CN103554654A - Polypropylene composite material containing polyphosphate organic-inorganic compounded copper-inhibitor and preparation method of polypropylene composite material - Google Patents
Polypropylene composite material containing polyphosphate organic-inorganic compounded copper-inhibitor and preparation method of polypropylene composite material Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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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- 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
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- C08K3/32—Phosphorus-containing compounds
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- C08K5/00—Use of organic ingredients
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- C08K5/20—Carboxylic acid amides
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- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
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- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/5399—Phosphorus bound to nitrogen
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C2948/00—Indexing scheme relating to extrusion moulding
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Abstract
The invention relates to a polypropylene composite material containing a polyphosphate organic-inorganic compounded copper-inhibitor and a preparation method of the polypropylene composite material. The polypropylene composite material is a blending material of the following materials in percent by mass: 70-90% of polypropylene, 0.01-1% of the organic-inorganic compounded copper inhibitor, 0.1-10% of an inorganic filling material, 0.1-0.5% of an anti-oxidant, 0.1-0.3% of a UV absorbent and 5-20% of a fire retardant. The preparation method comprises: mixing the various raw materials into a mixed material according to the ratio, extruding the mixed material by a double-screw extruder, performing cold-water drawing, cutting and granulating to form granules. According to the method, the organic-inorganic compounded copper inhibitor is employed for complexing with copper ions and further for generating a high-stability chelate, has extremely strong capability of inhibiting catalytic aging of heavy-metal ions, is substantial in copper-hazard resistant effect, and also has the advantages that the polyphosphate copper inhibitor is good in compatibility with resin, does not migrate, has no pollution, is resistant in water and good in oil extraction performance, does not influence electrical insulation property and other properties of resin, and the like.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of polypropylene composite material and preparation method thereof, particularly a kind of for electric wire containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic and preparation method thereof.
Background technology
In recent years, along with the development of electric power, the communications industry, make the demand of electric wire also progressively strengthen.What various cables, electrical equipment used mostly is copper core cable, and its external insulation coating layer is polyolefins plastics, and wherein propylene copolymer is showing the unrivaled advantage of other material aspect communication cable insulating material.But in polypropylene molecule, owing to having methyl and tertiary carbon atom, be very easily subject to light or thermal ageing, especially, in the situation that cupric ion exists, degradation with aging is rapider.Even when having added the polypropylene that adds oxidation inhibitor and anti ultraviolet agent and making copper core electric wire foreskin, its life-span is also shorter, cannot life-time service.Even if add oxidation inhibitor and anti ultraviolet agent, can not suppress copper to polyacrylic catalyzed degradation.Therefore improving polyacrylic anti-copper evil property is an important research direction of polypropylene material modification, has important scientific meaning and practical value.
Application number is that 201010612528.6 Chinese patent has been announced the anti-copper functional agglomerate of a kind of polypropylene, in master batch, the addition of anti copper agent is 9.5%-19.5%, this master batch not only can make cupric ion lose activity, reduce its side effect to copper core coating layer, there is Undec advantage within the scope of processing temperature simultaneously.Application number is that 200910193699.7 Chinese patent has been announced a kind of copper toxicity-resistant glass fiber reinforced polypropylene composite material and preparation method thereof.Its polypropylene content is 60-65%, the content of anti-copper evil agent is 0-0.2%, the preparation method of this matrix material is in high-speed mixer and mixing by polypropylene, compatilizer, composite antioxidant, the evil agent of anti-copper and processing aid, through twin screw extruder extruding pelletization, the matrix material of this invention has excellent heat-resistant aging and anti-copper evil property.
Anti copper agent is a kind of polymeric additive, has preventing and slow down metal ion polymkeric substance to be produced to the effect of initiated oxidation, is again metallic ion passivation agent, metal passivator or copper(greening)inhibitor.Can form and to be insoluble in polypropylene, metal complex that thermostability is high with metal, metal ion be lost activity, thereby played the effect of cupric ion to polypropylene catalyzed degradation that prevent.In order to prevent the catalyzed degradation of copper, need in polypropylene, add copper(greening)inhibitor.
This patent selects organic-inorganic compound composite as anti copper agent.Organic anti copper agent and matrix resin avidity are strong, contribute to it dispersed in matrix resin.Inorganic anti copper agent is strong with the avidity of mineral filler, contributes to its dispersion in mineral filler.In addition, inorganic anti copper agent has better stability.Adopt the composite anti copper agent that is used as of organic-inorganic compound, effectively the resistance to copper evil of Reinforced Polypropylene ability.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, provide a kind of containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic.
Of the present invention is blend containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic, and this blend comprises polypropylene, the composite anti copper agent of organic-inorganic, mineral filler, antioxidant, uv-absorbing agent, fire retardant; Each raw material at the quality percentage composition containing in the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic is: polypropylene 70～90 ﹪, composite anti copper agent 0.01～1 ﹪ of organic-inorganic, mineral filler 0.1～10 ﹪, antioxidant 0.1～0.5 ﹪, uv-absorbing agent 0.1～0.3 ﹪, fire retardant 5～20 ﹪;
Described polypropylene is the homopolymer of degree of isotacticity >=97 ﹪, and melting index is 3～40g/10min;
The composite anti copper agent of described organic-inorganic is that 1:10～10:1 forms by organic anti copper agent composition and inorganic anti copper agent composition according to mass ratio; Wherein organic anti copper agent composition is N, N '-bis-(o-hydroxy methyne) ethanedioyl two hydrazines, N, N'-is two, and [3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, (3,5-di-tert-butyl-hydroxy phenyl) propionic acid oxalyl (diimino-2,1-ethylidene ester), N, one or more in N-diacetyl adipic dihydrazide, salicylidene salicyl hydrazine; Inorganic anti copper agent composition is inorganic polyphosphate type, organophosphate type or both are composite, wherein inorganic polyphosphate type comprises one or more of tripoly phosphate sodium STPP, Sodium hexametaphosphate 99, trisodium phosphate, and organophosphate type comprises one or more in amino trimethylene methyl acid phosphate (ATMP), hydroxy ethylidene-diphosphate (HEDP), ethylenediamine tetramethylene phosphoric acid (EDTMP).
Described mineral filler is one or more in calcium carbonate, silicon oxide, talcum powder, attapulgite, polynite, zeolite, kaolin;
Described antioxidant is a kind of in antioxidant 1010, antioxidant b215, antioxidant b225, antioxidant 168, antioxidant 1076, antioxidant DLTP.
Described uv-absorbing agent is a kind of in UV-12, UV-326, UV-327, UV-328, UV-329, UV-770.
Described fire retardant is that nitrogen phosphorus is one or more in mixture, aluminium hydroxide, magnesium hydroxide; Nitrogen phosphorus is that mixture is that 3:1:1 forms by acid source, source of the gas, carbon source according to mass ratio, and acid source is phosphoric acid, Vanadium Pentoxide in FLAKES, phosphorus oxychloride or polyphosphoric acid amine, and source of the gas is trimeric cyanamide, and carbon source is tetramethylolmethane.
Another object of the present invention is just to provide the above-mentioned preparation method containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic.
Preparing these concrete steps containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic is:
Step (1). by polypropylene, the composite anti copper agent of organic-inorganic, mineral filler, antioxidant, uv-absorbing agent, fire retardant, be proportionally mixed into compound;
Prepare 100 weight parts containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic, each amount of substance used is: the polypropylene of 70～90 parts, the composite anti copper agent of organic-inorganic of 0.01～1 part, the mineral filler of 0.1～10 part, the antioxidant of 0.1～0.5 part, the uv-absorbing agent of 0.1～0.3 part, the fire retardant of 5～20 parts.
Step (2). compound is extruded by twin screw extruder, then through cold water drawing-off, granulation, obtained containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic.
The processing temperature of twin screw extruder is: 120～150 ℃ of feeding sections, 150～180 ℃ of fluxing zones, 180～205 ℃ of homogenizing zones, and head temperature is 180～195 ℃;
The bath temperature of cold water drawing-off is 10～40 ℃, and drawing-off multiplying power is 2～6 times.
The selected anti copper agent energy of the present invention chelated copper ion, it is lost activity, there is the very strong aging ability of inhibition heavy metal ion catalysis, anti-copper evil effect significantly and have with resin-phase dissolubility good, do not move, do not pollute, water-fast, oil extraction is good, does not affect the advantages such as the electrical insulation capability of resin and other performances.The desirable insulating material that can be used as copper core cable and line containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic provided by the invention, can be used for producing communication cable, undersea cable, oil field cable, power cable etc.
Embodiment
Below in conjunction with specific embodiment, the present invention is further analyzed to (polypropylene in following examples is the homopolymer of degree of isotacticity >=97 ﹪, and melting index is 3～40g/10min).
Embodiment 1.
Step (1). 85g polypropylene, 5g calcium carbonate, 0.1g uv-absorbing agent UV-12,9.9g fire retardant are mixed into 100g compound;
Step (2). compound is joined to twin screw extruder and extrude, the processing temperature of twin screw extruder is 120 ℃ of feeding sections, 150 ℃ of fluxing zones, 180 ℃ of homogenizing zones, and head temperature is 180 ℃; In 10 ℃ of water-baths, carry out cold water drawing-off again, drawing-off multiplying power is 2 times, and cutting machine cuts granulation, obtains polypropylene composite material.
From table 1 we, the polypropylene composite material that embodiment 1 prepares after testing known tensile strength is 32.4Mpa, elongation is 64 ﹪, oxygen uptake inductive phase is 2min at 200 ℃, the serious embrittlement of tablet after 150 ℃ of folder copper strip test 4d, it is green that copper sheet turns.
Embodiment 2.
Step (1). 84.7g polypropylene, the composite anti copper agent of 0.1g organic-inorganic, 5g calcium carbonate, 0.2g antioxidant 1010,0.1g uv-absorbing agent UV-12,9.9g fire retardant are mixed into 100g compound;
Step (2). compound is joined to twin screw extruder and extrude, the processing temperature of twin screw extruder is 120 ℃ of feeding sections, 150 ℃ of fluxing zones, 180 ℃ of homogenizing zones, and head temperature is 180 ℃; In 10 ℃ of water-baths, carry out cold water drawing-off again, drawing-off multiplying power is 2 times, and cutting machine cuts granulation, obtains polypropylene composite material.
From table 1 we, the polypropylene composite material that embodiment 2 prepares after testing known tensile strength is 34.6Mpa, elongation is 66 ﹪, oxygen uptake inductive phase is 45min at 200 ℃, after 150 ℃ of folder copper strip test 4d, tablet is not crisp, copper sheet is unchanged.
Embodiment 3.
Step (1). 84.5g polypropylene, the composite anti copper agent of 0.3g organic-inorganic, 5g calcium carbonate, 0.2g antioxidant 1010,0.1g uv-absorbing agent UV-12,9.9g fire retardant are mixed into 100g compound;
Step (2). compound is joined to twin screw extruder and extrude, the processing temperature of twin screw extruder is 120 ℃ of feeding sections, 150 ℃ of fluxing zones, 180 ℃ of homogenizing zones, and head temperature is 180 ℃; In 10 ℃ of water-baths, carry out cold water drawing-off again, drawing-off multiplying power is 2 times, and cutting machine cuts granulation, obtains polypropylene composite material.
From table 1 we, the polypropylene composite material that embodiment 3 prepares after testing known tensile strength is 35.1Mpa, elongation is 63 ﹪, oxygen uptake inductive phase is 53min at 200 ℃, after 150 ℃ of folder copper strip test 4d, tablet is not crisp, copper sheet is unchanged.
Embodiment 4.
Step (1). 84.3g polypropylene, the composite anti copper agent of 0.5g organic-inorganic, 5g calcium carbonate, 0.2g antioxidant 1010,0.1g uv-absorbing agent UV-12,9.9g fire retardant are mixed into 100g compound;
Step (2). compound is joined to twin screw extruder and extrude, the processing temperature of twin screw extruder is 120 ℃ of feeding sections, 150 ℃ of fluxing zones, 180 ℃ of homogenizing zones, and head temperature is 180 ℃; In 10 ℃ of water-baths, carry out cold water drawing-off again, drawing-off multiplying power is 2 times, and cutting machine cuts granulation, obtains polypropylene composite material.
From table 1 we, the polypropylene composite material that embodiment 4 prepares after testing known tensile strength is 33.6Mpa, elongation is 60 ﹪, oxygen uptake inductive phase is 75min at 200 ℃, after 150 ℃ of folder copper strip test 4d, tablet is not crisp, copper sheet is unchanged.
Embodiment 5.
Step (1). 84.8g polypropylene, 5g calcium carbonate, 0.2g antioxidant 1010,0.1g uv-absorbing agent UV-12,9.9g fire retardant are mixed into 100g compound;
Step (2). compound is joined to twin screw extruder and extrude, the processing temperature of twin screw extruder is 120 ℃ of feeding sections, 150 ℃ of fluxing zones, 180 ℃ of homogenizing zones, and head temperature is 180 ℃; In 10 ℃ of water-baths, carry out cold water drawing-off again, drawing-off multiplying power is 2 times, and cutting machine cuts granulation, obtains polypropylene composite material.
From table 1 we, the polypropylene composite material that embodiment 5 prepares after testing known tensile strength is 32.3Mpa, elongation is 59 ﹪, oxygen uptake inductive phase is 12min at 200 ℃, the serious embrittlement of tablet after 150 ℃ of folder copper strip test 4d, it is green that copper sheet turns.
The composite anti copper agent of organic-inorganic used in embodiment 1～5 is by N, and N '-bis-(o-hydroxy methyne) ethanedioyl two hydrazines and amino trimethylene methyl acid phosphate are that 1:10 forms according to mass ratio; Fire retardant is that 3:1:1 forms by phosphoric acid, trimeric cyanamide, tetramethylolmethane according to mass ratio.
The Properties of Polypropylene Composite parameter list that table 1 embodiment 1～5 obtains
Embodiment 1～5 is contrasted, and we are known makes polypropylene composite material have the very strong aging ability of inhibition heavy metal ion catalysis because added the composite anti copper agent of organic-inorganic and antioxidant, and anti-copper evil effect is remarkable.
Embodiment 6.
Step (1). by 70g polypropylene, the composite anti copper agent of 0.01g organic-inorganic (by N, N '-bis-(o-hydroxy methyne) ethanedioyl two hydrazines and tripoly phosphate sodium STPP are that 10:1 forms according to mass ratio), 10g silicon oxide, 0.1g antioxidant b215,0.19g uv-absorbing agent UV-326,19.7g aluminium hydroxide, be mixed into 100g compound;
Step (2). compound is joined to twin screw extruder and extrude, the processing temperature of twin screw extruder is 150 ℃ of feeding sections, 180 ℃ of fluxing zones, 205 ℃ of homogenizing zones, and head temperature is 195 ℃; In 40 ℃ of water-baths, carry out cold water drawing-off again, drawing-off multiplying power is 6 times, and last cutting machine cuts granulation, obtains containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic.
Embodiment 7.
Step (1). by 70g polypropylene, the composite anti copper agent of 1g organic-inorganic (by N, N'-is two, and [3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine and Sodium hexametaphosphate 99 be that 1:1 forms according to mass ratio), 8.5g talcum powder, 0.4g antioxidant b225,0.1g uv-absorbing agent UV-327,20g magnesium hydroxide, be mixed into 100g compound;
Step (2). compound is joined to twin screw extruder and extrude, the processing temperature of twin screw extruder is 125 ℃ of feeding sections, 155 ℃ of fluxing zones, 185 ℃ of homogenizing zones, and head temperature is 180 ℃; Through 15 ℃ of water-baths, carry out cold water drawing-off again, drawing-off multiplying power is 3 times, and last cutting machine cuts granulation, obtains containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic.
Embodiment 8.
Step (1). by 90g polypropylene, the composite anti copper agent of 1g organic-inorganic (by (3,5-di-tert-butyl-hydroxy phenyl) propionic acid oxalyl (diimino-2,1-ethylidene ester) according to mass ratio, be that 1:1 forms with trisodium phosphate), 0.1g attapulgite, 0.5g antioxidant 168,0.3g uv-absorbing agent UV-328,8.1g nitrogen phosphorus be mixture (being that 3:1:1 forms according to mass ratio by Vanadium Pentoxide in FLAKES, trimeric cyanamide, tetramethylolmethane), is mixed into 100g compound;
Step (2). compound is joined to twin screw extruder and extrude, the processing temperature of twin screw extruder is 130 ℃ of feeding sections, 160 ℃ of fluxing zones, 190 ℃ of homogenizing zones, and head temperature is 190 ℃; Through 20 ℃ of water-baths, carry out cold water drawing-off again, drawing-off multiplying power is 4 times, and last cutting machine cuts granulation, obtains containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic.
Embodiment 9.
Step (1). by 90g polypropylene, the composite anti copper agent of 1g organic-inorganic (by N, N-diacetyl adipic dihydrazide, tripoly phosphate sodium STPP and Sodium hexametaphosphate 99 are that 1:2:3 forms according to mass ratio), 3.5g polynite, 0.3g antioxidant 1076,0.2g uv-absorbing agent UV-329,5g nitrogen phosphorus be mixture (being that 3:1:1 forms according to mass ratio by phosphorus oxychloride, trimeric cyanamide, tetramethylolmethane), is mixed into 100g compound;
Step (2). compound is joined to twin screw extruder and extrude, the processing temperature of twin screw extruder is 135 ℃ of feeding sections, 165 ℃ of fluxing zones, 195 ℃ of homogenizing zones, and head temperature is 190 ℃; Through 25 ℃ of water-baths, carry out cold water drawing-off again, drawing-off multiplying power is 5 times, and last cutting machine cuts granulation, obtains containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic.
Embodiment 10.
Step (1). by 80g polypropylene, the composite anti copper agent of 0.5g organic-inorganic (being that 1:8 forms according to mass ratio by salicylidene salicyl hydrazine and amino trimethylene methyl acid phosphate), 0.7g polynite, 0.5g antioxidant DLTP, 0.3g uv-absorbing agent UV-770,18g nitrogen phosphorus, be mixture (being that 3:1:1 forms according to mass ratio by polyphosphoric acid amine, trimeric cyanamide, tetramethylolmethane), be mixed into 100g compound;
Step (2). compound is joined to twin screw extruder and extrude, the processing temperature of twin screw extruder is 140 ℃ of feeding sections, 170 ℃ of fluxing zones, 200 ℃ of homogenizing zones, and head temperature is 195 ℃; Through the drawing-off of 30 ℃ of water-bath cold water, drawing-off multiplying power is 6 times again, and last cutting machine cuts granulation, obtains containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic.
Embodiment 11.
Step (1). by 80g polypropylene, the composite anti copper agent of 1g organic-inorganic (by N, N '-bis-(o-hydroxy methyne) ethanedioyl two hydrazines, N, N'-is two, and [3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine and hydroxy ethylidene-diphosphate be that 0.5:0.5:10 forms according to mass ratio), 3.2g zeolite, 0.5g antioxidant b215,0.3g uv-absorbing agent UV-326,5g aluminium hydroxide, 10g magnesium hydroxide, be mixed into 100g compound;
Step (2). compound is joined to twin screw extruder and extrude, the processing temperature of twin screw extruder is 145 ℃ of feeding sections, 175 ℃ of fluxing zones, 205 ℃ of homogenizing zones, and head temperature is 195 ℃; Through 35 ℃ of water-baths, carry out cold water drawing-off again, drawing-off multiplying power is 6 times, and last cutting machine cuts granulation, obtains containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic.
Embodiment 12.
Step (1). by 80g polypropylene, the composite anti copper agent of 1g organic-inorganic (by N, N '-bis-(o-hydroxy methyne) ethanedioyl two hydrazines, salicylidene salicyl hydrazine and ethylenediamine tetramethylene phosphoric acid are that 0.5:0.5:10 forms according to mass ratio), 8.5g kaolin, 0.4g antioxidant b225,0.1g uv-absorbing agent UV-327,5g nitrogen phosphorus is mixture (being that 3:1:1 forms according to mass ratio by polyphosphoric acid amine, trimeric cyanamide, tetramethylolmethane), 5g aluminium hydroxide, is mixed into 100g compound;
Step (2). compound is joined to twin screw extruder and extrude, the processing temperature of twin screw extruder is 150 ℃ of feeding sections, 180 ℃ of fluxing zones, 205 ℃ of homogenizing zones, and head temperature is 195 ℃; In 40 ℃ of water-baths, carry out cold water drawing-off again, drawing-off multiplying power is 6 times, and last cutting machine cuts granulation, obtains containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic.
Embodiment 13.
Step (1). by 80g polypropylene, the composite anti copper agent of 1g organic-inorganic is (by N, N '-bis-(o-hydroxy methyne) ethanedioyl two hydrazines, N, N-diacetyl adipic dihydrazide, salicylidene salicyl hydrazine, amino trimethylene methyl acid phosphate ATMP and hydroxy ethylidene-diphosphate are that 0.2:0.3:0.5:5:5 forms according to mass ratio), 4.5g zeolite, 4g kaolin, 0.4g antioxidant b225, 0.1g uv-absorbing agent UV-327, 5g nitrogen phosphorus is that mixture is (by phosphorus oxychloride, trimeric cyanamide, tetramethylolmethane is that 3:1:1 forms according to mass ratio), 5g magnesium hydroxide, be mixed into 100g compound,
Step (2). compound is joined to twin screw extruder and extrude, the processing temperature of twin screw extruder is 150 ℃ of feeding sections, 180 ℃ of fluxing zones, 205 ℃ of homogenizing zones, and head temperature is 195 ℃; In 40 ℃ of water-baths, carry out cold water drawing-off again, drawing-off multiplying power is 6 times, and last cutting machine cuts granulation, obtains containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic.
Embodiment 14.
Step (1). by 80g polypropylene, the composite anti copper agent of 1g organic-inorganic (by N, N-diacetyl adipic dihydrazide, salicylidene salicyl hydrazine, trisodium phosphate and hydroxy ethylidene-diphosphate are that 0.5:0.5:5:5 forms according to mass ratio), 2.5g polynite, 2.5g zeolite, 3.5g kaolin, 0.4g antioxidant b225,0.1g uv-absorbing agent UV-327,5g nitrogen phosphorus be mixture (being that 3:1:1 forms according to mass ratio by phosphorus oxychloride, trimeric cyanamide, tetramethylolmethane), 3g magnesium hydroxide, 2g aluminium hydroxide, is mixed into 100g compound;
Step (2). compound is joined to twin screw extruder and extrude, the processing temperature of twin screw extruder is 150 ℃ of feeding sections, 180 ℃ of fluxing zones, 205 ℃ of homogenizing zones, and head temperature is 195 ℃; In 40 ℃ of water-baths, carry out cold water drawing-off again, drawing-off multiplying power is 6 times, and last cutting machine cuts granulation, obtains containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic.
Above-described embodiment is not that the present invention is not limited only to above-described embodiment for restriction of the present invention, as long as meet requirement of the present invention, all belongs to protection scope of the present invention.
Claims (10)
1. containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic, be blend, it is characterized in that this blend comprises polypropylene, the composite anti copper agent of organic-inorganic, mineral filler, antioxidant, uv-absorbing agent, fire retardant; Each raw material at the quality percentage composition containing in the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic is: polypropylene 70～90 ﹪, composite anti copper agent 0.01～1 ﹪ of organic-inorganic, mineral filler 0.1～10 ﹪, antioxidant 0.1～0.5 ﹪, uv-absorbing agent 0.1～0.3 ﹪, fire retardant 5～20 ﹪.
2. as claimed in claim 1 a kind of containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic, it is characterized in that described polypropylene is the homopolymer of degree of isotacticity >=97 ﹪, melting index is 3～40g/10min.
3. as claimed in claim 1 a kind of containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic, it is characterized in that the described composite anti copper agent of organic-inorganic is that 1:10～10:1 forms by organic anti copper agent composition and inorganic anti copper agent composition according to mass ratio; Wherein organic anti copper agent composition is N, N '-bis-(o-hydroxy methyne) ethanedioyl two hydrazines, N, N'-is two, and [3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, (3,5-di-tert-butyl-hydroxy phenyl) propionic acid oxalyl (diimino-2,1-ethylidene ester), N, one or more in N-diacetyl adipic dihydrazide, salicylidene salicyl hydrazine; Inorganic anti copper agent composition is inorganic polyphosphate type, organophosphate type or both is composite, wherein inorganic polyphosphate type comprises one or more of tripoly phosphate sodium STPP, Sodium hexametaphosphate 99, trisodium phosphate, and organophosphate type comprises one or more in amino trimethylene methyl acid phosphate, hydroxy ethylidene-diphosphate, ethylenediamine tetramethylene phosphoric acid.
4. as claimed in claim 1 a kind of containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic, it is characterized in that described mineral filler is one or more in calcium carbonate, silicon oxide, talcum powder, attapulgite, polynite, zeolite, kaolin.
5. as claimed in claim 1 a kind of containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic, it is characterized in that described antioxidant is a kind of in antioxidant 1010, antioxidant b215, antioxidant b225, antioxidant 168, antioxidant 1076, antioxidant DLTP.
6. as claimed in claim 1 a kind of containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic, it is characterized in that described uv-absorbing agent is a kind of in UV-12, UV-326, UV-327, UV-328, UV-329, UV-770.
7. as claimed in claim 1 a kind of containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic, it is characterized in that described fire retardant is that nitrogen phosphorus is one or more in mixture, aluminium hydroxide, magnesium hydroxide; Nitrogen phosphorus is that mixture is that 3:1:1 forms by acid source, source of the gas, carbon source according to mass ratio, and acid source is phosphoric acid, Vanadium Pentoxide in FLAKES, phosphorus oxychloride or polyphosphoric acid amine, and source of the gas is trimeric cyanamide, and carbon source is tetramethylolmethane.
8. prepare a kind of method containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic as claimed in claim 1, it is characterized in that the method comprises the following steps:
Step (1). by polypropylene, the composite anti copper agent of organic-inorganic, mineral filler, antioxidant, uv-absorbing agent, fire retardant, be proportionally mixed into compound;
Prepare 100 weight parts containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic, each amount of substance used is: the polypropylene of 70～90 parts, the composite anti copper agent of organic-inorganic of 0.01～1 part, the mineral filler of 0.1～10 part, the antioxidant of 0.1～0.5 part, the uv-absorbing agent of 0.1～0.3 part, the fire retardant of 5～20 parts;
Step (2). compound is extruded by twin screw extruder, then through cold water drawing-off, granulation, obtained containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic;
Described polypropylene is the homopolymer of degree of isotacticity >=97 ﹪, and melting index is 3～40g/10min;
The composite anti copper agent of described organic-inorganic is that 1:10～10:1 forms by organic anti copper agent composition and inorganic anti copper agent composition according to mass ratio; Wherein organic anti copper agent composition is N, N '-bis-(o-hydroxy methyne) ethanedioyl two hydrazines, N, N'-is two, and [3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine, (3,5-di-tert-butyl-hydroxy phenyl) propionic acid oxalyl (diimino-2,1-ethylidene ester), N, one or more in N-diacetyl adipic dihydrazide, salicylidene salicyl hydrazine; Inorganic anti copper agent composition is inorganic polyphosphate type, organophosphate type or both is composite, wherein inorganic polyphosphate type comprises one or more of tripoly phosphate sodium STPP, Sodium hexametaphosphate 99, trisodium phosphate, and organophosphate type comprises one or more in amino trimethylene methyl acid phosphate, hydroxy ethylidene-diphosphate, ethylenediamine tetramethylene phosphoric acid;
Described mineral filler is one or more in calcium carbonate, silicon oxide, talcum powder, attapulgite, polynite, zeolite, kaolin;
Described antioxidant is a kind of in antioxidant 1010, antioxidant b215, antioxidant b225, antioxidant 168, antioxidant 1076, antioxidant DLTP;
Described uv-absorbing agent is a kind of in UV-12, UV-326, UV-327, UV-328, UV-329, UV-770;
Described fire retardant is that nitrogen phosphorus is one or more in mixture, aluminium hydroxide, magnesium hydroxide; Nitrogen phosphorus is that mixture is that 3:1:1 forms by acid source, source of the gas, carbon source according to mass ratio, and acid source is phosphoric acid, Vanadium Pentoxide in FLAKES, phosphorus oxychloride or polyphosphoric acid amine, and source of the gas is trimeric cyanamide, and carbon source is tetramethylolmethane.
9. a kind of preparation method containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic as claimed in claim 8, the processing temperature that it is characterized in that twin screw extruder is: 120～150 ℃ of feeding sections, 150～180 ℃ of fluxing zones, 180～205 ℃ of homogenizing zones, head temperature is 180～195 ℃.
10. a kind of preparation method containing the composite anti copper agent polypropylene composite material of poly-phosphate organic-inorganic as claimed in claim 8, the bath temperature that it is characterized in that cold water drawing-off is 10～40 ℃, drawing-off multiplying power is 2～6 times.
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