CN103059466B - Ultraviolet-proof environmental-friendly polyvinyl chloride (PVC) modified material and preparation method thereof - Google Patents
Ultraviolet-proof environmental-friendly polyvinyl chloride (PVC) modified material and preparation method thereof 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
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- 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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Abstract
The invention relates to the technical field of polyvinyl chloride (PVC) composite materials, in particular to an ultraviolet-proof environmental-friendly PVC modified material and a preparation method of the ultraviolet-proof environmental-friendly PVC modified material. The modified material is composed of, by weight, 80-120 parts of PVC resin, 30-70 parts of filling agents, 41-80 parts of plasticizer, 1-10 parts of fire retardant, 1-10 parts of stabilizer, 5-15 parts of impact modifier, 0.2-2 parts of lubricating agents, 0.5-1.5 parts of light stabilizer and 0.2-1 part of antioxidant. The preparation method comprises the steps of weighing the raw materials according to the parts by weight, mixing the raw materials, after stirring, extruding prills through a twin-screw extruder, and obtaining the modified material. The modified material has the advantages of ultraviolet protection and oxygen resistance, service life of the PVC material exposed in air is greatly improved, environment is protected, strength is high, a fire retardant effect is good, compression performance and toughness are strong, processability is good, and an overall property is good.
Description
Technical field
The present invention relates to polyvinyl chloride composite materials technical field, it is material modified and preparation method thereof to be specifically related to a kind of antiultraviolet environment-friendly PVC.
Background technology
The advantages such as polyvinyl chloride (PVC) is one of industrialization the earliest, broad-spectrum general-purpose thermoplastic plastic, and it has, and quality is light, intensity is high, insulation, fire-retardant, corrosion-resistant, high comprehensive performance, cheap and raw material sources are extensive; But also there is following shortcoming: 1, poor toughness, very easily embrittlement when being hit, therefore can not be used as structured material, in addition, the fragility temperature influence of polyvinyl chloride is very large, and general PVC product uses lower limit to be-15 DEG C, and the use lower limit of flexible PVC is-30 DEG C; 2, poor heat stability, it just starts to decomposite HCl 100 DEG C time, more rapid higher than decomposing when 150 DEG C, and the melt temperature of PVC is about 210 DEG C; 3, the viscosity of PVC is high, mobility extreme difference, limits it to a certain extent and uses.People often adopt methods such as adding filler, elastomerics, softening agent, thermo-stabilizer, processing aid, heat-proof modifier and flow ability modifying agent to improve the performance of PVC.
Application number is 201110428758.1 disclose a kind of high-hydroscopicity PVC granule material and preparation method thereof, be prepared from by the raw material of following portions by weight: PVC SG ~ 3:90 ~ 100, carboxymethyl cellulose: 35 ~ 46, initiator DCP: 0.2 ~ 0.4, Third monomer TMPTMA:3 ~ 5, antioxidant 1010: 0.3 ~ 0.5, plasticizer DOP: 75 ~ 86, metal soap stablizer: 4 ~ 6.
Application number is 200810218876.8 disclose a kind of PVC plastic glue sealing material, be made up of the component of following parts by weight: polyvinyl chloride resin 100 parts, 55 ~ 85 parts, softening agent, calcium zinc metal soap stablizer 0.8 ~ 5 part, weighting agent 30 ~ 70 parts, thermoplastic elastomer 0 ~ 25 part, antiseptic-germicide 0.01 ~ 0.05 part, toner 0.5 ~ 1.5 part, composite synergist 0.5 ~ 2 part.
Application number is that 200710029001.9 to disclose a kind of PVC material modified and preparation method thereof, it is made up of following component and parts by weight: PVC 100, SAN 2 ~ 100, expanding material 0.2 ~ 30, modifier 1 ~ 10, mineral filler 5 ~ 80, thermo-stabilizer 0 ~ 10, lubricant 0 ~ 10, oxidation inhibitor 0 ~ 10, whipping agent 0 ~ 5.
At present, ultraviolet is one of the three large main harm of harm plastic cable, optical cable, and cause many accidents to occur every year, bring about great losses economically, the research therefore carrying out antiultraviolet PVC material is very necessary; And existing antiultraviolet PVC material can not accomplish the requirement of nontoxic environmental protection completely, research and develop that a kind of PVC of environmental protection is material modified also seems particularly important.
Summary of the invention
In order to overcome the shortcoming and defect existed in prior art, the object of the present invention is to provide a kind of antiultraviolet environment-friendly PVC material modified, what the present invention obtained material modifiedly has antiultraviolet and oxidation resistant characteristic, substantially increase the work-ing life of PVC material in exposure air, environmental protection, and intensity is high, good flame retardation effect, by force, processing characteristics is excellent, excellent combination property for compression performance and toughness.
Another object of the present invention is to the preparation method providing a kind of antiultraviolet environment-friendly PVC material modified, preparation method's technique of the present invention is simple, and convenient operation and control, steady quality, production efficiency is high, can large-scale industrial production.
Object of the present invention is achieved through the following technical solutions: a kind of antiultraviolet environment-friendly PVC is material modified, and it is made up of the raw material of following weight part:
Polyvinyl chloride resin 80 ~ 120 parts
Weighting agent 30 ~ 70 parts
41 ~ 80 parts, softening agent
Fire retardant 1 ~ 10 part
Stablizer 1 ~ 10 part
Impact modifier 5 ~ 15 parts
Lubricant 0.2 ~ 2 part
Photostabilizer 0.5 ~ 1.5 part
0.2 ~ 1 part, oxidation inhibitor.
Preferably, described polyvinyl chloride resin is SG-5 type polyvinyl chloride resin and/or SG-7 type polyvinyl chloride resin.
SG-5 type polyvinyl chloride resin is that platform is moulded S-65, is unified into US65, Dagu DG-1000, eastern Cao TG-1000 or eastern Cao TG-1300; white powder; mean polymerisation degree is 1100 ~ 1000; apparent density is 0.4 ~ 0.6g/mL, can be used for producing flexible film, leatheroid, sheet material, tubing, section bar, corrugated tube, cable protection pipe, flexible pipe, sole and various soft product.
SG-7 type polyvinyl chloride resin is that platform moulds S-70 or eastern Cao TG-800, and be white powder or white particles shape, mean polymerisation degree is 590 ~ 1500, and mean density is 1.40g/mL, can be used for the process for processing of polyvinyl chloride boardy product, soft goods, coating and tackiness agent.
Preferably, described weighting agent is calcene.
Calcene, also known as modified calcium carbonate, surface treatment calcium carbonate, calcene or calcene, is called for short calcium of living, is commonly used for the stopping composition of rubber, can make that rubber color and luster light is gorgeous, elongation is large, tensile strength is high, wear resisting property is good; Also be used as the filler of the industry such as imitation leather-making, electric wire, polyvinyl chloride, coating, ink and papermaking, finished product can be made to have certain tensile strength and smooth outward appearance.
Preferably, described softening agent is made up of Octyl adipate 40 ~ 70 parts and epoxy soybean oil 1 ~ 10 part.
Diisononyl phthalate (DINP), colourless oil liquid, molecular formula is C
26h
42o
4, molecular weight is 418.6, and density is 0.973 ~ 0.977, belongs to nontoxic epoxy plasticiser, and be a kind of universal primary plasticizer of excellent property, DINP can be used as vinyl resin plasticizer, paracril tenderizer, the tensile strength auxiliary agent etc. of celluloid lacquer.DINP, compared with o-phthalic acid dibutyl ester (DOP), has better aging resistance, ability of resisting to migration, anti-extraction ability, higher resistance to elevated temperatures, DINP is than DOP more environmental protection, be widely used in electric wire, film, all kinds of flexible PVC product such as toy and sheath.
Epoxy soybean oil (ESO), light yellow sticky oily liquids, molecular formula C
57h
106o
10, molecular weight is 951.46, viscosity 325mpa.S, refractive index 1.473(25 DEG C), be that a kind of most popular nontoxic polyvinyl chloride softening agent is held concurrently stablizer.ESO and polyvinyl chloride resin consistency good, volatility is low, transport property is little, has excellent thermostability and light stability, and water tolerance and oil-proofness are also good, the physical strength that goods are good can be given, weathering resistance and electrical property, and nontoxicity are the chemical technology auxiliary agents for packaging material for food of international endorsement, all polrvinyl chloride products can be widely used in, also can be used for special ink, paint, coating, synthetic rubber and liquid metal soap class stablizer etc.
Diisononyl phthalate and the composite use of epoxy soybean oil can make material have the advantages such as heat-resisting, cold-resistant, difficult volatilization, anti-extraction, flexibility and electrical insulation capability are good.
Preferably, described fire retardant is made up of antimonous oxide 0.5 ~ 4 part and magnesium hydroxide 0.5 ~ 4 part.
Antimonous oxide is the fire retardant applied the earliest, be applicable to epoxy resin, urethane, chloroprene rubber, polystyrene, polyvinyl chloride, polyester etc., when being used alone, consumption wants large, flame retardant effect difference (unless flame retardant Halogen), when with halide (R.HX) and the used time then have good synergistic effect, flame retardant effect significantly improves.
Magnesium hydroxide is widely used in PE, PP, PVC, ABS, PS, HIPS, PA, PBT, unsaturated polyester, epoxy resin, rubber, the flame retardant filler of paint, chemical industry, the industrial circles such as environmental protection; For excellent flame retardant and the weighting agent of the macromolecular material such as plastics, rubber, magnesium hydroxide can not only be fire-retardant as fire retardant, and can prevent from being fuming, do not produce dropping, do not produce toxic gas, therefore, obtains and apply more widely.
Antimonous oxide and magnesium hydroxide are inorganic environment-friendly fire retardant, and composite use can reach good flame retardant effect, can also improve Drawing abillity and mechanical property.
Preferably, described stablizer is made up of rare-earth stabilizer 0.5 ~ 5 part and metal soap stablizer 0.5 ~ 5 part.Rare-earth stabilizer is at least one in rare-earth stearate, fatty acid rare earth, Whitfield's ointment rare earth, citric acid rare earth, lauric acid rare earth and sad rare earth; At least one in metal soap stablizer barium stearate, barium laurate, calcium stearate, calcium laurate, Zinc Stearate and zinc laurate.
Rare-earth stabilizer has excellent thermal stability and has excellent coupled action, compared with lead salt, has good compatible role, for PVC-CaCO with PVC
3, system coupled action is better, is conducive to the raising of PVC plastic door and window profile material intensity.With good consistency and and the CaCO of polyvinyl chloride resin and toughening agent C PE
3coupled action, polyvinyl chloride resin work in-process is plastified evenly, and plasticization temperature is low, and the impact resistance of section bar is better; Rare earth element also has the ultraviolet function of absorption 230 ~ 320nm, makes rare-earth stabilizer can improve the weathering resistance of PVC, delays goods weathering process.
Metal soap stablizer is the second largest class main stabilizer that consumption is only second to lead salt, though its thermostability is not as lead salts, has oilness concurrently.Metal soap can be metal (lead, barium, cadmium, zinc, the calcium etc.) salt of lipid acid (lauric acid, stearic acid, naphthenic acid etc.), wherein conventional with stearate, is widely used in flexible PVC, as non-toxic type, transparent based article etc.
Rare-earth stabilizer and metal soap compound stabilizer use and can make material in the course of processing, have good dispersiveness, consistency and processing fluidity, make material good heat stability, have efficient weathering resistance.
Preferably, described impact modifier is that the chlorinatedpolyethylene 3 ~ 8 parts of 25% ~ 45% and the butyl acrylate/methylmethacrylate copolymer 2 ~ 7 parts of butyl acrylate units content 50% ~ 75% form by chlorinity.
Chlorinatedpolyethylene (CPE) is a kind of properties-correcting agent of thermoplastics, has good over-all properties.Appropriate CPE is added, the processing characteristics that can reduce the melt viscosity of resin, improve mobility, improve plastics in polyvinyl chloride (PVC) resin; The work-ing life of the shock strength of PVC, resistance to low temperature, weathering performance, prolongation goods can also be improved.CPE is added in calcic-plastic composite material, not only can replace Plasticizer DBP, also contributes to the dispersed of calcium carbonate and polyvinyl chloride resin.
Butyl acrylate-methyl ester copolymer is the class in acrylic acid esters co-polymer (ACR), is a kind of PVC impact modifier of high comprehensive performance.ACR is the additives for plastics having impact modification and processing modified dual-use function concurrently, because it has nucleocapsid structure, make its PVC product have excellent shock resistance, low-temperature flexibility, with PVC consistency, weathering resistance, stability, processibility, and performance and cost ratio moderate, can obviously improve PVC fluidity of molten, deformability, promote plasticizing, product surface is bright and clean attractive in appearance.
Chlorinatedpolyethylene and butyl acrylate-methyl ester copolymer can improve the weathering resistance of material as the composite use of impact modifier, namely antiultraviolet and the resistance of oxidation of material is improved, the processing characteristics that can also reduce the melt viscosity of material, improve mobility, improve plastics, improves the work-ing life of the shock strength of material, resistance to low temperature, weathering performance, prolongation goods.
Preferably, described lubricant is made up of saturated hydrocarbons lubricant 0.1 ~ 1.2 part and fatty acid lubricant 0.1 ~ 0.8 part.Saturated hydrocarbons lubricant is at least one in paraffin, oxidized petroleum wax, whiteruss, polyethylene wax, native paraffin and microcrystalline wax; Fatty acid lubricant is stearic acid.
Polyethylene wax (PE wax), white solid, density is 0.96 ~ 0.98, and fusing point is 92 DEG C, molecular weight is 2000 ~ 5000, has viscosity low, and softening temperature is high, the performances such as hardness is good, nontoxic, Heat stability is good, high-temperature volatile is low, to the dispersiveness of pigment, and existing extremely excellent external lubricity, have again stronger internal lubrication effect, can improve the production efficiency of plastic working, anti humility performance is good at normal temperatures, chemical-resistant resistance ability is strong, and electrical property is excellent, can improve the outward appearance of finished product.
Stearic acid is stearic acid 1801, is with the soft small pieces of glossiness white, and fusing point is 69.6 DEG C, boiling point is 376.1 DEG C, relative density is 0.9408, has good oilness and good light, heat stabilization, is widely used in the manufacture of PVC plastic pipe, sheet material, section bar, film.In plastic pvc pipe, stearic acid contributes to " coking " that prevent in the course of processing, and adding in PVC film processing is a kind of effective thermo-stabilizer, can defend cruelly to be placed in the caused finished films variable color of sulfide simultaneously.
Fatty acid lubricant is the metallic salt of higher fatty acid, is the one in conventional lubricants, except there is lubrication, or heat stabilizer for PVC, saponified for a certain metal, in conjunction with the carbochain of lipid acid longer, its oilness is better.
Saturated hydrocarbons lubricant is external lubricant, can reduce the friction of PVC melt and mould, machine barrel; Fatty acid lubricant is internal lubricant, can reduce the intermolecular friction of PVC melt; Two kinds of composite uses of lubricant can make material in the course of processing, improve the mobility of material and the release property of goods.
Preferably, described UV light absorber is made up of ultraviolet absorbent UV-531 0.1 ~ 0.3 part, UV light absorber UV-327 0.2 ~ 0.6 part and photostabilizer 744 0.2 ~ 0.6 part.
Ultraviolet absorbent UV-531 is Octabenzone, light yellow or white crystalline powder, can absorbing wavelength be the ultraviolet of 270 ~ 330nm consumingly, can be used for various plastics, the particularly multiple plastics such as polyethylene, polypropylene, polystyrene, ABS resin, polycarbonate and polyvinyl chloride, good with the consistency of resin, volatility is little.
UV light absorber UVP-327 be 2-(2 '-hydroxyl-3 ', 5 '-two tertiary phenyl)-5-chlorination benzotriazole, energy strong absorption wavelength is the ultraviolet of 270 ~ 380 nanometers, chemical stability is good, volatility is minimum, with polyolefinic compatible lover, be specially adapted to polyethylene and polypropylene.In addition, also can be used for polyvinyl chloride, polymethylmethacrylate, polyoxymethylene, urethane, unsaturated polyester, ABS resin, epoxy resin and celluosic resin etc.Also there is excellent heat-resisting sublimability, washing fastness, against gas transmission fadedness and mechanical property retentivity, with antioxidant and with being significant synergistic effect.
Photostabilizer 744 is 4-benzoyloxy-2,2,6,6-tetramethyl piperidine, white crystalline powder, these product are for being subject to resistance type photostabilizer, itself does not almost absorb ultraviolet ability, but effectively can catch the living radical that macromolecular material produces under action of ultraviolet radiation, thus performance light stablizes effectiveness, be applicable to the multiple plastics such as polypropylene, polyethylene, polystyrene, urethane, polymeric amide and polyester, in polyolefine, effect is particularly outstanding, and photostabilization is the several times of general UV light absorber.Not painted, do not pollute, resistance to hot workability is good, with oxidation inhibitor and UV light absorber and use, has excellent synergistic effect.
Ultraviolet absorbent UV-531 is benzophenone class photostabilizer, UV light absorber UVP-327 is benzotriazole light stabilizer, and photostabilizer 744 is hindered amine light stabilizer, three kinds of composite uses of photostabilizer, energy strong absorption ultraviolet, has excellent synergistic effect.
Preferably, described oxidation inhibitor is made up of antioxidant 1010 0.1 ~ 0.6 part and irgasfos 168 0.1 ~ 0.4 part.
Antioxidant 1010 is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, white crystalline powder, for Hinered phenols antioxidant, volatility is little, and resistance to extractable is good, thermostability is high, long-lasting is long, not painted, do not pollute, nontoxic, be one of outstanding kind of current oxidation inhibitor.Polyethylene has remarkable antioxidant property, effectively can prevent the thermooxidative degradation of polymer materials in long-term aging process, is also a kind of processing stabilizers efficiently simultaneously, can improves the discoloration-resistant of polymer materials under high temperature process condition.Antioxidant 1010 and anti-oxidant DLTP, irgasfos 168 with there being synergistic effect, effectively can extend the time limit of service of goods.
Irgasfos 168 is three [2; 4-di-tert-butyl-phenyl] phosphorous acid ester; white crystalline powder; it is a kind of auxiliary antioxidant; with primary antioxidant 1010 or antioxidant 1076 composite; there is good synergistic effect, effectively can prevent the thermal destruction in basic injection moulding of polypropylene, polyethylene, to the long-effective protection that polymkeric substance is extra.
Antioxidant 1010 and irgasfos 168 are environmental protection oxidation inhibitor, and composite use can delay or suppress the carrying out of material oxidation process, thus stop the aging of material and extend its work-ing life.
The preparation method that antiultraviolet environment-friendly PVC is material modified, comprises the steps:
(1) mixing of polyvinyl chloride resin, weighting agent, softening agent, fire retardant, stablizer, impact modifier, lubricant, photostabilizer and oxidation inhibitor is taken by the weight part of constitutive material;
(2) mixed raw material is put into high speed blender, at 100 ~ 140 DEG C of temperature, stir 15 ~ 25min;
(3) raw material after stirring is passed through twin screw extruder extruding pelletization, obtained antiultraviolet environment-friendly PVC is material modified.
Preferably, the extruder temperature of described twin screw extruder is: district's temperature 138 ~ 160 DEG C, two district's temperature 135 ~ 160 DEG C, three district's temperature 135 ~ 155 DEG C, four district's temperature 132 ~ 150 DEG CHe five district temperature 130 ~ 148 DEG C.
Beneficial effect of the present invention is: antiultraviolet environment-friendly PVC material modified employing ultraviolet absorbent UV-531, UV light absorber UVP-327 and photostabilizer 744 that the present invention obtains are as photostabilizer composite use energy strong absorption ultraviolet; Adopt antioxidant 1010 and the composite use of irgasfos 168 can delay or suppress the carrying out of material oxidation process, thus stop the aging of material and extend its work-ing life; Adopt chlorinatedpolyethylene and butyl acrylate-methyl ester copolymer can improve the weathering resistance of material as impact modifier, namely antiultraviolet and the resistance of oxidation of material is improved, the processing characteristics that can also reduce the melt viscosity of material, improve mobility, improve plastics, improves the work-ing life of the shock strength of material, resistance to low temperature, weathering performance, prolongation goods; Adopt rare-earth stabilizer also can absorb ultraviolet, improve the weathering resistance of material, rare-earth stabilizer and metal soap stablizer can also make material in the course of processing, have good dispersiveness, consistency and processing fluidity; Adopt diisononyl phthalate and the composite use of epoxy soybean oil that material can be made to have the advantages such as heat-resisting, cold-resistant, difficult volatilization, anti-extraction, flexibility and electrical insulation capability are good; Adopt calcene can improve hardness and the thermotolerance of material as weighting agent, surface luster and the profile pattern of material can also be improved; Adopt antimonous oxide and magnesium hydroxide can reach good flame retardant effect as the composite use of fire retardant, Drawing abillity and mechanical property can also be improved; Adopt saturated hydrocarbons lubricant and the composite use of fatty acid lubricant can make material in the course of processing, improve the mobility of material and the release property of goods.
The material modified properties of the antiultraviolet environment-friendly PVC that the present invention obtains is all beyond national standard, there is antiultraviolet and oxidation resistant characteristic, substantially increase the work-ing life of PVC material in exposure air, environmental protection, and intensity is high, good flame retardation effect, compression performance and toughness strong, processing characteristics is excellent, excellent combination property; The material modified smooth in appearance of antiultraviolet environment-friendly PVC that the present invention adopts multiple high-environmental material obtained, not containing phthalate, not containing polycyclic aromatic hydrocarbons, not containing free phenol, not halogen-containing flame retardant, without boron compound, environmental protection is better than the international standards such as European Union ROHS, DEHP, ATBC, can be widely used in the industrial circles such as automobile, electronic apparatus, instrument, weaving and building.
Preparation method's technique of the present invention is simple, and convenient operation and control, steady quality, production efficiency is high, can large-scale industrial production.
embodiment:
For the ease of the understanding of those skilled in the art, below in conjunction with embodiment, the present invention is further illustrated, and the content that embodiment is mentioned not is limitation of the invention.
Embodiment 1
Take raw material SG-5 type polyvinyl chloride resin 80Kg, calcene 30Kg, Octyl adipate 40Kg, epoxy soybean oil 1Kg, antimonous oxide 0.5Kg, magnesium hydroxide 0.5Kg, rare-earth stearate 0.5Kg, barium stearate 0.5Kg, chlorinity is the chlorinatedpolyethylene 3Kg of 25%, the butyl acrylate-methyl ester copolymer 2Kg of butyl acrylate units content 50%, paraffin 0.1Kg, stearic acid 0.1Kg, Octabenzone 0.1Kg, 2-(2 '-hydroxyl-3 ', 5 '-two tertiary phenyl)-5-chlorination benzotriazole 0.2Kg, 4-benzoyloxy-2, 2, 6, 6-tetramethyl piperidine 0.2Kg, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.1Kg, three [2, 4-di-tert-butyl-phenyl] phosphorous acid ester 0.1Kg mixes, mixed raw material is put into high speed blender, at 100 DEG C of temperature, stirs 25min, raw material after stirring is passed through twin screw extruder extruding pelletization, and obtained antiultraviolet environment-friendly PVC is material modified, the extruder temperature of described twin screw extruder is: district's temperature 138 DEG C, two district's temperature 135 DEG C, three district's temperature 135 DEG C, four district's temperature 132 DEG CHe five district temperature 130 DEG C.The material modified mechanical and physical performance of the antiultraviolet environment-friendly PVC that the present embodiment obtains is as shown in table 1.
Embodiment 2
Take raw material SG-7 type polyvinyl chloride resin 90Kg, calcene 28Kg, Octyl adipate 46Kg, epoxy soybean oil 2Kg, antimonous oxide 1Kg, magnesium hydroxide 2Kg, fatty acid rare earth 1Kg, barium laurate 1Kg, chlorinity is the chlorinatedpolyethylene 4Kg of 30%, the butyl acrylate-methyl ester copolymer 3Kg of butyl acrylate units content 55%, oxidized petroleum wax 0.3Kg, stearic acid 0.2Kg, Octabenzone 0.2Kg, 2-(2 '-hydroxyl-3 ', 5 '-two tertiary phenyl)-5-chlorination benzotriazole 0.4Kg, 4-benzoyloxy-2, 2, 6, 6-tetramethyl piperidine 0.4Kg, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.2Kg, three [2, 4-di-tert-butyl-phenyl] phosphorous acid ester 0.2Kg mixes, mixed raw material is put into high speed blender, at 140 DEG C of temperature, stirs 15min, raw material after stirring is passed through twin screw extruder extruding pelletization, and obtained antiultraviolet environment-friendly PVC is material modified, the extruder temperature of described twin screw extruder is: district's temperature 140 DEG C, two district's temperature 140 DEG C, three district's temperature 135 DEG C, four district's temperature 135 DEG CHe five district temperature 135 DEG C.The material modified mechanical and physical performance of the antiultraviolet environment-friendly PVC that the present embodiment obtains is as shown in table 1.
Embodiment 3
Take raw material SG-5 type polyvinyl chloride resin 100Kg, calcene 46Kg, Octyl adipate 52Kg, epoxy soybean oil 4Kg, antimonous oxide 2Kg, magnesium hydroxide 4Kg, Whitfield's ointment rare earth 2Kg, calcium stearate 2Kg, chlorinity is the chlorinatedpolyethylene 5Kg of 35%, the butyl acrylate-methyl ester copolymer 4Kg of butyl acrylate units content 60%, whiteruss 0.5Kg, stearic acid 0.4Kg, Octabenzone 0.3Kg, 2-(2 '-hydroxyl-3 ', 5 '-two tertiary phenyl)-5-chlorination benzotriazole 0.6Kg, 4-benzoyloxy-2, 2, 6, 6-tetramethyl piperidine 0.6Kg, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.3Kg, three [2, 4-di-tert-butyl-phenyl] phosphorous acid ester 0.3Kg mixes, mixed raw material is put into high speed blender, at 120 DEG C of temperature, stirs 20min, raw material after stirring is passed through twin screw extruder extruding pelletization, and obtained antiultraviolet environment-friendly PVC is material modified, the extruder temperature of described twin screw extruder is: district's temperature 160 DEG C, two district's temperature 160 DEG C, three district's temperature 155 DEG C, four district's temperature 150 DEG CHe five district temperature 148 DEG C.The material modified mechanical and physical performance of the antiultraviolet environment-friendly PVC that the present embodiment obtains is as shown in table 1.
Embodiment 4
Take raw material SG-5 type polyvinyl chloride resin 50Kg, SG-7 type polyvinyl chloride resin 50Kg, calcene 56Kg, Octyl adipate 58Kg, epoxy soybean oil 6Kg, antimonous oxide 2.5Kg, magnesium hydroxide 4Kg, citric acid rare earth 3Kg, calcium laurate 3Kg, chlorinity is the chlorinatedpolyethylene 6Kg of 35%, the butyl acrylate-methyl ester copolymer 5Kg of butyl acrylate units content 65%, polyethylene wax 0.7Kg, stearic acid 0.6Kg, Octabenzone 0.1Kg, 2-(2 '-hydroxyl-3 ', 5 '-two tertiary phenyl)-5-chlorination benzotriazole 0.2Kg, 4-benzoyloxy-2, 2, 6, 6-tetramethyl piperidine 0.2Kg, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.4Kg, three [2, 4-di-tert-butyl-phenyl] phosphorous acid ester 0.2Kg mixes, mixed raw material is put into high speed blender, at 120 DEG C of temperature, stirs 20min, raw material after stirring is passed through twin screw extruder extruding pelletization, and obtained antiultraviolet environment-friendly PVC is material modified, the extruder temperature of described twin screw extruder is: district's temperature 155 DEG C, two district's temperature 155 DEG C, three district's temperature 150 DEG C, four district's temperature 148 DEG CHe five district temperature 145 DEG C.The material modified mechanical and physical performance of the antiultraviolet environment-friendly PVC that the present embodiment obtains is as shown in table 1.
Embodiment 5
Take raw material SG-7 type polyvinyl chloride resin 110Kg, calcene 62Kg, Octyl adipate 64Kg, epoxy soybean oil 8Kg, antimonous oxide 3Kg, magnesium hydroxide 5Kg, lauric acid rare earth 4Kg, Zinc Stearate 4Kg, chlorinity is the chlorinatedpolyethylene 7Kg of 40%, the butyl acrylate-methyl ester copolymer 6Kg of butyl acrylate units content 70%, native paraffin 0.9Kg, stearic acid 0.7Kg, Octabenzone 0.2Kg, 2-(2 '-hydroxyl-3 ', 5 '-two tertiary phenyl)-5-chlorination benzotriazole 0.4Kg, 4-benzoyloxy-2, 2, 6, 6-tetramethyl piperidine 0.4Kg, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.5Kg, three [2, 4-di-tert-butyl-phenyl] phosphorous acid ester 0.3Kg mixes, mixed raw material is put into high speed blender, at 100 DEG C of temperature, stirs 25min, raw material after stirring is passed through twin screw extruder extruding pelletization, and obtained antiultraviolet environment-friendly PVC is material modified, the extruder temperature of described twin screw extruder is: district's temperature 150 DEG C, two district's temperature 150 DEG C, three district's temperature 145 DEG C, four district's temperature 140 DEG CHe five district temperature 140 DEG C.The material modified mechanical and physical performance of the antiultraviolet environment-friendly PVC that the present embodiment obtains is as shown in table 1.
Embodiment 6
Take raw material SG-5 type polyvinyl chloride resin 60Kg, SG-7 type polyvinyl chloride resin 60Kg, calcene 70Kg, Octyl adipate 70Kg, epoxy soybean oil 10Kg, antimonous oxide 4Kg, magnesium hydroxide 6Kg, sad rare earth 5Kg, zinc laurate 5Kg, chlorinity is the chlorinatedpolyethylene 8Kg of 45%, the butyl acrylate-methyl ester copolymer 7Kg of butyl acrylate units content 75%, microcrystalline wax 1.2Kg, stearic acid 0.8Kg, Octabenzone 0.3Kg, 2-(2 '-hydroxyl-3 ', 5 '-two tertiary phenyl)-5-chlorination benzotriazole 0.6Kg, 4-benzoyloxy-2, 2, 6, 6-tetramethyl piperidine 0.6Kg, four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.6Kg, three [2, 4-di-tert-butyl-phenyl] phosphorous acid ester 0.4Kg mixes, mixed raw material is put into high speed blender, at 140 DEG C of temperature, stirs 15min, raw material after stirring is passed through twin screw extruder extruding pelletization, and obtained antiultraviolet environment-friendly PVC is material modified, the extruder temperature of described twin screw extruder is: district's temperature 145 DEG C, two district's temperature 145 DEG C, three district's temperature 140 DEG C, four district's temperature 135 DEG CHe five district temperature 135 DEG C.The material modified mechanical and physical performance of the antiultraviolet environment-friendly PVC that the present embodiment obtains is as shown in table 1.
The mechanical and physical performance that the antiultraviolet environment-friendly PVC that table 1 embodiment 1 ~ 6 obtains is material modified
As can be seen from Table 1, the antiultraviolet environment-friendly PVC that the present invention obtains is material modified owing to have employed ultraviolet absorbent UV-531, UV light absorber UVP-327 and photostabilizer 744 are as photostabilizer, antioxidant 1010 and irgasfos 168 are as oxidation inhibitor, chlorinatedpolyethylene and butyl acrylate-methyl ester copolymer are as the composite use of impact modifier, rare-earth stabilizer and metal soap stablizer are as stablizer, this is made material modifiedly to have stronger antiultraviolet and resistance of oxidation, substantially increase the work-ing life of PVC material in exposure air, and this is material modified after accumulation sun exposure 240h, property indices is still better, the material modified properties of the antiultraviolet environment-friendly PVC that the present invention obtains is all beyond national standard, and intensity is high, good flame retardation effect, compression performance and toughness strong, processing characteristics is excellent, excellent combination property, the material modified smooth in appearance of antiultraviolet environment-friendly PVC that the present invention adopts multiple high-environmental material obtained, not containing phthalate, not containing polycyclic aromatic hydrocarbons, not containing free phenol, not halogen-containing flame retardant, without boron compound, environmental protection is better than the international standards such as European Union ROHS, DEHP, ATBC, can be widely used in the industrial circles such as automobile, electronic apparatus, instrument, weaving and building.
Preparation method's technique of the present invention is simple, and convenient operation and control, steady quality, production efficiency is high, can large-scale industrial production.
Above-described embodiment is the present invention's preferably implementation, and in addition, the present invention can also realize by alternate manner, and any apparent replacement is all within protection scope of the present invention without departing from the inventive concept of the premise.
Claims (4)
1. an antiultraviolet environment-friendly PVC is material modified, it is characterized in that: it is made up of the raw material of following weight part:
Polyvinyl chloride resin 80 ~ 120 parts
Weighting agent 30 ~ 70 parts
41 ~ 80 parts, softening agent
Fire retardant 1 ~ 10 part
Stablizer 1 ~ 10 part
Impact modifier 5 ~ 15 parts
Lubricant 0.2 ~ 2 part
Photostabilizer 0.5 ~ 1.5 part
0.2 ~ 1 part, oxidation inhibitor;
Wherein, described softening agent is made up of Octyl adipate 40 ~ 70 parts and epoxy soybean oil 1 ~ 10 part; Described fire retardant is made up of antimonous oxide 0.5 ~ 4 part and magnesium hydroxide 0.5 ~ 6 part;
Described stablizer is made up of rare-earth stabilizer 0.5 ~ 5 part and metal soap stablizer 0.5 ~ 5 part;
Described impact modifier is that the chlorinatedpolyethylene 3 ~ 8 parts of 25% ~ 45% and the butyl acrylate-methyl ester copolymer 2 ~ 7 parts of butyl acrylate units content 50% ~ 75% form by chlorinity;
Described lubricant is made up of saturated hydrocarbons lubricant 0.1 ~ 1.2 part and fatty acid lubricant 0.1 ~ 0.8 part;
Described photostabilizer is made up of ultraviolet absorbent UV-531 0.1 ~ 0.3 part, UV light absorber UV-327 0.2 ~ 0.6 part and photostabilizer 744 0.2 ~ 0.6 part.
2. a kind of antiultraviolet environment-friendly PVC according to claim 1 is material modified, it is characterized in that: described polyvinyl chloride resin is SG-5 type polyvinyl chloride resin and/or SG-7 type polyvinyl chloride resin; Described weighting agent is calcene.
3. a kind of antiultraviolet environment-friendly PVC according to claim 1 is material modified, it is characterized in that: described oxidation inhibitor is made up of antioxidant 1010 0.1 ~ 0.6 part and irgasfos 168 0.1 ~ 0.4 part.
4. the preparation method that a kind of antiultraviolet environment-friendly PVC described in any one of claim 1 ~ 3 is material modified, is characterized in that: comprise the steps:
(1) mixing of polyvinyl chloride resin, weighting agent, softening agent, fire retardant, stablizer, impact modifier, lubricant, photostabilizer and oxidation inhibitor is taken by the weight part of constitutive material;
(2) mixed raw material is put into high speed blender, at 100 ~ 140 DEG C of temperature, stir 15 ~ 25min;
(3) raw material after stirring is passed through twin screw extruder extruding pelletization, obtained antiultraviolet environment-friendly PVC is material modified;
Wherein, the extruder temperature of described twin screw extruder is: district's temperature 138 ~ 160 DEG C, two district's temperature 135 ~ 160 DEG C, three district's temperature 135 ~ 155 DEG C, four district's temperature 132 ~ 150 DEG CHe five district temperature 130 ~ 148 DEG C.
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