CN102219978A - Halogen-free flame retardant polyolefin elastomer composition used for cover material of wires and cables - Google Patents
Halogen-free flame retardant polyolefin elastomer composition used for cover material of wires and cables Download PDFInfo
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Abstract
The present invention relates to the technical field of cover materials of wires and cables, particularly to a halogen-free flame retardant polyolefin elastomer composition used for covering material of wires and cables. The raw materials comprise the following components by weight: 100 parts of styrene-butadiene polymer, 80 to 150 parts of polyene resin, 75 to 150 parts of softener, 60 to 140 parts of polyphenylene oxide resin, 100 to 200 parts of intumescent system fire retardant, 0 to 30 parts of organic phosphate fire retardant, 0 to 30 parts of grafted polyolefin and 0 to 40 parts of other additives. The invention has the advantages of good physical properties, flame retardation performance, heat-resisting deformation performance and soft performance, and is easy to process.
Description
Technical field
The present invention relates to the electric wire and cable covering materials technical field, particularly relate to a kind of electric wire and cable covering materials halogen-free anti-flaming polyolefin elastic composition.
Background technology
As everyone knows, electric wire has been widely used in the transmission of all kinds of power supplys and signal.Along with the demand rapid growth of global electric wire in recent years, electric wire burning and the fire failure that causes becomes an important social issue day by day.Abroad the fire retardant mechanism of electric wire is studied since nineteen sixties.The flame retardant cable of initial exploitation all is halogenous flame-retardant electric wire and cable, because polyvinyl chloride (PVC) has necessary mechanical strength, excellent flexible, cheap relatively price and sophisticated complete processing, be to be widely used in the insulation of making all kinds of electric wires and outward by material.
Contain halogen in the polyvinyl chloride resin structure, when by burning process PVC scrap electrical wires cable being handled, PVC scrap electrical wires cable can discharge obnoxious flavoures such as a large amount of cigarettes and hydrogenchloride, has caused serious " secondary pollution "; Secondly, the processing fluidity of polyvinyl chloride resin and heat-resistant stability can be relatively poor, need adding in the prescription of preparation PVC contains non-environment-friendly type interpolation such as the stablizer of heavy metals such as lead, cadmium, barium, the plasticizer that contains phthalate and some halogen flames composition and carries out modification, and this is unfavorable for developing the environment-friendly type electric wire and cable covering materials.Begin to limit PVC in succession in the use of making electric wire and cable covering materials in RoHS instruction and Reach rules etc. at present.
Simultaneously, enhancing along with people's environmental consciousness, macromolecular material and Non-halogen Flame Retardant Technology that the appearance in succession of relevant environmental regulation both at home and abroad, Halogen poison, low cigarette, burning do not discharge corrosive gases are just substituting the Halogen flame-retarded technology, become the dominant direction of the fire-retardant research and development of polymer materials.
At present existing many manufacturers and associated mechanisms are in development or developed the halogen-free flame-retardant cable material, but mostly are by fill a large amount of inorganic combustion inhibitor Mg (OH) in polymkeric substance
2With AL (OH)
3Prepare the halogen-free flame-retardant cable material, can cause the deterioration of composite materials property because of the existence of a large amount of mineral fillers.In order to reduce the content of inorganic combustion inhibitor, guarantee the high flame retardant properties of matrix material simultaneously again, adopt organic fire-retardant and inorganic combustion inhibitor to add in the base-material simultaneously usually.The patent No. is that the Chinese invention patent of ZL00122157.4 discloses " a kind of halogen-free flame-retardant cable preparation methods ", it is base-material with the polyolefine, and in expansible black lead and red phosphorus or the zinc borate one or both are made up co-production halogen-free flame-retardant cable material.Wherein, expansible black lead is an organic fire-retardant, and red phosphorus or zinc borate are inorganic combustion inhibitor, still, when expansible black lead and red phosphorus or zinc borate add in the base-material as fire retardant simultaneously, can influence physicals, heat-resistant deforming performance, softness of the halogen-free flame-retardant cable material that is prepared into etc.And in the above-mentioned patent, because its base-material polyolefine all is thermo-labile and polyolefin resin non-refractory, so can not test (heat-resistant deforming 150 degree, 2000 restrain) by UL758, shortcoming such as having pliability can not adjust, and feel is good inadequately, not wear-resisting.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, and a kind of electric wire and cable covering materials halogen-free anti-flaming polyolefin elastic composition is provided, it has good physicals, flame retardant properties, heat-resistant deforming performance, softness, and processing easily.
The present invention is achieved through the following technical solutions.
A kind of electric wire and cable covering materials halogen-free anti-flaming polyolefin elastic composition, its raw material and weight part are as follows:
100 parts of styrene butadiene base polymers
80 parts ~ 150 parts of polyolefin resines
75 parts ~ 150 parts of tenderizers
60 parts ~ 140 parts of polyphenylene oxide resins
100 parts ~ 200 parts of expanded polystyrene veneer system fire retardants
0 part ~ 30 parts of organophosphorous ester fire retardants
0 part ~ 30 parts of graft polyolefins
0 part ~ 40 parts of other additives.
Preferably, a kind of electric wire and cable covering materials halogen-free anti-flaming polyolefin elastic composition, its raw material and weight part are as follows:
100 parts of styrene butadiene base polymers
80 parts ~ 115 parts of polyolefin resines
75 parts ~ 105 parts of tenderizers
60 parts ~ 100 parts of polyphenylene oxide resins
100 parts ~ 150 parts of expanded polystyrene veneer system fire retardants
0 part ~ 15 parts of organophosphorous ester fire retardants
0 part ~ 15 parts of graft polyolefins
0 part ~ 20 parts of other additives.
Preferably, a kind of electric wire and cable covering materials halogen-free anti-flaming polyolefin elastic composition, its raw material and weight part are as follows:
100 parts of styrene butadiene base polymers
115 parts ~ 150 parts of polyolefin resines
105 parts ~ 150 parts of tenderizers
100 parts ~ 140 parts of polyphenylene oxide resins
150 parts ~ 200 parts of expanded polystyrene veneer system fire retardants
15 parts ~ 30 parts of organophosphorous ester fire retardants
15 parts ~ 30 parts of graft polyolefins
20 parts ~ 40 parts of other additives.
Preferably, a kind of electric wire and cable covering materials halogen-free anti-flaming polyolefin elastic composition, its raw material and weight part are as follows:
100 parts of styrene butadiene base polymers
100 parts ~ 130 parts of polyolefin resines
95 parts ~ 130 parts of tenderizers
80 parts ~ 120 parts of polyphenylene oxide resins
140 parts ~ 180 parts of expanded polystyrene veneer system fire retardants
10 parts ~ 20 parts of organophosphorous ester fire retardants
10 parts ~ 20 parts of graft polyolefins
15 parts ~ 35 parts of other additives
Wherein, the A-B-A structure that described styrene butadiene base polymer is a line style, comprise styrene-butadiene-styrene, styrene-isoprene-phenylethene, segmented copolymer styrene-ethylene/butylene-styrene, any one or more than one the mixture in segmented copolymer styrene-ethylene/propylene-styrene.
Wherein, described polyolefin resin be polypropylene, polyethylene, metallocene, contain the propylene composition copolymer substance, contain the ethene composition copolymer substance, contain any two or more the mixture in the copolymer substance of ethene and copolymerization of propylene.
Wherein, described tenderizer is any one or more than one the mixture in aromatic hydrocarbons base oil, naphthene base crude oil, paraffinic based oil, industrial white oil, the phosphoric acid ester liquid.Phosphoric acid ester liquid is trioctyl phosphate, oligomeric aromatic phosphate ester, any one or more than one the mixture in trimethyl phosphite 99, triethyl phosphate, tricresyl phosphate propyl ester, the tributyl phosphate.
Wherein, the limiting viscosity of described polyphenylene oxide resin (adopting chloroform to measure 25 ℃ the time as solvent) is 0.08dl/g ~ 0.6dl/g; Preferably, the limiting viscosity 0.12dl/g of polyphenylene oxide resin ~ 0.51dl/g.
Wherein, described expanded polystyrene veneer system fire retardant is the expanded polystyrene veneer system fire retardant that contains phosphorus, nitrogen, metal; Described organophosphorous ester fire retardant is any one or more than one the mixture in triphenylphosphate, dimethyl ethyl phosphoric acid ester, methyl two fourth phosphoric acid ester, ethyl dipropyl phosphoric acid ester, the phosphoric acid ester organic granular compound; The organophosphorous ester fire retardant is particle or pulverous fire retardant.
Wherein, described metal is one or both the mixture in phospho acid aluminium, the phospho acid zinc etc.
The expanded polystyrene veneer system fire retardant that contains phosphorus, nitrogen, metal, dominant mechanism becomes charcoal for produce source of the gas when this fire retardant material burns simultaneously with acid source, because of the synergistic effect between phosphorus, nitrogen, the multiple ignition-proof element of metal, charring rate and charcoal layer intensity have been improved, stop propagation of flame, reached fire-retardant purpose.The principal feature of organophosphorous ester fire retardant is to decompose heat before polyolefin resin, polyphenylene oxide resin dissolving, generate polyphosphoric acid, and generate dehydration reaction, form the uninflammability carburization zone with polyolefin resin, polyphenylene oxide resin, increase charring rate simultaneously, blocking oxygen and inflammable gas stop burning.
Wherein, described graft polyolefin is any one grafted maleic anhydride or the acrylic acid graft polyolefin in the composite grain, PP, PE, LLDPE, POE, EPDM, SBS, EVA of polyolefine SEBS particle, SEBS and TPU.
Wherein, described other additive comprises lubricant, tranquilizer, antioxidant, inorganic or pigment dyestuff, mineral filler, polystyrene resin, polyurethane resin.Lubricant is any one or more than one the mixture in organic oil, organo-silicic oil, stearic acid lubricant, the aliphatics lubricant, tranquilizer is calcium zinc tranquilizer or zinc oxide tranquilizer, antioxidant is any one or more than one the mixture in antioxidant 1010, oxidation inhibitor 168, the oxidation inhibitor 215, and mineral filler is polynite, talcum powder, lime carbonate, any one or more than one the mixture in elemental phosphorous.
Electric wire and cable covering materials of the present invention halogen-free anti-flaming polyolefin elastic composition preparation method, preferred following four kinds of preparation methods:
The preparation method one: earlier the styrene butadiene base polymer is put into the heating mixing equipment, elder generation's low speed or run up stirs more than 1 minute or 1 minute, add tenderizer while stirring then, after treating thorough mixing, powder raw material in the above-mentioned raw materials is added in the heating mixing equipment again, continue stirring at low speed 2 minutes ~ 5 minutes, again the particulate material in the above-mentioned raw materials is joined in the mixing equipment, continue low speed or high-speed stirring 2 minutes ~ 10 minutes, the temperature of heating mixing equipment is increased to more than 50 ℃, add the liquid starting material in the above-mentioned raw materials more while stirring, again raw materials mixed is put into forcing machine after mixing fully and extruded (forcing machine extrude temperature range be 160 ℃ ~ 215 ℃), cooling dries up or dries, the pelletizing moulding.
The preparation method two: earlier the styrene butadiene base polymer is put into the heating mixing equipment, elder generation's low speed or run up stirs more than 1 minute or 1 minute, then while stirring the liquid starting material that adds in tenderizer and the above-mentioned raw materials, after treating thorough mixing, again powder raw material in the above-mentioned raw materials and particulate material are added in the heating mixing equipment, continue low speed or high-speed stirring 2 minutes ~ 10 minutes, again raw materials mixed is put into forcing machine after mixing fully and extruded (forcing machine extrude temperature range be 160 ℃ ~ 215 ℃), cooling, dry up or dry, the pelletizing moulding.
The preparation method three: by said ratio polyphenylene oxide resin, styrene butadiene base polymer, polyolefin resin, expanded polystyrene veneer system fire retardant, organophosphorous ester fire retardant, graft polyolefin and other additive are added in the pre-mixing equipment together, continue to mix stirring 1 min ~ l0min, in the plasticization temperature scope, extrude, cool off then, finally through the pelletizing moulding through forcing machine.Pre-mixing equipment can adopt machine, tumbling mixer or other plastics mixer tool equipment of mixing at a high speed, preferred high-speed mixer; Described plasticization temperature scope is 160 ℃ ~ 215 ℃; The described type of cooling can be a water-cooled or air-cooled, preferably adopts water-cooling process.
The preparation method four: by said ratio polyphenylene oxide resin, styrene butadiene base polymer, polyolefin resin, expanded polystyrene veneer system fire retardant, organophosphorous ester fire retardant, graft polyolefin and other additive are added in the pre-mixing equipment together, continue to mix stirring 1 min ~ l0min, in the plasticization temperature scope, open refining, water cooling through banburying, two roller respectively then, final pelletizing moulding.The banburying link can be carried out in closed plastic banbury mixer or single screw extrusion machine, and the plasticization temperature scope is 160 ℃ ~ 215 ℃.
Beneficial effect of the present invention is: a kind of electric wire and cable covering materials halogen-free anti-flaming polyolefin elastic composition of the present invention, its raw material and weight part are as follows: 100 parts of styrene butadiene base polymers, 80 parts ~ 150 parts of polyolefin resines, 75 parts ~ 150 parts of tenderizers, 60 parts ~ 140 parts of polyphenylene oxide resins, 100 parts ~ 200 parts of expanded polystyrene veneer system fire retardants, 0 part ~ 30 parts of organophosphorous ester fire retardants, 0 part ~ 30 parts of graft polyolefins, 0 part ~ 40 parts of other additives.
The present invention has the following advantages:
1, tests (150 ℃ of thermal distortions, ballast 2000 grams, 1 hour deformation rate＜50%, actual measurement deformation rate＜20%) by the thermal distortion of UL758 regulation;
2, by UL standard and other extend anti-Zhang Yaoqiu test (the standard elongation〉200%, tensile strength〉8.4Mpa, actual elongation〉300%, tensile strength〉12.5Mpa);
3, flame retardant properties meet UL94-V0 requirement (actual measurement 1.1mm, thickness Pass, UL94V-0), oxygen index is more than 32;
4, do not add halogen or harmful heavy metal, have favorable compatibility, workability, shock-resistance;
5, has adjustable relatively pliability, by the soft durometer of the present invention that the consumption of adjusting tenderizer is adjusted, density low (material of identical weight can be produced more electric wire than other Halogen product more); Good processability need not changed or adjust electric wire extrusion board in electric wire manufacturer and just can carry out electric wire production smoothly, and additive can not take place the electric wire of producing separates out phenomenon;
6, have polystyrene end segment and soft middle segment, be gathered into tough plastics phase at peacetime state polystyrene segment, and making material form the continuous three-dimensional reticulated structure by the physical crosslinking effect, the structural strength height makes the present invention have good physicals, heat-resistant deforming performance;
7, meet electric wire standard UL1581 and UL758, meet relevant international environmental law rule RoHS2.0 standard, halogen (Halogen Free) standard, Reach-SVHC standard, EN-71 standard etc. simultaneously.
Description of drawings
Fig. 1 is polystyrene end segment and the soft middle segmental tridimensional network synoptic diagram of electric wire and cable covering materials of the present invention with the halogen-free anti-flaming polyolefin elastic composition.
Embodiment
The present invention is further illustrated below in conjunction with accompanying drawing.
Embodiment 1.
A kind of electric wire and cable covering materials halogen-free anti-flaming polyolefin elastic composition, its raw material and weight part are as follows: 100 parts of styrene butadiene base polymers, 150 parts of polyolefin resines, 150 parts of tenderizers, 140 parts of polyphenylene oxide resins, 200 parts of expanded polystyrene veneer system fire retardants, 30 parts of organophosphorous ester fire retardants, 30 parts of graft polyolefins, 40 parts of other additives.
Wherein, the A-B-A structure that described styrene butadiene base polymer is a line style is specially styrene-butadiene-styrene; Described polyolefin resin is the mixture of polypropylene, metallocene; Described tenderizer is the mixture of aromatic hydrocarbons base oil, naphthene base crude oil; Expanded polystyrene veneer system fire retardant is the expanded polystyrene veneer system fire retardant that contains phosphorus, nitrogen, metal, and particularly, metal is a phospho acid aluminium; The organophosphorous ester fire retardant is a triphenylphosphate; Described graft polyolefin is the graft polyolefin of PP grafted maleic anhydride; Described other additive comprises lubricant, tranquilizer, antioxidant, inorganic or pigment dyestuff, mineral filler, polystyrene resin, polyurethane resin, lubricant is an organic oil, tranquilizer is a calcium zinc tranquilizer, and antioxidant is an antioxidant 1010, and mineral filler is polynite.
The limiting viscosity of polyphenylene oxide resin (adopting chloroform to measure 25 ℃ the time as solvent) is 0.08dl/g.
The electric wire and cable covering materials of present embodiment is as follows with halogen-free anti-flaming polyolefin elastic composition preparation method: earlier the styrene butadiene base polymer is put into the heating mixing equipment, elder generation's low speed or run up stirs more than 1 minute or 1 minute, add tenderizer while stirring then, after treating thorough mixing, powder raw material in the above-mentioned raw materials is added in the heating mixing equipment again, continue stirring at low speed 2 minutes ~ 5 minutes, again the particulate material in the above-mentioned raw materials is joined in the heating mixing equipment, continue low speed or high-speed stirring 2 minutes ~ 10 minutes, the temperature of heating mixing equipment is increased to more than 50 ℃, while stirring the liquid starting material in the above-mentioned raw materials is joined again in the heating mixing equipment, after mixing fully, again mixed raw material is put into forcing machine and extruded (forcing machine extrude temperature be 160 ℃), cooling, dry up or dry, the pelletizing moulding makes the present invention.
Embodiment 2.
A kind of electric wire and cable covering materials halogen-free anti-flaming polyolefin elastic composition, its raw material and weight part are as follows: 100 parts of styrene butadiene base polymers, 115 parts of polyolefin resines, 105 parts of tenderizers, 100 parts of polyphenylene oxide resins, 150 parts of expanded polystyrene veneer system fire retardants, 15 parts of organophosphorous ester fire retardants, 15 parts of graft polyolefins, 20 parts of other additives.
Wherein, the A-B-A structure that described styrene butadiene base polymer is a line style is in particular the mixture of styrene-isoprene-phenylethene, segmented copolymer styrene-ethylene/butylene-styrene; Described polyolefin resin is metallocene, contain the mixture of the copolymer substance of propylene composition; Described tenderizer is a phosphoric acid ester liquid, and phosphoric acid ester liquid is in particular trioctyl phosphate; Expanded polystyrene veneer system fire retardant is the expanded polystyrene veneer system fire retardant that contains phosphorus, nitrogen, metal, and particularly, metal is a phospho acid zinc; The organophosphorous ester fire retardant is the mixture of methyl two fourth phosphoric acid ester, ethyl dipropyl phosphoric acid ester; Described graft polyolefin is that LLDPE connects the acrylic acid graft polyolefin of skill; Described other additive comprises lubricant, tranquilizer, antioxidant, inorganic or pigment dyestuff, mineral filler, polystyrene resin, polyurethane resin, lubricant is the mixture of organic oil, organo-silicic oil, tranquilizer is the zinc oxide tranquilizer, antioxidant is an oxidation inhibitor 168, and mineral filler is a talcum powder.
The limiting viscosity of polyphenylene oxide resin (adopting chloroform to measure 25 ℃ the time as solvent) is 0.12dl/g.
The electric wire and cable covering materials of present embodiment is as follows with halogen-free anti-flaming polyolefin elastic composition preparation method: earlier the styrene butadiene base polymer is put into the heating mixing equipment, elder generation's low speed or run up stirs more than 1 minute or 1 minute, then while stirring the liquid starting material that adds in tenderizer and the above-mentioned raw materials, after treating thorough mixing, again powder raw material in the above-mentioned raw materials and particulate material are added in the heating mixing equipment, continue low speed or high-speed stirring 2 minutes ~ 10 minutes, after mixing fully, again mixed raw material is put into forcing machine and extruded (forcing machine extrude temperature range be 180 ℃ ~ 200 ℃), cooling, dry up or dry, the pelletizing moulding makes the present invention.
Embodiment 3.
A kind of electric wire and cable covering materials halogen-free anti-flaming polyolefin elastic composition, its raw material and weight part are as follows: 100 parts of styrene butadiene base polymers, 130 parts of polyolefin resines, 95 parts of tenderizers, 120 parts of polyphenylene oxide resins, 130 parts of expanded polystyrene veneer system fire retardants, 20 parts of organophosphorous ester fire retardants, 10 parts of graft polyolefins, 35 parts of other additives.
Wherein, the A-B-A structure that described styrene butadiene base polymer is a line style is in particular the mixture in styrene-butadiene-styrene, styrene-isoprene-phenylethene, the segmented copolymer styrene-ethylene/propylene-styrene; Described polyolefin resin is polypropylene, polyethylene, contain the mixture of the copolymer substance of ethene and copolymerization of propylene; Described tenderizer is paraffinic based oil and phosphoric acid ester mixtures of liquids, and phosphoric acid ester liquid is in particular oligomeric aromatic phosphate ester, the mixture in tricresyl phosphate propyl ester, the tributyl phosphate; Expanded polystyrene veneer system fire retardant is the expanded polystyrene veneer system fire retardant that contains phosphorus, nitrogen, metal, and particularly, metal is the mixture of phospho acid aluminium and phospho acid zinc; The organophosphorous ester fire retardant is the mixture of triphenylphosphate, dimethyl ethyl phosphoric acid ester, methyl two fourth phosphoric acid ester, ethyl dipropyl phosphoric acid ester; Described graft polyolefin is polyolefine SEBS particle grafted maleic anhydride or acrylic acid graft polyolefin; Described other additive comprises lubricant, tranquilizer, antioxidant, inorganic or pigment dyestuff, mineral filler, polystyrene resin, polyurethane resin, lubricant is the aliphatics lubricant, tranquilizer is a calcium zinc tranquilizer, antioxidant is an oxidation inhibitor 215, and mineral filler is polynite, talcous mixture.
The limiting viscosity of polyphenylene oxide resin (adopting chloroform to measure 25 ℃ the time as solvent) is 0.3dl/g.
The electric wire and cable covering materials of present embodiment is as follows with halogen-free anti-flaming polyolefin elastic composition preparation method: earlier the styrene butadiene base polymer is put into the heating mixing equipment, elder generation's low speed or run up stirs more than 1 minute or 1 minute, add tenderizer while stirring then, after treating thorough mixing, powder raw material in the above-mentioned raw materials is added in the heating mixing equipment again, continue stirring at low speed 2 minutes ~ 5 minutes, again the particulate material in the above-mentioned raw materials is joined in the heating mixing equipment, continue low speed or high-speed stirring 2 minutes ~ 10 minutes, the temperature of heating mixing equipment is increased to more than 50 ℃, add the liquid starting material in the above-mentioned raw materials more while stirring, after mixing fully, more mixed raw material is put into forcing machine and extruded (forcing machine extrude temperature be 215 ℃), cooling, dry up or dry, the pelletizing moulding.
Embodiment 4.
A kind of electric wire and cable covering materials halogen-free anti-flaming polyolefin elastic composition, its raw material and weight part are as follows: 100 parts of styrene butadiene base polymers, 100 parts of polyolefin resines, 130 parts of tenderizers, 80 parts of polyphenylene oxide resins, 160 parts of expanded polystyrene veneer system fire retardants, 10 parts of organophosphorous ester fire retardants.
Wherein, the A-B-A structure that described styrene butadiene base polymer is a line style, be in particular styrene-butadiene-styrene, styrene-isoprene-phenylethene, segmented copolymer styrene-ethylene/butylene-styrene, the mixture in segmented copolymer styrene-ethylene/propylene-styrene; Described polyolefin resin is metallocene, contain the copolymer substance of propylene composition, contain the mixture of the copolymer substance of ethene composition; Described tenderizer is the mixture of aromatic hydrocarbons base oil, naphthene base crude oil, paraffinic based oil; Expanded polystyrene veneer system fire retardant is the expanded polystyrene veneer system fire retardant that contains phosphorus, nitrogen, metal, and particularly, metal is a kind of in the metals such as phospho acid aluminium, phospho acid zinc or more than one mixture; The organophosphorous ester fire retardant is the mixture of triphenylphosphate, dimethyl ethyl phosphoric acid ester.
The limiting viscosity of polyphenylene oxide resin (adopting chloroform to measure 25 ℃ the time as solvent) is 0.51dl/g.
The electric wire and cable covering materials of present embodiment is as follows with halogen-free anti-flaming polyolefin elastic composition preparation method: by said ratio polyphenylene oxide resin, styrene butadiene base polymer, polyolefin resin, expanded polystyrene veneer system fire retardant, organophosphorous ester fire retardant are added in the pre-mixing equipment together, continue to mix stirring 5min, in the plasticization temperature scope, extrude, cool off then, finally through the pelletizing moulding through forcing machine.Pre-mixing equipment can adopt machine, tumbling mixer or other plastics mixer tool equipment of mixing at a high speed, preferred high-speed mixer; Described plasticization temperature scope is 160 ℃; The described type of cooling can be a water-cooled or air-cooled, preferably adopts water-cooling process.
Embodiment 5.
A kind of electric wire and cable covering materials halogen-free anti-flaming polyolefin elastic composition, its raw material and weight part are as follows: 100 parts of styrene butadiene base polymers, 80 parts of polyolefin resines, 75 parts of tenderizers, 60 parts of polyphenylene oxide resins, 100 parts of expanded polystyrene veneer system fire retardants.
Wherein, the A-B-A structure that described styrene butadiene base polymer is a line style is in particular the segmented copolymer styrene-ethylene/butylene-styrene.
Wherein, described polyolefin resin be the copolymer substance that contains the ethene composition, the mixture in the copolymer substance that contains ethene and copolymerization of propylene; Described tenderizer is a paraffinic based oil; Expanded polystyrene veneer system fire retardant is the expanded polystyrene veneer system fire retardant that contains phosphorus, nitrogen, metal, and wherein, metal is a kind of in the metals such as phospho acid aluminium, phospho acid zinc or more than one mixture.
The limiting viscosity of described polyphenylene oxide resin (adopting chloroform to measure 25 ℃ the time as solvent) is 0.6dl/g.
The electric wire and cable covering materials of present embodiment is as follows with halogen-free anti-flaming polyolefin elastic composition preparation method: by said ratio polyphenylene oxide resin, styrene butadiene base polymer, polyolefin resin, expanded polystyrene veneer system fire retardant are added in the pre-mixing equipment together, continue to mix stirring l0min, in the plasticization temperature scope, open refining, water cooling through banburying, two roller respectively then, final pelletizing moulding.The banburying link can be carried out in closed plastic banbury mixer or single screw extrusion machine, and plasticization temperature is 200 ℃.
Should be noted that at last; above embodiment is only in order to illustrate technical scheme of the present invention; but not limiting the scope of the invention; although the present invention has been done to explain with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; can make amendment or be equal to replacement technical scheme of the present invention, and not break away from the essence and the scope of technical solution of the present invention.
Claims (10)
1. electric wire and cable covering materials halogen-free anti-flaming polyolefin elastic composition, it is characterized in that: its raw material and weight part are as follows:
100 parts of styrene butadiene base polymers
80 parts ~ 150 parts of polyolefin resines
75 parts ~ 150 parts of tenderizers
60 parts ~ 140 parts of polyphenylene oxide resins
100 parts ~ 200 parts of expanded polystyrene veneer system fire retardants
0 part ~ 30 parts of organophosphorous ester fire retardants
0 part ~ 30 parts of graft polyolefins
0 part ~ 40 parts of other additives.
2. electric wire and cable covering materials halogen-free anti-flaming polyolefin elastic composition according to claim 1, it is characterized in that: its raw material and weight part are as follows:
100 parts of styrene butadiene base polymers
80 parts ~ 115 parts of polyolefin resines
75 parts ~ 105 parts of tenderizers
60 parts ~ 100 parts of polyphenylene oxide resins
100 parts ~ 150 parts of expanded polystyrene veneer system fire retardants
0 part ~ 15 parts of organophosphorous ester fire retardants
0 part ~ 15 parts of graft polyolefins
0 part ~ 20 parts of other additives.
3. electric wire and cable covering materials halogen-free anti-flaming polyolefin elastic composition according to claim 1, it is characterized in that: its raw material and weight part are as follows:
100 parts of styrene butadiene base polymers
115 parts ~ 150 parts of polyolefin resines
105 parts ~ 150 parts of tenderizers
100 parts ~ 140 parts of polyphenylene oxide resins
150 parts ~ 200 parts of expanded polystyrene veneer system fire retardants
15 parts ~ 30 parts of organophosphorous ester fire retardants
15 parts ~ 30 parts of graft polyolefins
20 parts ~ 40 parts of other additives.
4. electric wire and cable covering materials halogen-free anti-flaming polyolefin elastic composition according to claim 1, it is characterized in that: its raw material and weight part are as follows:
100 parts of styrene butadiene base polymers
100 parts ~ 130 parts of polyolefin resines
95 parts ~ 130 parts of tenderizers
80 parts ~ 120 parts of polyphenylene oxide resins
140 parts ~ 180 parts of expanded polystyrene veneer system fire retardants
10 parts ~ 20 parts of organophosphorous ester fire retardants
10 parts ~ 20 parts of graft polyolefins
15 parts ~ 35 parts of other additives.
5. according to any described electric wire and cable covering materials halogen-free anti-flaming polyolefin elastic composition of claim 1 ~ 4, it is characterized in that: described styrene butadiene base polymer is styrene-butadiene-styrene, styrene-isoprene-phenylethene, styrene-ethylene/butylene-styrene, any one in styrene-ethylene/propylene-styrene or more than one mixture.
6. according to any described electric wire and cable covering materials halogen-free anti-flaming polyolefin elastic composition of claim 1 ~ 4, it is characterized in that: described polyolefin resin is polypropylene, polyethylene, metallocene, contain the copolymer substance of propylene composition, contain the ethene composition copolymer substance, contain any two or more the mixture in the copolymer substance of ethene and copolymerization of propylene.
7. according to any described electric wire and cable covering materials halogen-free anti-flaming polyolefin elastic composition of claim 1 ~ 4, it is characterized in that: described tenderizer is any one or more than one the mixture in aromatic hydrocarbons base oil, naphthene base crude oil, paraffinic based oil, industrial white oil, the phosphoric acid ester liquid.
8. according to any described electric wire and cable covering materials halogen-free anti-flaming polyolefin elastic composition of claim 1 ~ 4, it is characterized in that: described expanded polystyrene veneer system fire retardant is the expanded polystyrene veneer system fire retardant that contains phosphorus, nitrogen, metal; Described organophosphorous ester fire retardant is any one or more than one the mixture in triphenylphosphate, dimethyl ethyl phosphoric acid ester, methyl two fourth phosphoric acid ester, ethyl dipropyl phosphoric acid ester, the phosphoric acid ester organic granular compound.
9. electric wire and cable covering materials halogen-free anti-flaming polyolefin elastic composition according to claim 8 is characterized in that: described metal is one or both the mixture in phospho acid aluminium, the phospho acid zinc.
10. according to any described electric wire and cable covering materials halogen-free anti-flaming polyolefin elastic composition of claim 1 ~ 4, it is characterized in that: described graft polyolefin is any one grafted maleic anhydride or the acrylic acid graft polyolefin in the composite grain, PP, PE, LLDPE, POE, EPDM, SBS, EVA of polyolefine SEBS particle, SEBS and TPU; Described other additive comprises lubricant, tranquilizer, antioxidant, inorganic or pigment dyestuff, mineral filler, polystyrene resin, polyurethane resin.
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| CN102585428A (en) * | 2012-03-15 | 2012-07-18 | 浙江北化阻燃材料有限公司 | Flexible halogen-free flame-retardant polyphenyl ether electric wire cable shield material and preparation method thereof |
| CN102719049A (en) * | 2012-05-28 | 2012-10-10 | 深圳市盛嘉伦橡塑工业有限公司 | Non-flame-retardant thermoplastic elastomer material and preparation method thereof |
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| CN102585428A (en) * | 2012-03-15 | 2012-07-18 | 浙江北化阻燃材料有限公司 | Flexible halogen-free flame-retardant polyphenyl ether electric wire cable shield material and preparation method thereof |
| CN102719049A (en) * | 2012-05-28 | 2012-10-10 | 深圳市盛嘉伦橡塑工业有限公司 | Non-flame-retardant thermoplastic elastomer material and preparation method thereof |
| CN103540075A (en) * | 2012-07-18 | 2014-01-29 | 苏州朗创化工有限公司 | Highly flame-retardant TPE (Thermoplastic Polyurethane Elastomer) material |
| CN103102814A (en) * | 2013-01-28 | 2013-05-15 | 苏州井上高分子新材料有限公司 | EVA (ethylene-vinyl acetate) hot-melting adhesive and preparation method thereof |
| US9493621B2 (en) | 2013-07-23 | 2016-11-15 | Sabic Global Technologies B.V. | Rigid foam and associated article and method |
| US9175160B2 (en) | 2013-08-28 | 2015-11-03 | Sabic Global Technologies B.V. | Blend of poly(phenylene ether) particles and polyoxymethylene, article thereof, and method of preparation |
| CN103804885A (en) * | 2013-09-22 | 2014-05-21 | 东莞市安拓普塑胶聚合物科技有限公司 | Halogen-free flame-retardnat 105 DEG C high-temperature MPPE (modified polyphenyl ether) composition and preparation method thereof |
| CN103524978A (en) * | 2013-09-30 | 2014-01-22 | 芜湖航天特种电缆厂 | Thermosetting crosslinking environment-friendly type halogen-free low-smoke flame-retardant cable material |
| CN103524978B (en) * | 2013-09-30 | 2016-05-25 | 芜湖航天特种电缆厂 | A kind of Thermosetted cross-linked environment-protective halogen-free low-smoke flame-retardant cable material |
| US9447227B2 (en) | 2013-10-03 | 2016-09-20 | Sabic Global Technologies B.V. | Flexible polyurethane foam and associated method and article |
| CN105810309A (en) * | 2015-01-20 | 2016-07-27 | 王笑梅 | Cable and elastomer cable material for new energy vehicle internal connection |
| CN106189042A (en) * | 2016-08-31 | 2016-12-07 | 苏州亨利通信材料有限公司 | One has fire-retardant TPE cable material of heat conductivility and preparation method thereof |
| CN107057262A (en) * | 2017-02-14 | 2017-08-18 | 湖北科普达实业有限公司 | Special TPE elastomer CABLE MATERIALS of electric vehicle rapid charging machine and preparation method thereof |
| CN112029169A (en) * | 2020-08-18 | 2020-12-04 | 上海贝恩科电缆有限公司 | High-speed elevator cable material, material preparation method and cable manufacturing method |
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