CN103113704A - Preparation method of high temperature (110 DEG C) resistant silane naturally-crosslinked polyethylene cable material - Google Patents
Preparation method of high temperature (110 DEG C) resistant silane naturally-crosslinked polyethylene cable material Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92609—Dimensions
- B29C2948/92647—Thickness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/9298—Start-up, shut-down or parameter setting phase; Emergency shut-down; Material change; Test or laboratory equipment or studies
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Abstract
The invention relates to a preparation method of a high temperature (110 DEG C) resistant silane naturally-crosslinked polyethylene cable material, belonging to the technical field of preparation of an insulating high polymer material for wires and cables. The preparation method comprises the following steps: preparing a grafted component A; preparing a catalytic component B; and evenly mixing the grafted component A and the catalytic component B according to a weight ratio of (80-95):(5-20), extruding into sheets through a flow type sheet-producing instrument, controlling the thickness of the sheets, and naturally crosslinking to obtain the high temperature (110 DEG C) resistant silane naturally-crosslinked polyethylene cable material. The invention has the following advantages: the silane grafted content of the product is higher, the crosslinking speed under natural conditions is higher, the aging resistance is better, and the application range can be widened; and the process steps are short, and the process conditions are not severe.
Description
Technical field
The invention belongs to the insulating polymer material preparation technical field that electric wire is used, be specifically related to a kind of preparation method of silane natural-crosslinked polyethylene CABLE MATERIALS of anti-110 ℃ of high temperature.
Background technology
Polyethylene has the advantages such as good insulativity, workability, lower temperature resistance and resistance to deterioration, is a kind of very excellent insulating material.But exist equally that temperature resistant grade is low, creep-resistant property is poor, stress cracking resistance is poor and the shortcoming such as chemical resistance is poor.Polyethylene is after crosslinked, and its molecular structure becomes tridimensional network from two-dirnentional structure, and its electrical property, thermotolerance, chemical resistant properties and physical strength etc. all can be improved significantly, have widened its range of application.
Poly crosslinking method mainly contains three kinds, at first be that peroxide crosslinking is (as patent documentation CN1325540C and CN102093580C, etc.), peroxide crosslinking has comparatively widely in low pressure, medium and high voltage cable field to be used, especially in the mesohigh field, also do not have at present other method to substitute, but the method facility investment is too high, technology controlling and process is very complicated, need special vulcanizing equipment, while extrusion equipment and vulcanizing equipment take up room too large, and equipment cost is too high when producing low-voltage cable; Next is that cross-linking radiation is (as patent documentation CN1082699C, CN101724191A and CN101812208A, etc.), the irradiation technique technology controlling and process is comparatively simple, the product cleanliness factor is high, but need special irradiation apparatus, cost drops into higher, also exists in process of production degree of crosslinking simultaneously wayward, the problems such as radiation pollution, its application has certain limitation; The 3rd, crosslinked with silicane (as CN101585214A), the crosslinked with silicane technology is mainly to introduce crosslinkable groups by grafting or Copolysilane on the sub polyethylene subchain, then completes crosslinked under the effect of moisture and catalyzer.The method is few because of facility investment, and common forcing machine can be completed the production of cable, does not need special cross-linking apparatus, and simultaneously technology controlling and process is simple, is most widely used in the low-voltage cable field, is still now the focus of research.
Traditional organosilane cross-linked poly-ethylene cable material need to carry out crosslinkedly in 90 ℃ of water-baths or vaporium after cable cabling, crosslinking time is unusual according to insulation thickness from several hours to tens hours.Because crosslinking time is long, be easy to cause the copper conductor phenomenons such as oxidation blackout, insulation layer decreasing insulating of making moist because being heated, bring certain potential safety hazard for the life-time service of cable.At present domestic and international Patents (as CN101148522A) has been reported the preparation method of silane room temperature quickly cross-linked polyethylene cable material, report claims that just can complete crosslinked under field conditions (factors) by a couple of days after cable cabling for this material, need not high cooking, solved the existing defective of warm water crosslinking method (as CN102746548A).But by discovery that the silane room temperature quickly cross-linked polyethylene cable material of well-known producer of domestic and international several families and relevant cables producer are investigated, though this kind crosslinking time in steam ambient shortens to some extent, under natural condition, cross-linking effect is still undesirable.
Polyethylene is after crosslinked with silicane, and the temperature classification of material can be increased to 90 ℃ from 70 ℃, and resistance toheat has obtained certain raising.But at present in a lot of occasions because the operational throughput of unit cross section conductor current is large, thermal value is high, conductor long term operation temperature can reach 110 ℃, and is even higher.Australia cable manufacturer just explicitly calls for silanes cross-linked polyethylene insulated cable can reach 110 ℃ of long-term safety use temperatures, insulation layer must be aging by 150 ℃ * 168h, this just has higher requirement to the temperature classification of insulating material, and common silane cross-linked polyethylene insulating material makes it be subject to certain restriction in the application that the conductor working temperature is under the higher strip part just because of the defective on temperature classification.
Summary of the invention
Task of the present invention is to provide a kind of preparation method of silane natural-crosslinked polyethylene CABLE MATERIALS of anti-110 ℃ of high temperature, the CABLE MATERIALS that is obtained by the method helps to significantly improve temperature classification and uses and embody excellent ageing-resistant effect to satisfy conductor job requirement under long term high temperature, and method has the strong point that technique is terse, processing requirement is not harsh in addition.
Task of the present invention is completed like this, and a kind of preparation method of silane natural-crosslinked polyethylene CABLE MATERIALS of anti-110 ℃ of high temperature comprises the following steps:
A) the A material component of preparation grafting, it is dry that 100 parts of polyethylene compound resins that at first will take by weight are placed in the molecule plug, and control drying temperature and time of drying, obtain dry polyvinyl resin, the initiator 0.1-0.4 part that will take by weight again, dissolving and mixing in silane coupling agent 1.5-4 part that anti-precrosslinker 0.1-0.5 part and first oxidation inhibitor 0.2-0.6 part inputs take by weight, obtain the silane recombiner, then the polyvinyl resin of drying and silane recombiner are dropped in high-speed mixer and mix, and control the rotating speed of high-speed mixer and control mixing time, obtain compound, then compound is dropped in twin screw extruder and melt extrude, and control the temperature in head temperature He Yi district to eight district of twin screw extruder, after twin screw extruder is extruded successively through water cooling, pelletizing also dries the rear drying in molecular sieve of introducing, packing, obtain the A material component of grafting,
B) the B material component of preparation catalysis, 100 parts of polyvinyl resins, organic sulfonic acid catalyzer 1-3 part, organic bismuth catalyst 1-3 part, second oxidation inhibitor 0.5-2 part, anti copper agent 0.5-2 part and lubricant 1-4 part of taking are by weight dropped in high-speed mixer mix, and control rotating speed and the mixing time of high-speed mixer, obtain compound, compound is placed in twin screw extruder to be melt extruded, and control the extrusion temperature of twin screw extruder, extrude by tie rod pelletizing and drying, obtain the B material component of catalysis;
C) natural-crosslinked, will be by steps A) the A material component of the grafting that obtains with by step B) the B material component of the catalysis that obtains is by weight 80-95: 5-20 mixes, and drop into and squeeze sheet in the flow instrument, control the thickness of slice, thin piece, through natural-crosslinked, obtain the silane natural-crosslinked polyethylene CABLE MATERIALS of anti-110 ℃ of high temperature.
In a specific embodiment of the present invention, steps A) the polyethylene compound resin described in is two kinds or above combination of metallocene linear-low density polyethylene, bimodal medium density polyethylene, Low Density Polyethylene.
In another specific embodiment of the present invention, steps A) silane coupling agent described in is one or more combination of vinyltrimethoxy silane, vinyltriethoxysilane, vinyl trimethoxysilane oligomer, vinyl three (2-methoxyethoxy) silane.
In another specific embodiment of the present invention, steps A) initiator described in is one or more the combination in dicumyl peroxide, the benzoyl peroxide tert-butyl ester, dibenzoyl peroxide;
In another specific embodiment of the present invention, steps A) the anti-precrosslinker described in is one or more the combination in polycarbodiimide, ethylene glycol diglycidylether, polyvinyl alcohol; Described the first oxidation inhibitor is that two (3,5-di-tert-butyl-phenyl) pentaerythritol diphosphites and methacrylic acid (1,2,2,6,6-pentamethyl-piperidine alcohols) ester are the mixture that mutually mixes at 2: 1 by weight; Step B) the second oxidation inhibitor described in is two stearyl alcohol pentaerythritol diphosphites and/or 1,3,5-three (the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) 1,3,5-triazines-2,4,6-(1H, 3H, 5H)-triketone.
Also have a specific embodiment of the present invention, steps A) described in control drying temperature and time of drying be with drying temperature and be controlled to be respectively 65-75 ℃ and 100-130min time of drying; The rotating speed of described control high-speed mixer and control mixing time are that rotating speed is controlled to be 380-420r/min, and mixing time is controlled to be 4-6min; The temperature in head temperature He Yi district to eight district of described control twin screw extruder is that head temperature is controlled to be 195-205 ℃, the temperature in Jiang Yi district to eight district is controlled to be respectively: a district 105-115 ℃, two district 150-160 ℃, three district 170-180 ℃, four district 180-190 ℃, five district 185-195 ℃, six district 185-195 ℃, seven district 190-200 ℃, eight district 185-195 ℃; Dry drying temperature and be respectively 65-75 ℃ and 60-80min time of drying in described introducing molecular sieve.
More of the present invention and in specific embodiment, step B) the organic sulfonic acid catalyzer described in is tetrapropyl naphthene sulfonic acid and/or Witco 1298 Soft Acid; Described organic bismuth catalyst is three (2-p-methoxy-phenyl) bismuth and/or three (oxyethyl group) phenyl bismuths; Described anti copper agent is N, two [β (3,5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine and/or the N-salicylamide base phthalimides of N-; Described lubricant is one or more the combination in silicone oil, silicone powder, PPA rheological agent, amine hydroxybenzene, stearic amide and polyethylene wax.
Rotating speed and the mixing time of the control high-speed mixer in of the present invention and then specific embodiment, step B) are that rotating speed is controlled to be 350-400r/min, and mixing time is controlled to be 4-6min; The extrusion temperature of described control twin screw extruder is that the temperature in Jiang Yi district to five district is controlled to be respectively: a district 105-115 ℃, two district 135-145 ℃, three district 165-175 ℃, four district 175-185 ℃ He Wu district 180-190 ℃, head temperature is 185-195 ℃, the temperature of described drying is 65-75 ℃, and be 110-130min time of drying.
The thickness of the control slice, thin piece of the present invention again more and in specific embodiment, step C) is that the gauge control with slice, thin piece is 0.8-1.2 ㎜, and the described natural-crosslinked time is 2-3 days.
The advantage of technical scheme provided by the invention: due to the organic sulfonic acid that has adopted polyethylene compound resin, Effective Anti oxygen system and high molecular and organic bismuth catalyst synergistic catalyst system, make the Silane Grafted content of product higher, rate of crosslinking is faster under natural condition, ageing resistance is more excellent, can be aging by 150 ℃ * 168h, the insulating layer of conductor temperature classification can reach 110 ℃, and common organosilane crosslinked polyethylene can only be aging by 135 ℃ * 168h, the insulating layer of conductor temperature classification is only 90 ℃, thereby but the broaden application scope; Processing step is brief, processing condition are not harsh.
Embodiment
Embodiment 1:
A) the A material component of preparation grafting, 50 parts of the metallocene linear-low density polyethylenes that at first will take by weight, 30 parts of 20 parts of bimodal medium density polyethylenes and Low Density Polyethylenes jointly are placed in molecule plug dry 100min under 75 ℃, obtain dry polyvinyl resin, the initiator that will take by weight again is 0.3 part of dicumyl peroxide, anti-precrosslinker is that 0.45 part of polycarbodiimide and the first oxidation inhibitor are two (3, the 5-di-tert-butyl-phenyl) pentaerythritol diphosphites and methacrylic acid (1, 2, 2, 6, 6-pentamethyl-piperidine alcohols) ester is that the silane coupling agent that 0.3 part of input of mixture of mutually mixing at 2: 1 takes by weight is to dissolve and mixing in 2 parts of vinyltriethoxysilanes by weight, obtain the silane recombiner, then the polyvinyl resin of described drying and silane recombiner are dropped in high-speed mixer and mix, the rotating speed of high-speed mixer is controlled to be 400r/min, mixing time is 5min, obtain compound, then compound is dropped in twin screw extruder and melt extrude, the temperature in one district to eight district of twin screw extruder is respectively: 110 ℃, a district, two 155 ℃, districts, three 175 ℃, districts, four 185 ℃, districts, five 190 ℃, districts, six 190 ℃, districts, seven 190 ℃, He Ba district, 195 ℃, districts, the head temperature of twin screw extruder is 200 ℃, after twin screw extruder is extruded successively through water cooling, introduce 70 ℃ of dry 70min in molecular sieve after pelletizing and drying, packing, obtain the A material component of grafting,
B) the B material component of preparation catalysis, with 100 parts of the ldpe resins that take by weight, the organic sulfonic acid catalyzer is 1.5 parts of tetrapropyl naphthene sulfonic acid, organic bismuth catalyst is 1.8 parts of three (2-p-methoxy-phenyl) bismuths, 0.8 part of the namely two stearyl alcohol pentaerythritol diphosphites of the second oxidation inhibitor, anti copper agent is N, N-is two, and [β (3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] 1 part of hydrazine and lubricant be to mix in 2 parts of input high-speed mixers of silicone oil, the rotating speed of high-speed mixer is controlled to be 380r/min, mixing time is 5min, obtain compound, compound is placed in twin screw extruder to be melt extruded, the temperature in one district to five district of twin screw extruder is respectively: 110 ℃, a district, two 140 ℃, districts, three 170 ℃, districts, four 185 ℃, He Wu district, 180 ℃, districts, the head temperature of twin screw extruder is 190 ℃, extrude by tie rod, pelletizing and drying, drying temperature is 70 ℃, be 120min time of drying, obtain the B material component of catalysis,
C) natural-crosslinked, will be by steps A) the A material component of the grafting that obtains with by step B) the B material component of the catalysis that obtains mixed by weight 95: 5, and drop into and squeeze sheet (the present embodiment adopts single screw extrusion machine to extrude) in the flow instrument, the thickness of the slice, thin piece of extruding is 1 ㎜, natural-crosslinked through 2 days, obtain the silane natural-crosslinked polyethylene CABLE MATERIALS of anti-110 ℃ of high temperature.
Embodiment 2:
A) the A material component of preparation grafting, 30 parts of 70 parts of metallocene linear-low density polyethylenes that at first will take by weight and bimodal medium density polyethylenes are placed in molecule plug dry 130min under 65 ℃, obtain dry polyvinyl resin, the initiator that will take by weight again is 0.1 part of the benzoyl peroxide tert-butyl ester, 0.3 part of dibenzoyl peroxide, anti-precrosslinker is 0.05 part of ethylene glycol diglycidylether, 0.05 part of polyvinyl alcohol and the first oxidation inhibitor are two (3, the 5-di-tert-butyl-phenyl) pentaerythritol diphosphites and methacrylic acid (1, 2, 2, 6, 6-pentamethyl-piperidine alcohols) ester is that the silane coupling agent that 0.6 part of input of mixture of mutually mixing at 2: 1 takes by weight is 1 part of vinyltrimethoxy silane by weight, dissolve in 2 parts, 1 part of vinyl trimethoxysilane oligomer and vinyl three (2-methoxyethoxy) silane and mix, obtain the silane recombiner, then the polyvinyl resin of described drying and silane recombiner are dropped in high-speed mixer and mix, the rotating speed of high-speed mixer is 380r/min, mixing time is 6min, obtain compound, then compound is dropped in twin screw extruder and melt extrude, the temperature in one district to eight district of twin screw extruder is respectively: 115 ℃, a district, two 150 ℃, districts, three 180 ℃, districts, four 185 ℃, districts, five 185 ℃, districts, six 195 ℃, districts, seven 185 ℃, He Ba district, 200 ℃, districts, the head temperature of twin screw extruder is 205 ℃, after twin screw extruder is extruded successively through water cooling, introduce 75 ℃ of dry 60min in molecular sieve after pelletizing and drying, packing, obtain the A material component of grafting,
B) the B material component of preparation catalysis, with 100 parts of the ldpe resins that take by weight, the organic sulfonic acid catalyzer is 2 parts of 1 part of tetrapropyl naphthene sulfonic acid and Witco 1298 Soft Acids, organic bismuth catalyst i.e. 1 part of 2 parts of three (2-p-methoxy-phenyl) bismuths and three (oxyethyl group) phenyl bismuth, the second oxidation inhibitor is 1 part of two stearyl alcohol pentaerythritol diphosphites and 1, 3, 5-three (the 4-tertiary butyl-3-hydroxyl-2, the 6-dimethyl benzyl) 1, 3, 5-triazine-2, 4, 6-(1H, 3H, 5H)-1 part of triketone, anti copper agent is N, N-is two, and [β (3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] 0.25 part of 0.25 part of hydrazine and N-salicylamide base phthalimide and lubricant be 2 parts of amine hydroxybenzenes, mix in 1 part of input high-speed mixer of 1 part of stearic amide and polyethylene wax, the rotating speed of high-speed mixer is 400r/min, mixing time is 4min, obtain compound, compound is dropped in twin screw extruder melt extrude, the temperature in one district to five district of twin screw extruder is respectively: 105 ℃, a district, two 135 ℃, districts, three 175 ℃, districts, four 190 ℃, He Wu district, 175 ℃, districts, the head temperature of twin screw extruder is 195 ℃, extrude by tie rod, pelletizing, and through 65 ℃ of dry 130min, obtain the B material component of catalysis,
C) natural-crosslinked, will be by steps A) the A material component of the grafting that obtains with by step B) the B material component of the catalysis that obtains mixed by weight 90: 10, and extrude in the input single screw extrusion machine, the thickness of the slice, thin piece of extruding is 0.8 ㎜, natural-crosslinked through 3 days, obtain the silane natural-crosslinked polyethylene CABLE MATERIALS of anti-110 ℃ of high temperature.
Embodiment 3:
A) the A material component of preparation grafting, 50 parts of the Low Density Polyethylenes that at first will take by weight, 50 parts of bimodal medium density polyethylenes are placed in molecule plug dry 115min under 70 ℃, obtain dry polyvinyl resin, the initiator that will take by weight again is 0.1 part of dibenzoyl peroxide, anti-precrosslinker is that 0.5 part of polyvinyl alcohol and the first oxidation inhibitor are two (3, the 5-di-tert-butyl-phenyl) pentaerythritol diphosphites and methacrylic acid (1, 2, 2, 6, 6-pentamethyl-piperidine alcohols) ester is that the silane coupling agent that 0.46 part of input of mixture of mutually mixing at 2: 1 takes by weight is to dissolve in 1.5 parts of vinyl trimethoxysilane oligomers to mix by weight, obtain the silane recombiner, then the polyvinyl resin of described drying and silane recombiner are dropped in high-speed mixer and mix, the rotating speed of high-speed mixer is 420r/min, mixing time is 5min, obtain compound, then compound is dropped in twin screw extruder and melt extrude, the temperature in one district to eight district of twin screw extruder is respectively: 105 ℃, a district, two 160 ℃, districts, three 170 ℃, districts, four 180 ℃, districts, five 195 ℃, districts, six 195 ℃, districts, seven 195 ℃, He Ba district, 195 ℃, districts, the head temperature of twin screw extruder is 195 ℃, after twin screw extruder is extruded successively through water cooling, introduce 65 ℃ of dry 80min in molecular sieve after pelletizing and drying, packing, obtain the A material component of grafting,
B) the B material component of preparation catalysis, with 100 parts of the ldpe resins that take by weight, the organic sulfonic acid catalyzer is 1 part of Witco 1298 Soft Acid, organic bismuth catalyst is 1 part of three (2-p-methoxy-phenyl) bismuth, the second oxidation inhibitor is 1, 3, 5-three (the 4-tertiary butyl-3-hydroxyl-2, the 6-dimethyl benzyl) 1, 3, 5-triazine-2, 4, 6-(1H, 3H, 5H)-0.5 part of triketone, anti copper agent is that 2 parts of N-salicylamide base phthalimides and lubricant are to mix in 1 part of input high-speed mixer of polyethylene wax, the rotating speed of high-speed mixer is 350r/min, mixing time is 6min, obtain compound, compound is dropped in twin screw extruder melt extrude, the temperature in one district to five district of twin screw extruder is respectively: 115 ℃, a district, two 145 ℃, districts, three 165 ℃, districts, four 185 ℃, He Wu district, 185 ℃, districts, the head temperature of twin screw extruder is 185 ℃, extrude by tie rod, pelletizing, and through 75 ℃ of dry 110min, obtain the B material component of catalysis,
C) natural-crosslinked, will be by steps A) the A material component of the grafting that obtains with by step B) the B material component of the catalysis that obtains mixed by weight 80: 20, and extrude in the input single screw extrusion machine, the thickness of the slice, thin piece of extruding is 1.2 ㎜, natural-crosslinked through 2.5 days, obtain the silane natural-crosslinked polyethylene CABLE MATERIALS of anti-110 ℃ of high temperature.
Comparative example:
Only with steps A) in polyvinyl resin use the hybrid resin that parts by weight are the Low Density Polyethylene (DJ210) of the Low Density Polyethylene (2102NT26) of 50 parts and 50 parts instead, use silane coupling agent instead vinyltrimethoxy silane 2.5 parts, the first oxidation inhibitor uses 4,4 instead
,0.3 part of-thiobis (the 6-tertiary butyl-3-cresols), initiator is 0.3 part of dicumyl peroxide, anti-precrosslinker is 0.4 part of polycarbodiimide; Step B) polyvinyl resin in is with step A), using sulfonic acid catalyst and bismuth catalyst instead tin catalyst is 2 parts of dibutyl tin laurates, use anti copper agent instead N, N-is two, and [β (3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] 1.2 parts of hydrazines, the second oxidation inhibitor is 1 part of β (3,5-di-t-butyl-4-hydroxyl) propionic acid pentaerythritol ester, lubricant is 3 parts of silicone oil, and all the other are all with the description to embodiment 1.
150 ℃ * 168h of the heat aging performance reference standard AS/NZS 5000.1:2005 of the silane natural-crosslinked polyethylene CABLE MATERIALS of the anti-110 ℃ of high temperature that obtained by above-described embodiment 1 to 3 and comparative example, all the other test requests are with reference to testing standard JB/T10437, and test result is by shown in following table:
As can be seen from the above table, embodiment 1 to embodiment 3 is that comparative example is common silane cross-linked polyethylene insulating material by the resulting organosilane crosslinked polyethylene insulation material of preparation method of the present invention.Adopt single Screw Extrusion trier dummycable to extrude unit and extrude the test piece that thickness is the 0.8-1.2mm left and right, after test piece is natural-crosslinked through 2-3 days, reference standard JB/T10437, AS/NZS 5000.1:2005 carry out performance test to sample, can find out, embodiment and comparative example can be by physicals and the aging resistance of JB/T10437 industry standard defined.Comparative example and comparative example, can obviously find out, the aging resistance of embodiment will be significantly better than comparative example, under 150 ℃ * 168h of thermal ageing condition severe condition, embodiment still can keep less velocity of variation, and comparative example is excessive due to the elongation at break velocity of variation, can't reach the aging necessary requirement of AS/NZS 5000.1:2005.Simultaneously, can find out specific heat extension and degree of crosslinking, the heat of embodiment is extended index will be significantly less than comparative example, and the degree of crosslinking that embodiment is corresponding obviously will be higher than comparative example, and this illustrates that also rate of crosslinking and the crosslinking degree of embodiment all are better than comparative example under field conditions (factors).
In concrete production process, can select suitable formula according to production unit and performance requirement.The present invention is mainly when retention reaches industry standard, overcome the heat-resisting defective of the crosslinked material of conventional silanes in hot environment, by selecting various molecular weights distribution polyvinyl resin wide, that the degree of branching is higher, processing fluidity is good to carry out compound, improve the Silane Grafted content of resin, guarantee that polyethylene reaches higher crosslinking degree, and then improve its thermotolerance; By selecting efficient oxidation inhibitor, when preventing that the excessive C-C of polyethylene molecule is crosslinked, guaranteeing the graft reaction high efficiency, suppress too fast aging under hot conditions of material; By adopting high molecular organic sulfonic acid and organo-bismuth synergistic catalyzer, further improved rate of crosslinking and the cross-linking density of material.
Claims (9)
1. the preparation method of the silane natural-crosslinked polyethylene CABLE MATERIALS of anti-110 ℃ of high temperature is characterized in that comprising the following steps:
A) the A material component of preparation grafting, it is dry that 100 parts of polyethylene compound resins that at first will take by weight are placed in the molecule plug, and control drying temperature and time of drying, obtain dry polyvinyl resin, the initiator 0.1-0.4 part that will take by weight again, dissolving and mixing in silane coupling agent 1.5-4 part that anti-precrosslinker 0.1-0.5 part and first oxidation inhibitor 0.2-0.6 part inputs take by weight, obtain the silane recombiner, then the polyvinyl resin of drying and silane recombiner are dropped in high-speed mixer and mix, and control the rotating speed of high-speed mixer and control mixing time, obtain compound, then compound is dropped in twin screw extruder and melt extrude, and control the temperature in head temperature He Yi district to eight district of twin screw extruder, after twin screw extruder is extruded successively through water cooling, pelletizing also dries the rear drying in molecular sieve of introducing, packing, obtain the A material component of grafting,
B) the B material component of preparation catalysis, 100 parts of polyvinyl resins, organic sulfonic acid catalyzer 1-3 part, organic bismuth catalyst 1-3 part, second oxidation inhibitor 0.5-2 part, anti copper agent 0.5-2 part and lubricant 1-4 part of taking are by weight dropped in high-speed mixer mix, and control rotating speed and the mixing time of high-speed mixer, obtain compound, compound is placed in twin screw extruder to be melt extruded, and control the extrusion temperature of twin screw extruder, extrude by tie rod pelletizing and drying, obtain the B material component of catalysis;
C) natural-crosslinked, will be by steps A) the A material component of the grafting that obtains with by step B) the B material component of the catalysis that obtains is by weight 80-95: 5-20 mixes, and drop into and squeeze sheet in the flow instrument, control the thickness of slice, thin piece, through natural-crosslinked, obtain the silane natural-crosslinked polyethylene CABLE MATERIALS of anti-110 ℃ of high temperature.
2. the preparation method of the silane natural-crosslinked polyethylene CABLE MATERIALS of anti-110 ℃ of high temperature according to claim 1, is characterized in that steps A) described in the polyethylene compound resin be two kinds or above combination of metallocene linear-low density polyethylene, bimodal medium density polyethylene, Low Density Polyethylene.
3. the preparation method of the silane natural-crosslinked polyethylene CABLE MATERIALS of anti-110 ℃ of high temperature according to claim 1, is characterized in that steps A) described in silane coupling agent be one or more combination of vinyltrimethoxy silane, vinyltriethoxysilane, vinyl trimethoxysilane oligomer, vinyl three (2-methoxyethoxy) silane.
4. the preparation method of the silane natural-crosslinked polyethylene CABLE MATERIALS of anti-110 ℃ of high temperature according to claim 1, is characterized in that steps A) described in initiator be one or more combination in dicumyl peroxide, the benzoyl peroxide tert-butyl ester, dibenzoyl peroxide.
5. the preparation method of the silane natural-crosslinked polyethylene CABLE MATERIALS of anti-110 ℃ of high temperature according to claim 1, is characterized in that steps A) described in anti-precrosslinker be one or more combination in polycarbodiimide, ethylene glycol diglycidylether, polyvinyl alcohol; Described the first oxidation inhibitor is that two (3,5-di-tert-butyl-phenyl) pentaerythritol diphosphites and methacrylic acid (1,2,2,6,6-pentamethyl-piperidine alcohols) ester are the mixture that mutually mixes at 2: 1 by weight; Step B) the second oxidation inhibitor described in is two stearyl alcohol pentaerythritol diphosphites and/or 1,3,5-three (the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzyl) 1,3,5-triazines-2,4,6-(1H, 3H, 5H)-triketone.
6. the preparation method of the silane natural-crosslinked polyethylene CABLE MATERIALS of anti-110 ℃ of high temperature according to claim 1, is characterized in that steps A) described in control drying temperature and time of drying be with drying temperature and be controlled to be respectively 65-75 ℃ and 100-130min time of drying; The rotating speed of described control high-speed mixer and control mixing time are that rotating speed is controlled to be 380-420r/min, and mixing time is controlled to be 4-6min; The temperature in head temperature He Yi district to eight district of described control twin screw extruder is that head temperature is controlled to be 195-205 ℃, the temperature in Jiang Yi district to eight district is controlled to be respectively: a district 105-115 ℃, two district 150-160 ℃, three district 170-180 ℃, four district 180-190 ℃, five district 185-195 ℃, six district 185-195 ℃, seven district 190-200 ℃, eight district 185-195 ℃; Dry drying temperature and be respectively 65-75 ℃ and 60-80min time of drying in described introducing molecular sieve.
7. the preparation method of the silane natural-crosslinked polyethylene CABLE MATERIALS of anti-110 ℃ of high temperature according to claim 1, is characterized in that step B) described in the organic sulfonic acid catalyzer be tetrapropyl naphthene sulfonic acid and/or Witco 1298 Soft Acid; Described organic bismuth catalyst is three (2-p-methoxy-phenyl) bismuth and/or three (oxyethyl group) phenyl bismuths; Described anti copper agent is N, two [β (3,5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine and/or the N-salicylamide base phthalimides of N-; Described lubricant is one or more the combination in silicone oil, silicone powder, PPA rheological agent, amine hydroxybenzene, stearic amide and polyethylene wax.
8. the preparation method of the silane natural-crosslinked polyethylene CABLE MATERIALS of anti-110 ℃ of high temperature according to claim 1, it is characterized in that step B) described in rotating speed and the mixing time of control high-speed mixer be that rotating speed is controlled to be 350-400r/min, mixing time is controlled to be 4-6min; The extrusion temperature of described control twin screw extruder is that the temperature in Jiang Yi district to five district is controlled to be respectively: a district 105-115 ℃, two district 135-145 ℃, three district 165-175 ℃, four district 175-185 ℃ He Wu district 180-190 ℃, head temperature is 185-195 ℃, the temperature of described drying is 65-75 ℃, and be 110-130min time of drying.
9. the preparation method of the silane natural-crosslinked polyethylene CABLE MATERIALS of anti-110 ℃ of high temperature according to claim 1, it is characterized in that step C) described in the thickness of control slice, thin piece be that gauge control with slice, thin piece is 0.8-1.2 ㎜, the described natural-crosslinked time is 2-3 days.
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| CN105295184A (en) * | 2015-05-14 | 2016-02-03 | 欧宝聚合物江苏有限公司 | High-abrasion-resistant cross-linked low smoke zero halogen cable material processed under irradiation of 125 DEG C and preparation method |
| CN106220988A (en) * | 2016-08-23 | 2016-12-14 | 江苏鑫丰塑业有限公司 | A kind of improvement warm water crosslinking black insulated aerial cable material |
| CN109749215A (en) * | 2018-12-17 | 2019-05-14 | 上海新上化高分子材料有限公司 | Anti- precrosslink two-step method silane natural-crosslinked polyethylene Insulation Material and preparation method thereof |
| CN112375284A (en) * | 2020-11-16 | 2021-02-19 | 苏州亨利通信材料有限公司 | Cross-linked polyethylene insulating material for large and small wires universal at 3KV and below and preparation method thereof |
| CN116751417A (en) * | 2023-06-19 | 2023-09-15 | 杭州科佳新材料股份有限公司 | Silane crosslinked polyethylene material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105295184A (en) * | 2015-05-14 | 2016-02-03 | 欧宝聚合物江苏有限公司 | High-abrasion-resistant cross-linked low smoke zero halogen cable material processed under irradiation of 125 DEG C and preparation method |
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| CN112375284A (en) * | 2020-11-16 | 2021-02-19 | 苏州亨利通信材料有限公司 | Cross-linked polyethylene insulating material for large and small wires universal at 3KV and below and preparation method thereof |
| CN116751417A (en) * | 2023-06-19 | 2023-09-15 | 杭州科佳新材料股份有限公司 | Silane crosslinked polyethylene material and preparation method thereof |
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