CN103013021B - A kind of preparation method of phosphorus flame retardant etc. of crosslinked with silicane - Google Patents
A kind of preparation method of phosphorus flame retardant etc. of crosslinked with silicane Download PDFInfo
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- CN103013021B CN103013021B CN201210592121.0A CN201210592121A CN103013021B CN 103013021 B CN103013021 B CN 103013021B CN 201210592121 A CN201210592121 A CN 201210592121A CN 103013021 B CN103013021 B CN 103013021B
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Abstract
The invention provides a kind of polyolefin cable feed composition of halogen-free flameproof of crosslinked with silicane, described polyolefin cable feed composition comprises A material and B material, and composition and the parts by weight of described A material are: polyolefine 100 weight part of Silane Grafted; Modified flame-retardant agent 50 ~ 150 weight part; Described modified flame-retardant agent is the fire retardant of aluminate coupling agent modification; A expects oxidation inhibitor 0.1 ~ 0.5 weight part; A expects processing aid 0.5 ~ 2 weight part; Composition and the parts by weight of described B material are: polyolefine 100 weight part; Catalyzer 0.5 ~ 5 weight part; Anti copper agent 0.01 ~ 5 weight part; B expects oxidation inhibitor 0.1 ~ 0.5 weight part; B expects processing aid 5 ~ 10 weight part; Wherein said A material adopts reciprocating singe screw mixing 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 applicable to producing the flexible cable such as electric wire and transmission line series products, belong to the production technique field of CABLE MATERIALS preparation method.
Background technology
Flame-proof polyolefine cable material is a large amount of for electric wire, and the mechanical property excellent due to polyethylene itself and processing characteristics, flame-proof polyolefine cable material is used widely in the production of power cable.
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, has radiation pollution, the more difficult control of production technique; To processing temperature control overflow accurately, accurately, the performance change of manufacturing process slightly deviation product is comparatively large, and the loss caused is huge for peroxide crosslinking method.
Patent about crosslinked with silicane fireproofing cable material without halide has the polyolefin electric wire and cable material of 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.Traditional preparation method, first the first step adopts twin screw extruder by Silane Grafted on polyethylene molecular chain, forms A material, secondly catalyzer and polyethylene is expected at twin screw extruder mixing formation B.Second step is extruded after A material and the mixing by a certain percentage of B material, and shaping product is hydrolyzed crosslinked under hot water bath or water vapour.Existing silane crosslinked halogen-free flame-retardant A expects to produce employing twin screw extruder, twin screw extruder internal thread is continuous print, can only radial motion, and there is no axial motion, its poly mixing occurs in radial direction again, so a large amount of fire retardant dispersions, the shear effect of melt is all not ideal, meanwhile, because its screw thread is continuous print, it is very large that it acts on polyolefinic pressure, and relevant device energy consumption also strengthens.
Traditional two-step approach manufactures crosslinked with silicane fireproofing cable material without halide following shortcoming: 1, Silane Grafted process has the side reaction of peroxide crosslinking, and grafting A expects poor fluidity, not easily processes; 2, the A material of silane cross-linked polyolefin is produced and is adopted double-screw extruding pelletizing, and the dispersion effect of silane crosslinker, initiator is poor, screw thread is continuous print, and it is very large that it acts on poly pressure, and 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, from the angle flame retardant properties of commodity and feel not good.
In sum, this area lacks a kind of environmental stress cracking resistance improving polyolefin cable preparation method for material, dispersed, the applicable phosphorus flame retardant etc. of producing the crosslinked with silicane of the flexible cable such as electric wire and transmission line series products of fire retardant.
Summary of the invention
The first object of the present invention is to obtain a kind of environmental stress cracking resistance improving polyolefin cable preparation method for material, dispersed, the applicable phosphorus flame retardant etc. composition producing the crosslinked with silicane of the flexible cable such as electric wire and transmission line series products of fire retardant.
The second object of the present invention is to obtain a kind of environmental stress cracking resistance improving polyolefin cable preparation method for material, dispersed, the applicable phosphorus flame retardant etc. of producing the crosslinked with silicane of the flexible cable such as electric wire and transmission line series products of fire retardant.
The third object of the present invention is to obtain a kind of environmental stress cracking resistance improving polyolefin cable preparation method for material, dispersed, the applicable preparation method producing the phosphorus flame retardant etc. of the crosslinked with silicane of the flexible cable such as electric wire and transmission line series products of fire retardant.
The fourth object of the present invention is to obtain a kind of environmental stress cracking resistance improving polyolefin cable preparation method for material, dispersed, the applicable halogen-free anti-flaming polyolefin cable producing the crosslinked with silicane of the flexible cable such as electric wire and transmission line series products 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 part of Silane Grafted;
Modified flame-retardant agent 50 ~ 150 weight part; Described modified flame-retardant agent is the fire retardant of aluminate coupling agent modification;
A expects oxidation inhibitor 0.1 ~ 0.5 weight part;
A expects processing aid 0.5 ~ 2 weight part;
Composition and the parts by weight of described B material are:
Polyolefine 100 weight part;
Catalyzer 0.5 ~ 5 weight part;
Anti copper agent 0.01 ~ 5 weight part;
B expects oxidation inhibitor 0.1 ~ 0.5 weight part;
B expects processing aid 5 ~ 10 weight part;
Wherein said A material adopts reciprocating singe screw mixing extrusion.
In a specific embodiment of the present invention, the composition of one or more in the aluminium hydroxide of aluminate coupling agent surface modification treatment, magnesium hydroxide or zinc borate is selected in described modified flame-retardant agent.
In a specific embodiment of the present invention, in 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, the described preparation method through aluminate coupling agent surface modification treatment: join in homogenizer by fire retardant, evenly adds the aluminate coupling agent solution that quality is the 1%-3% of fire retardant quality under high velocity agitation.
In a specific embodiment of the present invention, the polyolefine of described Silane Grafted obtains 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 part,
Silane crosslinker 0.2 ~ 5 weight part,
Initiator 0.01 ~ 1 weight part,
Grafting oxidation inhibitor 0.1 ~ 0.5 weight part.
The cable material of polyolefin of the halogen-free flameproof of the crosslinked with silicane that a second aspect of the present invention provides a kind of composition of the present invention to obtain.
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 that A expects and B expects is provided;
Described A expects that each component carries out reciprocating Single screw extrusion granulation at 100 ~ 150 DEG C, and the A obtaining fire-retardant grafting expects particulate material;
Described B expects that each component carries out mixing granulator at 140 ~ 190 DEG C, obtains B and expects particulate material;
The A of described fire-retardant grafting expects that particulate material and B expect particulate material dispersing and mixing, obtains the phosphorus flame retardant etc. of crosslinked with silicane.
In an embodiment, comprise the steps:
(1) preparation of silane grafted polyolefin: by silane grafted polyolefin obtained on Silane Grafted to polyolefin resin;
(2) take silane grafted polyolefin 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 Single screw extrusion granulation unit; carry out at 100-150 DEG C mixing, shear, extrude; then carry out granulation with spraying pelletizing, through overcooling, centrifuge dehydration, fluidized drying, realize fully-automatic packaging by automatic weighing and packing system.
(3) be that main raw material added the mixing of the processing aid such as catalyzer, oxidation inhibitor after 3-5 minute with polyolefine, be delivered to twin screw, mixing granulator in 140-190 DEG C, obtain B and expect particulate material;
(4) the fire-retardant grafting A that B material step (3) obtained and step (2) obtain expects, obtains product in mixing machine dispersing and mixing.
In described step (1), silane grafted polyolefin preparation process is: polyolefin resin, silane, initiator, oxidation inhibitor obtain silane grafted polyethylene through batch mixing, extruding pelletization, drying process.
In described step (1), extruding and pelletizing process temperature is 130-200 DEG C, drying process temperature 60-70 DEG C.
In described step (2), silane grafted polyolefin preparation process is: take silane grafted polyolefin as raw material; mix by proportioning with modified flame-retardant agent, processing aid etc.; through the weightless system of high-precision feeding; enter reciprocating Single screw extrusion granulation unit; carry out at 100-140 DEG C mixing, shear, extrude; then carry out granulation with spraying pelletizing, through overcooling, centrifuge dehydration, fluidized drying, realize fully-automatic packaging by automatic weighing and packing system.
Described reciprocating Single screw extrusion granulation unit technological temperature is 100-150 DEG C, drying process temperature 50-65 DEG C.
In described step (3), uncatalyzed master batch preparation process is: polyolefine is that main raw material added the mixing of the processing aid such as catalyzer, oxidation inhibitor after 3-5 minute, is delivered to twin screw, mixing granulator in 140-190 DEG C, obtains B and expects particulate material;
Described step (4), the fire-retardant grafting A that uncatalyzed master batch B step (3) obtained expects and step (2) obtains expects, obtains product in mixing machine dispersing and mixing.
Fire-retardant grafting A expects and uncatalyzed master batch B expects (90-95): send into mixing machine again after the ratio extraction of (5-10) and be fully mixed to get compound, and send into single screw extrusion machine and extrude at 140-190 DEG C and obtain finished product.
In a specific embodiment of the present invention, the A of described fire-retardant grafting expects that particulate material and B expect that particulate material is according to (90-95): the part by weight dispersing and mixing of (5-10), extrudes in 140-190 DEG C the phosphorus flame retardant etc. obtaining crosslinked with silicane.
In an embodiment, fire-retardant grafting A expects that particulate material and B expect (90-95) of particulate material (catalysis masterbatch): the ratio of (5-10) is sent into mixing machine again after extracting and is fully mixed to get compound, and sends into single screw extrusion machine and extrude at 140-190 DEG C and obtain finished product.
A fourth aspect of the present invention provides a kind of cable obtained by cable material of polyolefin of halogen-free flameproof of crosslinked with silicane of the present invention.
Accompanying drawing explanation
The production technological process of Fig. 1 silane grafted polyolefin;
Fig. 2 Silane Grafted fire retardant polyolefin A material manufacturing technique schema; Adopt reciprocating singe screw mixing extrusion (being also " two steps type is extruded ");
The production technological process that Fig. 3 uncatalyzed master batch B expects.
Embodiment
The present inventor is through extensive and deep research, by improving preparation technology, obtain a kind of environmental stress cracking resistance improving polyolefin cable preparation method for material, dispersed, the applicable phosphorus flame retardant etc. of producing the crosslinked with silicane of the flexible cable such as electric wire and transmission line series products of fire retardant.Complete the present invention on this basis.
Technical conceive of the present invention is as follows:
Relate to a kind of preparation method 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 expected by fire-retardant grafting A and catalysis masterbatch B expects to form.Most preferably, fire-retardant grafting A expects that preparation comprises the following steps: first prepare 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 Single screw extrusion granulation unit; carry out at 100-150 DEG C mixing, shear, extrude; then carry out granulation with spraying pelletizing, through overcooling, centrifuge dehydration, fluidized drying, realize fully-automatic packaging by automatic weighing and packing system.Uncatalyzed master batch B expects: be that main raw material added the mixing of the processing aid such as catalyzer, oxidation inhibitor after 3-5 minute with polyolefine, be delivered to twin screw, mixing granulator in 140-190 DEG C, obtains B and expects 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 provided has soft feel, good flame retardant resistance, is applicable to producing the flexible cable such as electric wire and transmission line series products.
In the present invention, term " contains " or " comprising " represents that various composition can be applied in mixture of the present invention or composition together.Therefore, term " primarily of ... composition " and " by ... form " be included in term and " contain " 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 part of Silane Grafted;
Modified flame-retardant agent 50 ~ 150 weight part; Described modified flame-retardant agent is the fire retardant of aluminate coupling agent modification;
A expects oxidation inhibitor 0.1 ~ 0.5 weight part;
A expects processing aid 0.5 ~ 2 weight part;
Composition and the parts by weight of described B material are:
Polyolefine 100 weight part;
Catalyzer 0.5 ~ 5 weight part;
Anti copper agent 0.01 ~ 5 weight part;
B expects oxidation inhibitor 0.1 ~ 0.5 weight part;
B expects processing aid 5 ~ 10 weight part;
Wherein said A material adopts reciprocating singe screw mixing extrusion.
the polyolefine of Silane Grafted
In a specific embodiment of the present invention, the polyolefine of described Silane Grafted obtains 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 part,
Silane crosslinker 0.2 ~ 5 weight part,
Initiator 0.01 ~ 1 weight part,
Oxidation inhibitor 0.1 ~ 0.5 weight part.
In 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.
In the present invention, " polyolefine " in " polyolefine of Silane Grafted " in A material can be identical with the polyolefine that B expects, also can be different.
In the present invention, described " silane crosslinker " includes but not limited to: vinyltrimethoxy silane or vinyltriethoxysilane.
In the present invention, described " initiator " includes but not limited to: the one in dicumyl peroxide, di-tert-butyl peroxide, benzoyl peroxide selected by described initiator.
In the present invention, described " oxidation inhibitor " includes but not limited to: 1010,1135,300#, 168, the composition of one or more in DLTP, 1076.Described " oxidation inhibitor " can be identical with " B expects oxidation inhibitor ", also can be different.
In the present invention, the step of described " grafting " (or crosslinked) comprising: polyolefin resin, silane, initiator, oxidation inhibitor are obtained through batch mixing, extruding pelletization, drying process.Described " batch mixing, extruding pelletization, drying process " is the ordinary skill in the art.
modified flame-retardant agent
In a specific embodiment of the present invention, the composition of one or more in the aluminium hydroxide of aluminate coupling agent surface modification treatment, magnesium hydroxide or zinc borate is selected in described modified flame-retardant agent.
In the present invention, described " Aluminate " is this area routine, includes but not limited to aluminic acid trimethyl, aluminic acid three isopropyl ester, aluminic acid three benzyl ester.
In an embodiment, in described modified flame-retardant agent, the modification consumption of described aluminate coupling agent is the 1%-3% of fire retardant quality.
In an embodiment, the described preparation method through aluminate coupling agent surface modification treatment: join in homogenizer by fire retardant, evenly adds the aluminate coupling agent solution that quality is the 1%-3% of fire retardant quality under high velocity agitation.
other components
In 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.
In the present invention, described " B expects processing aid " includes but not limited to the composition of one or more in the fluorine-containing PPA of amine hydroxybenzene, polyethylene wax, Poly Propylene Wax or rheological agent.
In 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 select one or more the composition of polyethylene with lubricator in the fluorine-containing PPA of amine hydroxybenzene, polyethylene wax, Poly Propylene Wax, organosilicon or rheological agent.
In the present invention, described " anti copper agent " includes but not limited to MDA-5, MDA-1024.
In the present invention, described " A expects oxidation inhibitor " includes but not limited to four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (1010), β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid isooctyl alcohol ester (1135), three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester (168), 4, 4 '-thiobis (6-tertiary butyl meta-cresol (300#), the two dodecane ester (DLTP) of thio-2 acid, β-(3, 5-di-tert-butyl-hydroxy phenyl) composition of one or more in the positive octadecanol ester (1076) of propionic acid.
In the present invention, described " B expects oxidation inhibitor " includes but not limited to four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (1010), β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid isooctyl alcohol ester (1135), three ［ 2.4-di-tert-butyl-phenyl ］ phosphorous acid ester (168), 4, 4 '-thiobis (6-tertiary butyl meta-cresol (300#), the two dodecane ester (DLTP) of thio-2 acid, β-(3, 5-di-tert-butyl-hydroxy phenyl) composition of one or more in the positive octadecanol ester (1076) of propionic acid.
In the present invention, described " A expects oxidation inhibitor " can be identical with described " B expects oxidation inhibitor ", also can be different.
In the present invention, described " catalyzer " for B material include but not limited in positive tetrabutyl zirconate, dioctyl dibutyl tin, dibutyltin diacetate, dibutyl tin laurate one or more.
reciprocating singe screw mixing extrusion (being also " two steps type is extruded ")
In the present invention, described " reciprocating singe screw mixing extrusion " refers to that employing can do radial motion, and A material produced by the reciprocating forcing machine doing again axial motion.Described " reciprocating forcing machine " is that this area is existing, the commercially available reciprocating forcing machine of such as SJW-70/SJ-120 unit model.
The present inventor finds, described A material adopts reciprocating single-screw intermixing extruder greatly can improve the performance of cross-linked polyolefin of the present invention.Compared with existing twin screw extruder, reciprocating screw makes discontinuous screw structure, makes screw rod also do axial motion according to certain rules at continuous rotation simultaneously, and its polyolefinic mixture is subject to uniform shearing stress; Reciprocating single-screw intermixing extruder self-cleaning is good, when pin is near spiral shell rib, can play the effect scraping and accumulate in spiral shell rib side-walls material, ensure that reciprocating single spiral shell reed pin forcing machine has good self-cleaning property; The little pin of length-to-diameter ratio of screw rod and each shearing of material and shunting, impel the rapid melting of material; Temperature controls the distribution of material temperature of the stirring action homogenizing of precision dowel pins; So silane crosslinker, DCP initiator are uniformly dispersed, the shear effect of the polyethylene material of melt is good, and meanwhile, because screw rod has interrupted screw thread, its effect pressure is on polymer very little, and corresponding equipment energy consumption is also less.This production method substantially increases crosslinked with silicane degree, makes complete processing flexibly very convenient, operates simple and easy.
Contriver finds, adopt the combination of " modified flame-retardant agent " and " polyolefine of Silane Grafted ", and adopt " reciprocating singe screw mixing extrusion ", the environmental stress cracking resistance of the cable material of polyolefin that the present invention is obtained, fire retardant dispersiveness improves, and the phosphorus flame retardant etc. of the crosslinked with silicane provided has soft feel, good flame retardant resistance, is applicable to producing the flexible cable such as electric wire and transmission line series products.
CABLE MATERIALS and preparation method thereof
The cable material of polyolefin of the halogen-free flameproof of the crosslinked with silicane that a second aspect of the present invention provides a kind of composition of the present invention to obtain.
In a preference, the performance of described " cable material of polyolefin of the halogen-free flameproof of crosslinked with silicane " is the features such as resisting environmental stress and cracking is good, flexibility is splendid, good hand touch.(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 that A expects and B expects is provided;
Described A expects that each component carries out reciprocating Single screw extrusion granulation at 100 ~ 150 DEG C, and the A obtaining fire-retardant grafting expects particulate material;
Described B expects that each component carries out mixing granulator at 140 ~ 190 DEG C, obtains B and expects particulate material;
The A of described fire-retardant grafting expects that particulate material and B expect particulate material dispersing and mixing, obtains the phosphorus flame retardant etc. of crosslinked with silicane.
In an embodiment, comprise the steps:
(1) preparation of silane grafted polyolefin: by silane grafted polyolefin obtained on Silane Grafted to polyolefin resin;
(2) take silane grafted polyolefin 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 Single screw extrusion granulation unit; carry out at 100-150 DEG C mixing, shear, extrude; then carry out granulation with spraying pelletizing, through overcooling, centrifuge dehydration, fluidized drying, realize fully-automatic packaging by automatic weighing and packing system.
(3) be that main raw material added the mixing of the processing aid such as catalyzer, oxidation inhibitor after 3-5 minute with polyolefine, be delivered to twin screw, mixing granulator in 140-190 DEG C, obtain B and expect particulate material;
(4) the fire-retardant grafting A that B material step (3) obtained and step (2) obtain expects, obtains product in mixing machine dispersing and mixing.
In described step (1), silane grafted polyolefin preparation process is: polyolefin resin, silane, initiator, oxidation inhibitor obtain silane grafted polyethylene through batch mixing, extruding pelletization, drying process.
In described step (1), extruding and pelletizing process temperature is 130-200 DEG C, drying process temperature 60-70 DEG C.
In described step (2), silane grafted polyolefin preparation process is: take silane grafted polyolefin as raw material; mix by proportioning with modified flame-retardant agent, processing aid etc.; through the weightless system of high-precision feeding; enter reciprocating Single screw extrusion granulation unit; carry out at 100-140 DEG C mixing, shear, extrude; then carry out granulation with spraying pelletizing, through overcooling, centrifuge dehydration, fluidized drying, realize fully-automatic packaging by automatic weighing and packing system.
Described reciprocating Single screw extrusion granulation unit technological temperature is 100-150 DEG C, drying process temperature 50-65 DEG C.
In described step (3), uncatalyzed master batch preparation process is: polyolefine is that main raw material added the mixing of the processing aid such as catalyzer, oxidation inhibitor after 3-5 minute, is delivered to twin screw, mixing granulator in 140-190 DEG C, obtains B and expects particulate material;
Described step (4), the fire-retardant grafting A that uncatalyzed master batch B step (3) obtained expects and step (2) obtains expects, obtains product in mixing machine dispersing and mixing.
Fire-retardant grafting A expects and uncatalyzed master batch B expects (90-95): send into mixing machine again after the ratio extraction of (5-10) and be fully mixed to get compound, and send into single screw extrusion machine and extrude at 140-190 DEG C and obtain finished product.
In a specific embodiment of the present invention, the A of described fire-retardant grafting expects that particulate material and B expect that particulate material is according to (90-95): the part by weight dispersing and mixing of (5-10), extrudes in 140-190 DEG C the phosphorus flame retardant etc. obtaining crosslinked with silicane.
In an embodiment, fire-retardant grafting A expects that particulate material and B expect (90-95) of particulate material (catalysis masterbatch): the ratio of (5-10) is sent into mixing machine again after extracting and is fully mixed to get compound, and sends into single screw extrusion machine and extrude at 140-190 DEG C and obtain finished product.
A fourth aspect of the present invention provides a kind of cable obtained by cable material of polyolefin of halogen-free flameproof of crosslinked with silicane of the present invention.
The object of the invention is to overcome the shortcoming in existing technology, a kind of preparation method of crosslinked phosphorus flame retardant etc. of silane is provided.Mainly provide a kind of screw rod to do radial motion, A material produced by the reciprocating forcing machine doing again axial motion.Compared with existing twin screw extruder, reciprocating screw makes discontinuous screw structure, make screw rod also do axial motion according to certain rules at continuous rotation simultaneously, 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 effect pressure is on polymer very little, and corresponding equipment energy consumption is also less.This production method substantially increases crosslinked with silicane degree, makes complete processing flexibly very convenient, operates simple and easy.Cable insulation material thermotolerance, aging resistance and the good processability produced by this production method, preparation technology is simple, and energy consumption is low, have good economic benefit.
The preferred embodiment of the present invention
A polyolefin cable preparation method for material for the halogen-free flameproof of crosslinked with silicane, comprises the steps:
(1) preparation of silane grafted polyolefin: by silane grafted polyolefin obtained on Silane Grafted to polyolefin resin;
(2) take silane grafted polyolefin as raw material; mix by proportioning with fire retardant, processing aid etc.; through the weightless system of high-precision K-TRON feeding; enter reciprocating Single screw extrusion granulation unit; carry out at 100-150 DEG C mixing, shear, extrude; then carry out granulation with spraying pelletizing, through overcooling, centrifuge dehydration, fluidized drying, realize fully-automatic packaging by automatic weighing and packing system.
(3) be that main raw material added the mixing of the processing aid such as catalyzer, oxidation inhibitor after 3-5 minute with polyolefine, be delivered to twin screw, mixing granulator in 140-190 DEG C, obtain B and expect particulate material;
(4) the fire-retardant grafting A that B material step (3) obtained and step (2) obtain expects, obtains product in mixing machine dispersing and mixing.
The preparation process of the middle silane grafted polyolefin of described step (1) is polyolefin resin, silane, initiator, oxidation inhibitor obtain silane grafted polyolefin through batch mixing, extruding pelletization, drying process.
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 ethylene-vinyl acetate resin is that in molecule, vinyl acetate content is the ethylene-vinyl acetate copolymer resin of 24-28%.
Preferably, described polyolefin resin is the melting means 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 extruding and pelletizing process temperature is 130-200 DEG C, drying process temperature 60-70 DEG C.
Preferably, in described step (1), also need that Aluminum-plastic composite bag is carried out to obtained silane grafted polyethylene and vacuumize packaging.
In described step (2), silane grafted polyolefin preparation process is: take silane grafted polyolefin 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 Single screw extrusion granulation unit; carry out at 100-140 DEG C mixing, shear, extrude; then carry out granulation with spraying pelletizing, through overcooling, centrifuge dehydration, fluidized drying, realize fully-automatic packaging by automatic weighing and packing system.
Preferably, the individual ingredient names of the raw material of the flame-proof polyolefine cable material of described step (2) and parts by weight are: silane grafted polyolefin 100, modified flame-retardant agent 50-150, oxidation inhibitor 0.1-0.5.
Described modified flame-retardant agent is selected from the aluminium hydroxide of aluminate coupling agent process, magnesium hydroxide or zinc borate, preferably through the mixture of aluminate coupling agent surface treatment aluminium hydroxide and magnesium hydroxide.
The described preparation method through aluminate coupling agent surface modification treatment: join in homogenizer by fire retardant, evenly adds the aluminate coupling agent solution that quality is the 1%-3% of fire retardant quality under high velocity agitation.
Described oxidation inhibitor is 1010,1135,168,300#, DLTP, 1076, preferably, described oxidation inhibitor is the Irganox1010 type oxidation inhibitor that Switzerland's vapour Bagong department produces.
Preferably, described technique is reciprocating Single screw extrusion granulation unit technological temperature is 100-150 DEG C, drying process temperature 50-65 DEG C.
In described step (3), uncatalyzed master batch preparation process is: polyolefine is that main raw material added the mixing of the processing aid such as catalyzer, oxidation inhibitor after 3-5 minute, is delivered to twin screw, mixing granulator in 140-190 DEG C, obtains B and expects particulate material;
Preferably, the individual ingredient names of raw material prepared by the uncatalyzed master batch of described step (3) and parts by weight are: polyolefine 100, catalyzer 0.5-5, oxidation inhibitor 0.1-0.5, processing aid 0.01-5.
Preferably, described polyolefin resin is the melting means 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 catalyzer dibutyltin diacetate that described catalyzer is;
Described processing aid is lubricant, and described lubricant is selected from the composition of one or more in the fluorine-containing PPA of amine hydroxybenzene, polyethylene wax, Poly Propylene Wax, organosilicon or rheological agent;
Described step (4), the fire-retardant grafting A that uncatalyzed master batch B step (3) obtained expects and step (2) obtains expects, obtains product in mixing machine dispersing and mixing.
Preferably, send into mixing machine again after the ratio extraction of the 95:5-that described fire-retardant grafting A expects and uncatalyzed master batch B expects and be fully mixed to get compound, and send into single screw extrusion machine and extrude at 140-190 DEG C and obtain finished product.
Compared with prior art; method of the present invention has following advantage: one, utilize silane; grafting is carried out to polyolefin resin; it is made to add to after in flame-proof polyolefine cable material; better receive fire retardant and adopt reciprocating Single screw extrusion granulation unit fire retardant to be uniformly dispersed; ensure the stability of quality product, improve the mechanical property of flame-proof polyolefine cable material.Two, adopt crosslinked with silicane mode can extend the fire retardant polyolefin resisting environmental stress and cracking time, avoid flame-proof polyolefine cable material to cause sheath cracking phenomena owing to adding a large amount of inorganic combustion inhibitors; What three, improve fire retardant polyolefin to a certain extent extrudes surface.
As no specific instructions, various raw material of the present invention all can be obtained by commercially available; Or prepare according to the ordinary method of this area.Unless otherwise defined or described herein, all specialties used herein and scientific words and those skilled in the art the same meaning be familiar with.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.
Other aspects of the present invention, due to disclosure herein, are apparent to those skilled in the art.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, measures according to national standard usually.If there is no corresponding national standard, then according to general international standard, normal condition or carry out according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all numbers are weight part, and all per-cent is weight percentage, and described polymericular weight is number-average molecular weight.
Unless otherwise defined or described herein, all specialties used herein and scientific words and those skilled in the art the same meaning be familiar with.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.
Embodiment 1
The present embodiment provides a kind of preparation method of low smoke halogen-free fire retardant polyolefin cable material of crosslinked with silicane, the raw material of employing and consumption see table, wherein:
Ethylene-vinyl acetate resin is that in molecule, vinyl acetate content is the ethylene-vinyl acetate copolymer resin of 24-28%.
The melting means 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.
Modified flame-retardant agent is prepared by following process: joined by aluminium hydroxide in homogenizer, evenly adds the aluminate coupling agent solution that quality is 2% of aluminium hydroxide quality under high velocity agitation.
Oxidation inhibitor is the Irganox1010 type oxidation inhibitor that Switzerland's vapour Bagong department produces.
Ethylene-octene copolymer melting index 5g/10min, hardness is 75A.
Catalyzer is dibutyltin diacetate;
Lubricant, described lubricant is selected from the composition of one or more in 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, first click formula and prepare silane grafted polyolefin: ethylene-vinyl acetate copolymer resin, linear low density polyethylene, silane (VTMO of Degussa), initiator (DCP in Aksu), oxidation inhibitor; During batch mixing under 40 DEG C of conditions, first pour ethylene-vinyl acetate resin into high mixer, slowly run, silane, DCP and antioxidant 1010 are added dropwise in resin at leisure, equably, mix 5 minutes at high mixer, then blanking, carry out extruding pelletization, pelletizing and packaging.Production technological process as shown in Figure 1.
Processing temperature is set as follows:
| One district | 2nd district | 3rd district | 4th district | 5th district | 6th district | 7th district | 8th district | 9th district | Head |
| 100 | 120 | 150 | 170 | 180 | 185 | 185 | 190 | 190 | 190 |
Twin screw engine speed is not more than 300rpm, and Main motor current is not more than 350A, and filter screen 90 order, vacuum tightness is not more than 0.02MPa.
2, prepare burden according to following formula: silane grafted polyolefin multipolymer, modified flame-retardant agent aluminium hydroxide, antioxidant 1010, processing aid (lubricant: amine hydroxybenzene), black masterbatch; in input feed bin; through the weightless system of high-precision K-TRON feeding; enter reciprocating Single screw extrusion granulation unit; carry out at 100-145 DEG C mixing, shear, extrude; then carry out granulation with spraying pelletizing, expect through overcooling, centrifuge dehydration, fluidized drying, obtained fire-retardant grafting A.Production technological process as shown in Figure 2.
Processing temperature is set as follows:
| One district | 2nd district | 3rd district | 4th district | 5th district | 6th district | 7th district | 8th district | 9th district | 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, first pour polyolefin resin into high mixer, slowly run, catalyzer, lubricant, processing aid and antioxidant 1010 are added dropwise in resin at leisure, equably, 3 minutes are mixed at high mixer, then blanking, carries out extruding pelletization, pelletizing and packaging.Production technological process as shown in Figure 1.
Processing temperature is set as follows:
| One district | 2nd district | 3rd district | 4th district | 5th district | 6th district | 7th district | 8th district | 9th district | Head |
| 100 | 120 | 125 | 130 | 130 | 135 | 135 | 140 | 140 | 140 |
Twin screw engine speed is not more than 300rpm, and Main motor current is not more than 350A, and filter screen 40 order, vacuum tightness is not less than 0.02MPa.
4, step (2) obtained flame-retardant grafting A material and step (3) gained uncatalyzed master batch B are expected that 95:5 mixes by weight ratio, through cable forcing machine stranding, be silane crosslinked halogen-free flame-retardant CABLE MATERIALS.
Embodiment 2
The present embodiment provides a kind of preparation method of cable material of polyolefin of halogen-free flameproof of crosslinked with silicane, and its raw material adopted and consumption are see table, and the raw material outside modified flame-retardant agent is all identical with embodiment 1.
In this example, modified flame-retardant agent is prepared by following process: join in homogenizer by aluminium hydroxide and magnesium hydroxide (weight ratio 2:1), evenly adds at homogenizer the 1.5% aluminate coupling agent solution that quality is magnesium hydroxide and aluminium hydroxide total mass.
The preparation process of the low smoke halogen-free fire retardant polyolefin cable material of crosslinked with silicane is with embodiment 1.
Embodiment 3
The present embodiment provides a kind of preparation method of cable material of polyolefin of halogen-free flameproof of crosslinked with silicane, and its raw material adopted and consumption are see table, and the raw material outside modified flame-retardant agent is all identical with embodiment 1.
In this example, modified flame-retardant agent is prepared by following process: join in homogenizer by aluminium hydroxide and magnesium hydroxide (weight ratio 1:1), evenly adds at homogenizer the 1% aluminate coupling agent solution that quality is magnesium hydroxide and aluminium hydroxide total mass.
The preparation process of the low smoke halogen-free fire retardant polyolefin cable material of crosslinked with silicane is with embodiment 1.
Embodiment 4
The present embodiment provides a kind of preparation method of cable material of polyolefin of halogen-free flameproof of crosslinked with silicane, and its raw material adopted and consumption are see table, and the raw material outside modified flame-retardant agent is all identical with embodiment 1.
In this example, modified flame-retardant agent is prepared by following process: join in homogenizer by aluminium hydroxide and magnesium hydroxide (weight ratio 1:2), evenly adds at homogenizer the 1% aluminate coupling agent solution that quality is magnesium hydroxide and aluminium hydroxide total mass.
The preparation process of the low smoke halogen-free fire retardant polyolefin cable material of crosslinked with silicane is with embodiment 1.
Embodiment 5
The present embodiment provides a kind of preparation method of cable material of polyolefin of halogen-free flameproof of crosslinked with silicane, and its raw material adopted and consumption are see table, and the raw material outside modified flame-retardant agent is all identical with embodiment 1.
In this example, modified flame-retardant agent is prepared by following process: joined by magnesium hydroxide in homogenizer, evenly adds at homogenizer the 1% aluminate coupling agent solution that quality is magnesium hydroxide and aluminium hydroxide total mass.
The preparation process of the low smoke halogen-free fire retardant polyolefin cable material of crosslinked with silicane is with embodiment 1.
Embodiment 6
The present embodiment provides a kind of preparation method of cable material of polyolefin of halogen-free flameproof of crosslinked with silicane, and its raw material adopted and consumption are see table, and the raw material outside modified flame-retardant agent is all identical with embodiment 1.
In this example, modified flame-retardant agent is prepared by following process: join in homogenizer by aluminium hydroxide and zinc borate (weight ratio 5:1), evenly adds at homogenizer the 2% aluminate coupling agent solution that quality is magnesium hydroxide and aluminium hydroxide total mass.
The preparation process of the low smoke halogen-free fire retardant polyolefin cable material of crosslinked with silicane is with embodiment 1.
Performance comparision embodiment
The properties of the low smoke halogen-free fire retardant polyolefin cable material of the crosslinked with silicane of embodiment 1-6 is tested.Result sees table.
Correlative value is the test value of the crosslinked with silicane fireproofing cable material without halide that common double screw rod manufactures, and embodiment 1-6 is each performance number of obtained product.
Conclusion:
As can be seen from table, the crosslinked with silicane fireproofing cable material without halide adopting reciprocating single-bolt extruder unit obtained 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, easy processing, contrast simultaneously 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, the surface of crosslinked with silicane fireproofing cable material without halide obtained by the crosslinked with silicane fireproofing cable material without halide surface ratio common double screw rod obtained by reciprocating single-bolt extruder unit is adopted to improve to some extent.
The foregoing is only preferred embodiment of the present invention, and be not used to limit substantial technological context of the present invention, substantial technological content of the present invention is broadly defined in the right of application, any technology entities that other people complete or method, if with application right define identical, also or a kind of change of equivalence, be all covered by being regarded as among this right.
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read foregoing of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (6)
1. a polyolefin cable feed composition for the halogen-free flameproof of crosslinked with silicane, is characterized in that, described polyolefin cable feed composition comprises A material and B material,
Described A material comprises with weight parts:
Polyolefine 100 weight part of Silane Grafted;
Modified flame-retardant agent 50 ~ 150 weight part; The composition of one or more in the aluminium hydroxide of aluminate coupling agent surface modification treatment, magnesium hydroxide or zinc borate is selected in described modified flame-retardant agent;
A expects oxidation inhibitor 0.1 ~ 0.5 weight part;
A expects processing aid 0.5 ~ 2 weight part;
Composition and the parts by weight of described B material are:
Wherein said A material adopts reciprocating singe screw mixing extrusion;
The polyolefine of described Silane Grafted obtains by the following method: the polyolefine of described Silane Grafted carries out grafting by the component comprising following parts by weight and obtains:
Polyolefin resin 100 weight part,
Silane crosslinker 0.2 ~ 5 weight part,
Initiator 0.01 ~ 1 weight part,
Grafting oxidation inhibitor 0.1 ~ 0.5 weight part.
2. composition as claimed in claim 1, it is characterized in that, in described modified flame-retardant agent, the modification consumption of described aluminate coupling agent is the 1%-3 % by weight of fire retardant quality.
3. the cable material of polyolefin of the halogen-free flameproof of crosslinked with silicane that obtains of a composition as claimed in claim 1.
4. a preparation method for the phosphorus flame retardant etc. of crosslinked with silicane as claimed in claim 3, is characterized in that, comprises the steps:
Each component that A expects and B expects is provided;
Described A expects that each component carries out reciprocating Single screw extrusion granulation at 100 ~ 150 DEG C, and the A obtaining fire-retardant grafting expects particulate material;
Described B expects that each component carries out mixing granulator at 140 ~ 190 DEG C, obtains B and expects particulate material;
The A of described fire-retardant grafting expects that particulate material and B expect particulate material dispersing and mixing, obtains the phosphorus flame retardant etc. of crosslinked with silicane.
5. method as claimed in claim 4, it is characterized in that, the A of described fire-retardant grafting expects that particulate material and B expect that particulate material is according to (90-95): the part by weight dispersing and mixing of (5-10), extrudes in 140-190 DEG C the phosphorus flame retardant etc. obtaining crosslinked with silicane.
6. the cable obtained by cable material of polyolefin of the halogen-free flameproof of crosslinked with silicane as claimed in claim 3.
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| CN103724759B (en) * | 2013-12-05 | 2016-04-20 | 上海至正道化高分子材料股份有限公司 | A kind of halogen-free flame-retardant organosilane self crosslinking polyolefin cable material and preparation method thereof |
| CN106751056A (en) * | 2016-11-14 | 2017-05-31 | 安徽建筑大学 | A kind of ester modified fireproofing cable material without halide of phosphate trimethylbenzene |
| CN106782893B (en) * | 2017-01-18 | 2018-08-17 | 重庆鸽牌电线电缆有限公司 | A kind of manufacturing method of high-performance high life electric wire |
| 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 |
| CN110951201A (en) * | 2019-11-22 | 2020-04-03 | 上海至正道化高分子材料股份有限公司 | Anti-shrinkage intelligent building cloth wire silane halogen-free flame-retardant insulated cable material |
| CN111117137B (en) * | 2019-12-27 | 2022-10-28 | 上海至正新材料有限公司 | Preparation method of anti-shrinkage silane cross-linked low-smoke halogen-free flame-retardant insulating material for intelligent building cloth wires |
| CN112778607B (en) * | 2020-12-31 | 2022-06-24 | 浙江万马高分子材料集团有限公司 | Tracking-resistant cable material and preparation method thereof |
| CN114213743A (en) * | 2022-01-05 | 2022-03-22 | 四川安费尔高分子材料科技有限公司 | Production process of low-smoke halogen-free flame-retardant cable material |
| CN115926299A (en) * | 2022-10-31 | 2023-04-07 | 上海凯波电缆特材股份有限公司 | Silane crosslinking halogen-free flame-retardant polyolefin material for photovoltaic cable and preparation method thereof |
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| CN102532664A (en) * | 2011-12-31 | 2012-07-04 | 上海至正道化高分子材料有限公司 | Silane cross-linked polyethylene insulating material and production method thereof |
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