polymkeric substance is very little, and corresponding equipment energy consumption is also less.This production method has greatly improved the crosslinked with silicane degree, has made complete processing very convenient flexibly, operates simple and easy.
The contriver finds, adopt the combination of " modified flame-retardant agent " and " polyolefine of Silane Grafted ", and employing " reciprocating type single screw mixing is extruded ", so that the environmental stress cracking resistance of the cable material of polyolefin that the present invention obtains, fire retardant is dispersed to be improved, and the phosphorus flame retardant etc. of the crosslinked with silicane that provides has soft feel, good flame retardant resistance, the suitable flexible cable series products such as electric wire and transmission line of producing.
CABLE MATERIALS and preparation method thereof
A second aspect of the present invention provides the cable material of polyolefin of the halogen-free flameproof of the crosslinked with silicane that a kind of composition of the present invention makes.
In a preference, the performance of described " cable material of polyolefin of the halogen-free flameproof of crosslinked with silicane " is good, the characteristics such as flexibility is splendid, good hand touch of resisting environmental stress and cracking.(examination criteria GB/T2951.41-2008).
A third aspect of the present invention provides a kind of preparation method of phosphorus flame retardant etc. of crosslinked with silicane of the present invention, and it comprises the steps:
Each component of A material and B material is provided;
Described A expects that each component carries out reciprocating type single Screw Extrusion granulation under 100～150 ℃, obtains the A material particulate material of fire-retardant grafting;
Described B expects that each component carries out mixing granulator under 140～190 ℃, obtains B material particulate material;
A material particulate material and the B of described fire-retardant grafting expect the particulate material dispersing and mixing, obtain the phosphorus flame retardant etc. of crosslinked with silicane.
In an embodiment, comprise the steps:
(1) the polyolefinic preparation of Silane Grafted: Silane Grafted is made the Silane Grafted polyolefine to polyolefin resin;
(2) take the Silane Grafted polyolefine as raw material; mix by proportioning with modified flame-retardant agent, processing aid etc.; through the weightless system of high-precision K-TRON feeding; enter reciprocating type single screw extruder pelletizer group; under 100-150 ℃, carry out mixing, shear, extrude; then carry out granulation with the spraying pelletizing, through overcooling, centrifuge dehydration, fluidized drying, realize fully-automatic packaging by automatic weighing and packing system.
(3) add the processing aid mixing such as catalyzer, oxidation inhibitor take polyolefine as main raw material after 3-5 minute, be delivered to twin screw, mixing granulator in 140-190 ℃ obtains B material particulate material;
(4) the fire-retardant grafting A material that the B material that step (3) is obtained and step (2) obtain obtains product in the mixing machine dispersing and mixing.
Silane Grafted polyolefine preparation process is in the described step (1): polyolefin resin, silane, initiator, oxidation inhibitor make silane grafted polyethylene through batch mixing, extruding pelletization, drying process.
In the described step (1), the extruding and pelletizing process temperature is 130-200 ℃, 60-70 ℃ of drying process temperature.
Silane Grafted polyolefine preparation process is in the described step (2): take the Silane Grafted polyolefine as raw material; mix by proportioning with modified flame-retardant agent, processing aid etc.; through the weightless system of high-precision feeding; enter reciprocating type single screw extruder pelletizer group; under 100-140 ℃, carry out mixing, shear, extrude; then carry out granulation with the spraying pelletizing, through overcooling, centrifuge dehydration, fluidized drying, realize fully-automatic packaging by automatic weighing and packing system.
Described reciprocating type single screw extruder pelletizer group technological temperature is 100-150 ℃, 50-65 ℃ of drying process temperature.
Catalysis master batch preparation process is in the described step (3): polyolefine is that main raw material added the processing aid mixing such as catalyzer, oxidation inhibitor after 3-5 minute, is delivered to twin screw, and mixing granulator in 140-190 ℃ obtains B material particulate material;
Described step (4) with the catalysis mother particle B material of step (3) acquisition and the fire-retardant grafting A material of step (2) acquisition, obtains product in the mixing machine dispersing and mixing.
(90-95) of fire-retardant grafting A material and catalysis mother particle B material: send into again mixing machine after the ratio extraction (5-10) and fully be mixed to get compound, and send into single screw extrusion machine and extrude at 140-190 ℃ and obtain finished product.
In a specific embodiment of the present invention, the A of described fire-retardant grafting material particulate material and B material particulate material are according to (90-95): part by weight dispersing and mixing (5-10), extrude the phosphorus flame retardant etc. that obtains crosslinked with silicane in 140-190 ℃.
In an embodiment, (90-95) of fire-retardant grafting A material particulate material and B material particulate material (catalysis masterbatch): send into again mixing machine after ratio (5-10) is extracted and fully be mixed to get compound, and send into single screw extrusion machine and extrude at 140-190 ℃ and obtain finished product.
A fourth aspect of the present invention provides a kind of prepared cable of cable material of polyolefin of halogen-free flameproof of crosslinked with silicane of the present invention.
The objective of the invention is to overcome the shortcoming in the existing technology, a kind of preparation method of crosslinked phosphorus flame retardant etc. of silane is provided.Mainly provide a kind of screw rod can do radial motion, can make again the reciprocating type machine of extruding of axial motion and produce the A material.Compare with existing twin screw extruder, reciprocating screw is made the discontinuous screw structure, make screw rod also do according to certain rules simultaneously axial motion at continuous rotation, its poly mixture is subject to uniform shearing stress, so the processing aids such as silane crosslinker, DCP initiator, fire retardant are uniformly dispersed, the shear effect of the polyolefine material of melt is good, simultaneously, because screw rod has interrupted screw thread, its pressure that acts on the polymkeric substance is very little, and corresponding equipment energy consumption is also less.This production method has greatly improved the crosslinked with silicane degree, has made complete processing very convenient flexibly, operates simple and easy.With cable insulation material thermotolerance, aging resistance and good processability that this production method is produced, preparation technology is simple, and energy consumption is low, have preferably economic benefit.
Preferred implementation of the present invention
A kind of polyolefin cable preparation method for material of halogen-free flameproof of crosslinked with silicane comprises the steps:
(1) the polyolefinic preparation of Silane Grafted: Silane Grafted is made the Silane Grafted polyolefine to polyolefin resin;
(2) take the Silane Grafted polyolefine as raw material; mix by proportioning with fire retardant, processing aid etc.; through the weightless system of high-precision K-TRON feeding; enter reciprocating type single screw extruder pelletizer group; under 100-150 ℃, carry out mixing, shear, extrude; then carry out granulation with the spraying pelletizing, through overcooling, centrifuge dehydration, fluidized drying, realize fully-automatic packaging by automatic weighing and packing system.
(3) add the processing aid mixing such as catalyzer, oxidation inhibitor take polyolefine as main raw material after 3-5 minute, be delivered to twin screw, mixing granulator in 140-190 ℃ obtains B material particulate material;
(4) the fire-retardant grafting A material that the B material that step (3) is obtained and step (2) obtain obtains product in the mixing machine dispersing and mixing.
The polyolefinic preparation process of Silane Grafted is that polyolefin resin, silane, initiator, oxidation inhibitor make the Silane Grafted polyolefine through batch mixing, extruding pelletization, drying process in the described step (1).
Preferably, the polyolefin cable preparation method for material of the halogen-free flameproof of described crosslinked with silicane, it is characterized in that the parts by weight of described polyolefin resin, silane, initiator, oxidation inhibitor are respectively: polyolefin resin 100, silane crosslinker 0.2-5, initiator 0.01-1, oxidation inhibitor 0.1-0.5.
Preferably, described polyolefin resin is that ethylene-vinyl acetate resin is that vinyl acetate content is the ethylene-vinyl acetate copolymer resin of 24-28% in the molecule.
Preferably, described polyolefin resin is that the molten finger of ldpe resin is 2 ± 0.5g/10min, originates from China Petrochemical Industry.
Preferably, described silane is the VTMO of Degussa.
Preferably, described initiator is the DCP in Aksu.
Preferably, described complete processing is that the extruding and pelletizing process temperature is 130-200 ℃, 60-70 ℃ of drying process temperature.
Preferably, in the described step (1), need that also the silane grafted polyethylene that makes is carried out Aluminum-plastic composite bag and vacuumize packing.
Silane Grafted polyolefine preparation process is in the described step (2): take the Silane Grafted polyolefine as raw material; mix by proportioning with modified flame-retardant agent, processing aid etc.; through the weightless system of high-precision K-TRON feeding; enter reciprocating type single screw extruder pelletizer group; under 100-140 ℃, carry out mixing, shear, extrude; then carry out granulation with the spraying pelletizing, through overcooling, centrifuge dehydration, fluidized drying, realize fully-automatic packaging by automatic weighing and packing system.
Preferably, individual component title and the parts by weight of the raw material of the flame-proof polyolefine cable material of described step (2) are: Silane Grafted polyolefine 100, modified flame-retardant agent 50-150, oxidation inhibitor 0.1-0.5.
Described modified flame-retardant agent is selected from aluminium hydroxide, magnesium hydroxide or the zinc borate that aluminate coupling agent is processed, preferred mixture through aluminate coupling agent surface treatment aluminium hydroxide and magnesium hydroxide.
Described preparation method through the aluminate coupling agent surface modification treatment: fire retardant is joined in the homogenizer, and evenly adding quality under high-speed stirring is the aluminate coupling agent solution of the 1%-3% of fire retardant quality.
Described oxidation inhibitor is 1010,1135,168,300#, DLTP, 1076, and is preferred, and described oxidation inhibitor is the Irganox1010 type oxidation inhibitor of Switzerland vapour Bagong department production.
Preferably, described technique is that reciprocating type single screw extruder pelletizer group technological temperature is 100-150 ℃, 50-65 ℃ of drying process temperature.
Catalysis master batch preparation process is in the described step (3): polyolefine is that main raw material added the processing aid mixing such as catalyzer, oxidation inhibitor after 3-5 minute, is delivered to twin screw, and mixing granulator in 140-190 ℃ obtains B material particulate material;
Preferably, individual component title and the parts by weight of the raw material of the catalysis master batch of described step (3) preparation are: polyolefine 100, catalyzer 0.5-5, oxidation inhibitor 0.1-0.5, processing aid 0.01-5.
Preferably, described polyolefin resin is that the molten finger of ldpe resin is 2 ± 0.5g/10min, originates from China Petrochemical Industry.
Preferably, described polyolefin resin is ethylene-octene copolymer melting index 5g/10min, and hardness is 75A.
Preferably, the described catalyzer catalyzer dibutyltin diacetate that is;
Described processing aid is lubricant, and described lubricant is selected from one or more the composition among the fluorine-containing PPA of amine hydroxybenzene, polyethylene wax, Poly Propylene Wax, organosilicon or rheological agent;
Described step (4) with the catalysis mother particle B material of step (3) acquisition and the fire-retardant grafting A material of step (2) acquisition, obtains product in the mixing machine dispersing and mixing.
Preferably, send into again mixing machine after the ratio extraction of the 95:5-of described fire-retardant grafting A material and catalysis mother particle B material and fully be mixed to get compound, and send into single screw extrusion machine and extrude at 140-190 ℃ and obtain finished product.
Compared with prior art; method of the present invention has following advantage: one, utilize silane; polyolefin resin is carried out grafting; after making it add in the flame-proof polyolefine cable material; better receive fire retardant and adopt reciprocating type single screw extruder pelletizer group fire retardant to be uniformly dispersed; guarantee the stability of quality product, improved the mechanical property of flame-proof polyolefine cable material.Two, adopt the crosslinked with silicane mode can prolong the fire retardant polyolefin resisting environmental stress and cracking time, avoid flame-proof polyolefine cable material owing to add a large amount of inorganic combustion inhibitors and cause the sheath cracking phenomena; Three, improved to a certain extent the surface of extruding of fire retardant polyolefin.
Specify such as nothing, various raw materials of the present invention all can obtain by commercially available; Or prepare according to the ordinary method of this area.Unless otherwise defined or explanation, same meanings of being familiar with of all specialties used herein and scientific words and those skilled in the art.Any method similar or impartial to described content and material all can be applicable in the inventive method in addition.
Other aspects of the present invention are because the disclosure of this paper is apparent to those skilled in the art.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example is measured according to national standard usually.If there is not corresponding national standard, then carry out according to general international standard, normal condition or according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all umbers are weight part, and all per-cents are weight percentage, and described polymericular weight is number-average molecular weight.
Unless otherwise defined or explanation, same meanings of being familiar with of all specialties used herein and scientific words and those skilled in the art.Any method similar or impartial to described content and material all can be applicable in the inventive method in addition.
Embodiment 1
Present embodiment provides a kind of preparation method of low smoke halogen-free fire retardant polyolefin cable material of crosslinked with silicane, and the raw material of employing and consumption are referring to table, wherein:
Ethylene-vinyl acetate resin is that vinyl acetate content is the ethylene-vinyl acetate copolymer resin of 24-28% in the molecule.
The molten finger of ldpe resin is 2 ± 0.5g/10min, originates from China Petrochemical Industry.
Silane is the VTMO of Degussa.
Initiator is the DCP in Aksu.
The modified flame-retardant agent prepares by following process: aluminium hydroxide is joined in the homogenizer, evenly add quality and be 2% aluminate coupling agent solution of aluminium hydroxide quality under high-speed stirring.
Oxidation inhibitor is the Irganox1010 type oxidation inhibitor that Switzerland vapour Bagong department produces.
Ethylene-octene copolymer melting index 5g/10min, hardness is 75A.
Catalyzer is dibutyltin diacetate;
Lubricant, described lubricant are selected from one or more the composition among the fluorine-containing PPA of amine hydroxybenzene, polyethylene wax, Poly Propylene Wax, organosilicon or rheological agent;
The preparation method of the low smoke halogen-free fire retardant polyolefin cable material of crosslinked with silicane comprises the steps:
1, clicks first prescription preparation Silane Grafted polyolefine: ethylene-vinyl acetate copolymer resin, linear low density polyethylene, silane (VTMO of Degussa), initiator (DCP in Aksu), oxidation inhibitor; Under 40 ℃ of conditions, pour ethylene-vinyl acetate resin into high mixer first during batch mixing, slowly run, silane, DCP and antioxidant 1010 are added dropwise in the resin at leisure, equably, mixed 5 minutes at high mixer, extruding pelletization, pelletizing and packing are carried out in then blanking.Production technological process as shown in Figure 1.
Processing temperature is set as follows:
| One district | Two districts | Three districts | Four districts | Five districts | Six districts | Seven districts | Eight districts | Nine districts | Head |
| 100 | 120 | 150 | 170 | 180 | 185 | 185 | 190 | 190 | 190 |
The twin screw engine speed is not more than 300rpm, and Main motor current is not more than 350A, filter screen 90 orders, and vacuum tightness is not more than 0.02MPa.
Amine hydroxybenzene), black masterbatch 2, prepare burden according to following prescription: Silane Grafted polyolefin copolymer, modified flame-retardant agent aluminium hydroxide, antioxidant 1010, processing aid (lubricant:; in the input feed bin; through the weightless system of high-precision K-TRON feeding; enter reciprocating type single screw extruder pelletizer group; under 100-145 ℃, carry out mixing, shear, extrude; then carry out granulation with the spraying pelletizing, through overcooling, centrifuge dehydration, fluidized drying, make fire-retardant grafting A material.Production technological process as shown in Figure 2.
Processing temperature is set as follows:
| One district | Two districts | Three districts | Four districts | Five districts | Six districts | Seven districts | Eight districts | Nine districts | Head |
| 140 | 140 | 125 | 110 | 130 | 135 | 110 | 120 | 130 | 140 |
3, prepare burden according to following proportioning: when ethylene-octene copolymer, linear low density polyethylene, dibutyl tin dilaurate, antioxidant 1010, lubricant PE wax, processing aid organosilicon batch mixing under normal temperature, pour polyolefin resin into high mixer first, slowly run, catalyzer, lubricant, processing aid and antioxidant 1010 are added dropwise in the resin at leisure, equably, mixed 3 minutes at high mixer, then extruding pelletization, pelletizing and packing are carried out in blanking.Production technological process as shown in Figure 1.
Processing temperature is set as follows:
| One district | Two districts | Three districts | Four districts | Five districts | Six districts | Seven districts | Eight districts | Nine districts | Head |
| 100 | 120 | 125 | 130 | 130 | 135 | 135 | 140 | 140 | 140 |
The twin screw engine speed is not more than 300rpm, and Main motor current is not more than 350A, filter screen 40 orders, and vacuum tightness is not less than 0.02MPa.
4, with step (2) obtained flame-retardant grafting A material and step (3) gained catalysis mother particle B material by weight ratio 95:5 mix, through cable forcing machine stranding, be the silane crosslinked halogen-free flame-retardant CABLE MATERIALS.
Embodiment 2
Present embodiment provides a kind of preparation method of cable material of polyolefin of halogen-free flameproof of crosslinked with silicane, and the raw material that it adopts and consumption are referring to table, and the raw material outside the modified flame-retardant agent is all identical with embodiment 1.
In this example, the modified flame-retardant agent prepares by following process: aluminium hydroxide and magnesium hydroxide (weight ratio 2:1) are joined in the homogenizer, evenly add the 1.5% aluminate coupling agent solution that quality is magnesium hydroxide and aluminium hydroxide total mass at homogenizer.
The preparation process of the low smoke halogen-free fire retardant polyolefin cable material of crosslinked with silicane is with embodiment 1.
Embodiment 3
Present embodiment provides a kind of preparation method of cable material of polyolefin of halogen-free flameproof of crosslinked with silicane, and the raw material that it adopts and consumption are referring to table, and the raw material outside the modified flame-retardant agent is all identical with embodiment 1.
In this example, the modified flame-retardant agent prepares by following process: aluminium hydroxide and magnesium hydroxide (weight ratio 1:1) are joined in the homogenizer, evenly add the 1% aluminate coupling agent solution that quality is magnesium hydroxide and aluminium hydroxide total mass at homogenizer.
The preparation process of the low smoke halogen-free fire retardant polyolefin cable material of crosslinked with silicane is with embodiment 1.
Embodiment 4
Present embodiment provides a kind of preparation method of cable material of polyolefin of halogen-free flameproof of crosslinked with silicane, and the raw material that it adopts and consumption are referring to table, and the raw material outside the modified flame-retardant agent is all identical with embodiment 1.
In this example, the modified flame-retardant agent prepares by following process: aluminium hydroxide and magnesium hydroxide (weight ratio 1:2) are joined in the homogenizer, evenly add the 1% aluminate coupling agent solution that quality is magnesium hydroxide and aluminium hydroxide total mass at homogenizer.
The preparation process of the low smoke halogen-free fire retardant polyolefin cable material of crosslinked with silicane is with embodiment 1.
Embodiment 5
Present embodiment provides a kind of preparation method of cable material of polyolefin of halogen-free flameproof of crosslinked with silicane, and the raw material that it adopts and consumption are referring to table, and the raw material outside the modified flame-retardant agent is all identical with embodiment 1.
In this example, the modified flame-retardant agent prepares by following process: magnesium hydroxide is joined in the homogenizer, evenly add the 1% aluminate coupling agent solution that quality is magnesium hydroxide and aluminium hydroxide total mass at homogenizer.
The preparation process of the low smoke halogen-free fire retardant polyolefin cable material of crosslinked with silicane is with embodiment 1.
Embodiment 6
Present embodiment provides a kind of preparation method of cable material of polyolefin of halogen-free flameproof of crosslinked with silicane, and the raw material that it adopts and consumption are referring to table, and the raw material outside the modified flame-retardant agent is all identical with embodiment 1.
In this example, the modified flame-retardant agent prepares by following process: aluminium hydroxide and zinc borate (weight ratio 5:1) are joined in the homogenizer, evenly add the 2% aluminate coupling agent solution that quality is magnesium hydroxide and aluminium hydroxide total mass at homogenizer.
The preparation process of the low smoke halogen-free fire retardant polyolefin cable material of crosslinked with silicane is with embodiment 1.
The performance comparing embodiment
Properties to the low smoke halogen-free fire retardant polyolefin cable material of the crosslinked with silicane of embodiment 1-6 is tested.The result sees table.
Correlative value is the test value of the crosslinked with silicane fireproofing cable material without halide of common double screw rod manufacturing, and embodiment 1-6 is each performance number that makes product.
Conclusion:
Can be found out by table, the crosslinked with silicane fireproofing cable material without halide that employing reciprocating single-bolt extruder unit makes in the present embodiment after testing, the melting index of A material is all greater than the crosslinked with silicane fireproofing cable material without halide of common double screw rod granulation, indicate the good fluidity of material, easily processing, simultaneously contrast and other performance perameters, its mechanical property has lifting by a relatively large margin, environmental stress cracking resistance is better, and through factory's unwrapping wire checking, adopt the surface of the obtained crosslinked with silicane fireproofing cable material without halide of reciprocating single-bolt extruder unit prepared crosslinked with silicane fireproofing cable material without halide surface ratio common double screw rod to improve to some extent.
The above only is preferred embodiment of the present invention, be not to limit essence technology contents scope of the present invention, essence technology contents of the present invention is broadly to be defined in the claim scope of application, any technology entity or method that other people finish, if defined identical with the claim scope of application, also or a kind of change of equivalence, all will be regarded as being covered by among this claim scope.
All quote in this application as a reference at all documents that the present invention mentions, just as each piece document is quoted separately as a reference.Should be understood that in addition after having read foregoing of the present invention, those skilled in the art can make various changes or modifications the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (8)
1. the polyolefin cable feed composition of the halogen-free flameproof of a crosslinked with silicane is characterized in that, described polyolefin cable feed composition comprises A material and B material,
Described A material comprises in parts by weight:
Polyolefine 100 weight parts of Silane Grafted;
Modified flame-retardant agent 50～150 weight parts; Described modified flame-retardant agent is the fire retardant of aluminate coupling agent modification;
A material oxidation inhibitor 0.1～0.5 weight part;
A material processing aid 0.5～2 weight part;
Composition and the parts by weight of described B material are:
Polyolefine 100 weight parts;
Catalyzer 0.5～5 weight part;
Anti copper agent 0.01～5 weight part;
B material oxidation inhibitor 0.1～0.5 weight part;
B material processing aid 5～10 weight parts;
Wherein said A material adopts reciprocating type single screw mixing to extrude.
2. composition as claimed in claim 1 is characterized in that, one or more the composition in aluminium hydroxide, magnesium hydroxide or the zinc borate of aluminate coupling agent surface modification treatment is selected in described modified flame-retardant agent.
3. composition as claimed in claim 2 is characterized in that, in the described modified flame-retardant agent, the modification consumption of described aluminate coupling agent is the 1%-3 % by weight of fire retardant quality.
4. composition as claimed in claim 1 is characterized in that, the polyolefine of described Silane Grafted makes by the following method: the polyolefine of described Silane Grafted carries out grafting by the component that comprises following parts by weight and obtains:
Polyolefin resin 100 weight parts,
Silane crosslinker 0.2～5 weight part,
Initiator 0.01～1 weight part,
Grafting oxidation inhibitor 0.1～0.5 weight part.
5. the cable material of polyolefin of the halogen-free flameproof of the crosslinked with silicane that makes of a composition as claimed in claim 1.
6. the preparation method of the phosphorus flame retardant etc. of a crosslinked with silicane as claimed in claim 5 is characterized in that, comprises the steps:
Each component of A material and B material is provided;
Described A expects that each component carries out reciprocating type single Screw Extrusion granulation under 100～150 ℃, obtains the A material particulate material of fire-retardant grafting;
Described B expects that each component carries out mixing granulator under 140～190 ℃, obtains B material particulate material;
A material particulate material and the B of described fire-retardant grafting expect the particulate material dispersing and mixing, obtain the phosphorus flame retardant etc. of crosslinked with silicane.
7. method as claimed in claim 6, it is characterized in that, the A of described fire-retardant grafting material particulate material and B material particulate material are according to (90-95): part by weight dispersing and mixing (5-10), extrude the phosphorus flame retardant etc. that obtains crosslinked with silicane in 140-190 ℃.
8. prepared cable of cable material of polyolefin of the halogen-free flameproof of crosslinked with silicane as claimed in claim 5.
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| CN103724759A (en) * | 2013-12-05 | 2014-04-16 | 上海至正道化高分子材料有限公司 | Halogen-free flame retardant organosilane self-crosslinked polyolefin cable material and preparation method thereof |
| CN106751056A (en) * | 2016-11-14 | 2017-05-31 | 安徽建筑大学 | Triphenyl phosphate modified low-smoke halogen-free flame-retardant cable material |
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| CN103724759A (en) * | 2013-12-05 | 2014-04-16 | 上海至正道化高分子材料有限公司 | Halogen-free flame retardant organosilane self-crosslinked polyolefin cable material and preparation method thereof |
| CN106751056A (en) * | 2016-11-14 | 2017-05-31 | 安徽建筑大学 | Triphenyl phosphate modified low-smoke halogen-free flame-retardant cable material |
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| CN107033432A (en) * | 2017-04-28 | 2017-08-11 | 成都鑫成鹏高分子科技股份有限公司 | A kind of room temperature crosslinked with silicane halide-free fireproof composite polyolefine material and preparation method thereof |
| CN110724330B (en) * | 2018-07-16 | 2022-08-12 | 中国石油化工股份有限公司 | Flame-retardant rotational molding polyolefin composition and preparation method thereof |
| CN110724330A (en) * | 2018-07-16 | 2020-01-24 | 中国石油化工股份有限公司 | Flame-retardant rotational molding polyolefin composition and preparation method thereof |
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