CN103059466A - 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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- CN103059466A CN103059466A CN2012105692067A CN201210569206A CN103059466A CN 103059466 A CN103059466 A CN 103059466A CN 2012105692067 A CN2012105692067 A CN 2012105692067A CN 201210569206 A CN201210569206 A CN 201210569206A CN 103059466 A CN103059466 A CN 103059466A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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 the polyvinyl chloride composite materials technical field, be specifically related to a kind of antiultraviolet environment-friendly PVC material modified and preparation method thereof.
Background technology
Polyvinyl chloride (PVC) is one of the earliest industrialization, broad-spectrum general-purpose thermoplastic plastic, the advantage such as it has, and quality is light, intensity is high, insulation, fire-retardant, corrosion-resistant, high comprehensive performance, cheap and starting material wide material sources; But also there is following shortcoming: 1, poor toughness, therefore very easily embrittlement when being hit can not be used as structured material, and in addition, the fragility temperature influence of polyvinyl chloride is very large, and general PVC goods are limited to-15 ℃ under using, and are limited to-30 ℃ under the use of flexible PVC; 2, poor heat stability, it just begins to decomposite HCl in the time of 100 ℃, decompose rapidlyer when being higher than 150 ℃, and the melt temperature of PVC is about 210 ℃; 3, the viscosity of PVC is high, and mobile extreme difference has limited its use to a certain extent.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 to disclose a kind of high-hydroscopicity PVC particulate material and preparation method thereof, raw material by following portions by weight is prepared from: PVC SG～3:90～100, carboxymethyl cellulose: 35～46, initiator DCP: 0.2～0.4, the 3rd monomer TMPTMA:3～5, antioxidant 1010: 0.3～0.5, plasticizer DOP: 75～86, metal soap stablizer: 4～6.
Application number is 200810218876.8 to disclose a kind of PVC plastic sealing material, component by following parts by weight is made: 100 parts of polyvinyl chloride resins, 55～85 parts in softening agent, 0.8～5 part of calcium zinc metal soap stablizer, 30～70 parts of weighting agents, 0～25 part of thermoplastic elastomer, 0.01～0.05 part of antiseptic-germicide, 0.5～1.5 part of toner, 0.5～2 part of composite synergist.
Application number is that 200710029001.9 to disclose a kind of PVC material modified and preparation method thereof, it is comprised 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 ray is one of three large main harm of harm plastic cable, optical cable, causes every year many accidents to occur, and brings about great losses economically, and the research of therefore carrying out antiultraviolet PVC material is very necessary; And existing antiultraviolet PVC material can not be accomplished the requirement of nontoxic environmental protection fully, researches and develops that a kind of PVC of environmental protection is material modified also to seem particularly important.
Summary of the invention
In order to overcome the shortcoming and defect that exists in the prior art, the object of the present invention is to provide a kind of antiultraviolet environment-friendly PVC material modified, the present invention makes material modifiedly has antiultraviolet and an oxidation resistant characteristic, greatly improved the work-ing life of PVC material in exposure air, environmental protection, and intensity is high, good flame retardation effect, compression performance and toughness are strong, and processing characteristics is good, excellent combination property.
Another object of the present invention is to provide a kind of antiultraviolet environment-friendly PVC material modified preparation method, preparation method's technique of the present invention is simple, convenient operation and control, and steady quality, production efficiency is high, but large-scale industrial production.
Purpose of the present invention is achieved through the following technical solutions: a kind of antiultraviolet environment-friendly PVC is material modified, and it is comprised of the raw material of following weight part:
80 ~ 120 parts of polyvinyl chloride resins
30 ~ 70 parts of weighting agents
41 ~ 80 parts in softening agent
1 ~ 10 part of fire retardant
1 ~ 10 part of stablizer
5 ~ 15 parts of impact modifiers
0.2 ~ 2 part of lubricant
0.5 ~ 1.5 part of photostabilizer
0.2 ~ 1 part in 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 is moulded S-70 or eastern Cao TG-800, is white powder or white particles shape, and 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 claims again modified calcium carbonate, surface treatment calcium carbonate, calcene or calcene, and the calcium of be called for short 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 as the filler of the industry such as imitation leather-making, electric wire, polyvinyl chloride, coating, printing ink and papermaking, can make finished product have certain tensile strength and smooth outward appearance.
Preferably, described softening agent is comprised of 1 ~ 10 part of 40 ~ 70 parts of Octyl adipates and epoxy soybean oil.
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, is a kind of universal primary plasticizer of excellent property, and DINP can be used as vinyl resin plasticizer, paracril tenderizer, the tensile strength auxiliary agent of celluloid lacquer etc.DINP compares 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 more environmental protection of DOP, be widely used in electric wire, film, all kinds of flexible PVC products 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 ℃), be a kind of most popular nontoxic polyvinyl chloride softening agent stablizer of holding concurrently.ESO and polyvinyl chloride resin consistency are good, volatility is low, transport property is little, has good thermostability and light stability, and water tolerance and oil-proofness are also good, can give goods good physical strength, weathering resistance and electrical property, and nontoxicity are the chemical technology auxiliary agents that is used for packaging material for food of international endorsement, all polrvinyl chloride products be can be widely used in, special ink, paint, coating, synthetic rubber and liquid metal soap class stablizer etc. also can be used for.
The composite use of diisononyl phthalate and 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 comprised of 0.5 ~ 4 part of 0.5 ~ 4 part of antimonous oxide and magnesium hydroxide.
Antimonous oxide is the fire retardant of using the earliest, be applicable to Resins, epoxy, urethane, chloroprene rubber, polystyrene, polyvinyl chloride, polyester etc., consumption wants large when using separately, flame retardant effect poor (unless flame retardant Halogen), when with halogen compound (R.HX) and time spent good synergistic effect being arranged then, flame retardant effect obviously improves.
Magnesium hydroxide is widely used in PE, PP, PVC, ABS, PS, HIPS, PA, PBT, unsaturated polyester, Resins, epoxy, rubber, the flame retardant filler of paint, chemical industry, the industrial circles such as environmental protection; Be used for good fire retardant and the weighting agent of the macromolecular materials 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 to use more widely.
Antimonous oxide and magnesium hydroxide are the 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 comprised of 0.5 ~ 5 part of 0.5 ~ 5 part of rare-earth stabilizer and metal soap stablizer.Rare-earth stabilizer is at least a in rare-earth stearate, fatty acid rare earth, Whitfield's ointment rare earth, citric acid rare earth, lauric acid rare earth and the sad rare earth; At least a in metal soap stablizer barium stearate, barium laurate, calcium stearate, calcium laurate, Zinc Stearate and the zinc laurate.
Rare-earth stabilizer has excellent thermal stability and has good coupled action, compares with lead salt, with PVC good compatible role is arranged, for PVC-CaCO
3, the system coupled action is better, is conducive to the raising of PVC plastic door and windows profile intensity.Good consistency and and CaCO with polyvinyl chloride resin and toughening agent C PE
3Coupled action, make polyvinyl chloride resin work in-process plasticizing evenly, plasticization temperature is low, the impact resistance of section bar is better; Rare earth element also has the ultraviolet function of the 230 ~ 320nm of absorption, makes rare-earth stabilizer can improve the weathering resistance of PVC, delays the goods weathering process.
The metal soap stablizer is the second largest class main stabilizer that consumption is only second to lead salt, though its thermostability has oilness concurrently not as lead salts.Metal soap can be metal (lead, barium, cadmium, zinc, the calcium etc.) salt of lipid acid (lauric acid, stearic acid, naphthenic acid etc.), and is wherein commonly used with stearate, is widely used in the flexible PVC, such as non-toxic type, transparent based article etc.
Rare-earth stabilizer and metal soap compound stabilizer use and can make material that good dispersiveness, consistency and processing fluidity are arranged in the course of processing, make the material good heat stability, have efficient weathering resistance.
Preferably, described impact modifier is that 2 ~ 7 parts of the butyl acrylate/methylmethacrylate copolymers of 3 ~ 8 parts of 25% ~ 45% chlorinatedpolyethylenees and 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.In polyvinyl chloride (PVC) resin, add an amount of CPE, can reduce resin melt viscosity, improve processing characteristics mobile, that improve plastics; Can also improve PVC shock strength, resistance to low temperature, weather resisteant energy, prolong work-ing life of goods.CPE is added in the calcic-plastic composite material, not only can replace Plasticizer DBP, also helps the Uniform Dispersion of calcium carbonate and polyvinyl chloride resin.
Butyl acrylate-methylmethacrylate copolymer is the class in the acrylic acid esters co-polymer (ACR), is a kind of PVC impact modifier of high comprehensive performance.ACR is the additives for plastics that has impact modification and processing modified dual-use function concurrently, because it has nucleocapsid structure, make its PVC goods have good shock resistance, low-temperature flexibility, with PVC consistency, weathering resistance, stability, processibility, and performance and cost ratio are moderate, can obviously improve PVC fluidity of molten, thermal distortion, promotion plastifies, product surface is bright and clean attractive in appearance.
Composite use can improve the weathering resistance of material as impact modifier for chlorinatedpolyethylene and butyl acrylate-methylmethacrylate copolymer, namely improve antiultraviolet and the resistance of oxidation of material, can also reduce material melt viscosity, improve processing characteristics mobile, that improve plastics, improve material shock strength, resistance to low temperature, weather resisteant energy, prolong work-ing life of goods.
Preferably, described lubricant is comprised of 0.1 ~ 0.8 part of 0.1 ~ 1.2 part of saturated hydrocarbons lubricant and fatty acid lubricant.The saturated hydrocarbons lubricant is at least a in paraffin, oxidized petroleum wax, whiteruss, polyethylene wax, native paraffin and the microcrystalline wax; The fatty acid lubricant is stearic acid.
Polyethylene wax (PE wax), white solid, density is 0.96 ~ 0.98, fusing point is 92 ℃, 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 lubrication, stronger internal lubrication effect is arranged again, can improve the production efficiency of plastic working, anti humility performance is good at normal temperatures, the chemical-resistant resistance ability is strong, and electrical property is good, 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 ℃, boiling point is 376.1 ℃, relative density is 0.9408, has good oilness and preferably light, heat stabilization, is widely used in the manufacturing of PVC plastic pipe, sheet material, section bar, film.In the plastic pvc pipe, stearic acid helps to prevent " coking " in the course of processing, and adding in the PVC processing film is a kind of effective thermo-stabilizer, can defend cruelly to place simultaneously the caused finished films variable color of sulfide.
The fatty acid lubricant is the metallic salt of higher fatty acid, is a kind of in the conventional lubricants, except having lubrication, or the PVC thermo-stabilizer, and saponified for a certain metal, the carbochain of the lipid acid of institute's combination is longer, and its oilness is better.
The saturated hydrocarbons lubricant is external lubricant, can reduce the friction of PVC melt and mould, machine barrel; The fatty acid lubricant is internal lubricant, can reduce the intermolecular friction of PVC melt; Two kinds of composite uses of lubricant can make material improve the flowability of material and the release property of goods in the course of processing.
Preferably, described UV light absorber is comprised of 744 0.2 ~ 0.6 part of 0.2 ~ 0.6 part of 0.1 ~ 0.3 part of ultraviolet absorbent UV-531, UV light absorber UV-327 and photostabilizer.
Ultraviolet absorbent UV-531 is Octabenzone, light yellow or white crystalline powder, absorbing wavelength is the ultraviolet ray of 270～330nm consumingly, can be used for various plastics, multiple plastics such as polyethylene, polypropylene, polystyrene, ABS resin, polycarbonate and polyvinyl chloride particularly, good with the consistency of resin, volatility is little.
UV light absorber UVP-327 be 2-(2 '-hydroxyl-3 ', 5 '-two uncle's phenyl)-5-chlorination benzotriazole, can strong absorption wavelength be the ultraviolet ray of 270～380 nanometers, chemical stability is good, volatility is minimum, with polyolefinic compatible lover, is specially adapted to polyethylene and polypropylene.In addition, also can be used for polyvinyl chloride, polymethylmethacrylate, polyoxymethylene, urethane, unsaturated polyester, ABS resin, Resins, epoxy and celluosic resin etc.Also have good heat-resisting sublimability, washing fastness, gasproof body fadedness and mechanical property retentivity are with antioxidant and with being significant synergistic effect.
Photostabilizer 744 is 4-benzoyloxy-2,2,6, the 6-tetramethyl piperidine, white crystalline powder, these product are for being subjected to the resistance type photostabilizer, itself does not almost absorb ultraviolet ability, but can effectively catch the living radical that macromolecular material produces under action of ultraviolet radiation, thereby performance light is stablized effectiveness, be applicable to the multiple plastics such as polypropylene, polyethylene, polystyrene, urethane, polymeric amide and polyester, effect is particularly outstanding in polyolefine, and photostabilization is the several times of general UV light absorber.Not painted, not pollute, heat-resisting processibility is good, with oxidation inhibitor and UV light absorber and usefulness, has good 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, the ultraviolet ray of energy strong absorption has good synergistic effect.
Preferably, described oxidation inhibitor is comprised of 0.1 ~ 0.4 part of 0.1 ~ 0.6 part of antioxidant 1010 and irgasfos 168.
Antioxidant 1010 is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, white crystalline powder, be Hinered phenols antioxidant, volatility is little, and anti-extractable is good, thermostability is high, long-lasting is long, and is not painted, do not pollute, nontoxic, be one of outstanding kind of present oxidation inhibitor.Polyethylene has remarkable antioxidant property, can effectively prevent the thermooxidative degradation of polymer materials in the long-term aging process, also is a kind of efficient processing stabilizers simultaneously, can improve the discoloration-resistant of polymer materials under the high temperature process condition.Antioxidant 1010 and anti-oxidant DLTP, irgasfos 168 can prolong the time limit of service of goods effectively also with synergistic effect is arranged.
Irgasfos 168 is three [2; the 4-di-tert-butyl-phenyl] phosphorous acid ester; white crystalline powder; it is a kind of auxiliary antioxidant; composite with primary antioxidant 1010 or antioxidant 1076; good synergistic effect is arranged, can effectively prevent polypropylene, the thermal destruction of polyethylene in basic injection moulding, give the extra long-effective protection of polymkeric substance.
Antioxidant 1010 and irgasfos 168 are environmental protection oxidation inhibitor, and composite use can delay or suppress the carrying out of material oxidation process, thereby stop the aging of material and prolong its work-ing life.
The material modified preparation method of a kind of antiultraviolet environment-friendly PVC comprises the steps:
(1) weight part by constitutive material takes by weighing polyvinyl chloride resin, weighting agent, softening agent, fire retardant, stablizer, impact modifier, lubricant, UV light absorber and oxidation inhibitor mixing;
(2) mixed raw material is put into the high speed blender, under 100 ~ 140 ℃ of temperature, stir 15 ~ 25min;
(3) raw material after will stirring makes the antiultraviolet environment-friendly PVC material modified by the twin screw extruder extruding pelletization.
Preferably, the extruder temperature of described twin screw extruder is: 138 ~ 160 ℃ of district's temperature, 135 ~ 160 ℃ of two district's temperature, 135 ~ 155 ℃ of three district's temperature, 130 ~ 148 ℃ of 132 ~ 150 ℃ of He Wu districts of four district's temperature temperature.
Beneficial effect of the present invention is: the material modified employing ultraviolet absorbent UV-531 of the antiultraviolet environment-friendly PVC that the present invention makes, UV light absorber UVP-327 and photostabilizer 744 are as the ultraviolet ray of the composite use energy of photostabilizer strong absorption; Adopt antioxidant 1010 and the composite use of irgasfos 168 can delay or suppress the carrying out of material oxidation process, thereby stop the aging of material and prolong its work-ing life; Adopt chlorinatedpolyethylene and butyl acrylate-methylmethacrylate copolymer can improve the weathering resistance of material as impact modifier, namely improve antiultraviolet and the resistance of oxidation of material, can also reduce material melt viscosity, improve processing characteristics mobile, that improve plastics, improve material shock strength, resistance to low temperature, weather resisteant energy, prolong work-ing life of goods; Adopt rare-earth stabilizer also can absorb ultraviolet ray, improve the weathering resistance of material, rare-earth stabilizer and metal soap stablizer can also make material that good dispersiveness, consistency and processing fluidity are arranged in the course of processing; Adopt 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; The employing calcene can improve hardness and the thermotolerance of material as weighting agent, can also improve surface luster and the profile pattern of material; Composite use can reach good flame retardant effect as fire retardant to adopt antimonous oxide and magnesium hydroxide, can also improve Drawing abillity and mechanical property; Adopt saturated hydrocarbons lubricant and the composite use of fatty acid lubricant can make material in the course of processing, improve the flowability of material and the release property of goods.
The material modified properties of the antiultraviolet environment-friendly PVC that the present invention makes has all exceeded national standard, have antiultraviolet and oxidation resistant characteristic, greatly improved the work-ing life of PVC material in exposure air, environmental protection, and intensity is high, good flame retardation effect, and compression performance and toughness are strong, processing characteristics is good, excellent combination property; The material modified smooth in appearance of antiultraviolet environment-friendly PVC that the present invention adopts multiple high-environmental material to make, do not contain phthalate, do not contain polycyclic aromatic hydrocarbons, do not contain free phenol, halogen-containing flame retardant not, without boron compound, environmental protection is better than the international standards such as the ROHS of European Union, 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, convenient operation and control, and steady quality, production efficiency is high, but large-scale industrial production.
Embodiment:
For the ease of those skilled in the art's understanding, the present invention is further illustrated below in conjunction with embodiment, and the content that embodiment is mentioned not is limitation of the invention.
Embodiment 1
Take by weighing 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 25% chlorinatedpolyethylene 3Kg, the butyl acrylate of butyl acrylate units content 50%-methylmethacrylate copolymer 2Kg, paraffin 0.1Kg, stearic acid 0.1Kg, Octabenzone 0.1Kg, 2-(2 '-hydroxyl-3 ', 5 '-two uncle's 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 the high speed blender, under 100 ℃ of temperature, stir 25min; Raw material after stirring by the twin screw extruder extruding pelletization, is made the antiultraviolet environment-friendly PVC material modified; The extruder temperature of described twin screw extruder is: 138 ℃ of district's temperature, 135 ℃ of two district's temperature, 135 ℃ of three district's temperature, 130 ℃ of 132 ℃ of He Wu districts of four district's temperature temperature.The material modified mechanical and physical performance of the antiultraviolet environment-friendly PVC that the present embodiment makes is as shown in table 1.
Embodiment 2
Take by weighing 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 30% chlorinatedpolyethylene 4Kg, the butyl acrylate of butyl acrylate units content 55%-methylmethacrylate copolymer 3Kg, oxidized petroleum wax 0.3Kg, stearic acid 0.2Kg, Octabenzone 0.2Kg, 2-(2 '-hydroxyl-3 ', 5 '-two uncle's 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 the high speed blender, under 140 ℃ of temperature, stir 15min; Raw material after stirring by the twin screw extruder extruding pelletization, is made the antiultraviolet environment-friendly PVC material modified; The extruder temperature of described twin screw extruder is: 140 ℃ of district's temperature, 140 ℃ of two district's temperature, 135 ℃ of three district's temperature, 135 ℃ of 135 ℃ of He Wu districts of four district's temperature temperature.The material modified mechanical and physical performance of the antiultraviolet environment-friendly PVC that the present embodiment makes is as shown in table 1.
Embodiment 3
Take by weighing 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 35% chlorinatedpolyethylene 5Kg, the butyl acrylate of butyl acrylate units content 60%-methylmethacrylate copolymer 4Kg, whiteruss 0.5Kg, stearic acid 0.4Kg, Octabenzone 0.3Kg, 2-(2 '-hydroxyl-3 ', 5 '-two uncle's 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 the high speed blender, under 120 ℃ of temperature, stir 20min; Raw material after stirring by the twin screw extruder extruding pelletization, is made the antiultraviolet environment-friendly PVC material modified; The extruder temperature of described twin screw extruder is: 160 ℃ of district's temperature, 160 ℃ of two district's temperature, 155 ℃ of three district's temperature, 148 ℃ of 150 ℃ of He Wu districts of four district's temperature temperature.The material modified mechanical and physical performance of the antiultraviolet environment-friendly PVC that the present embodiment makes is as shown in table 1.
Embodiment 4
Take by weighing 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 35% chlorinatedpolyethylene 6Kg, the butyl acrylate of butyl acrylate units content 65%-methylmethacrylate copolymer 5Kg, polyethylene wax 0.7Kg, stearic acid 0.6Kg, Octabenzone 0.1Kg, 2-(2 '-hydroxyl-3 ', 5 '-two uncle's 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 the high speed blender, under 120 ℃ of temperature, stir 20min; Raw material after stirring by the twin screw extruder extruding pelletization, is made the antiultraviolet environment-friendly PVC material modified; The extruder temperature of described twin screw extruder is: 155 ℃ of district's temperature, 155 ℃ of two district's temperature, 150 ℃ of three district's temperature, 145 ℃ of 148 ℃ of He Wu districts of four district's temperature temperature.The material modified mechanical and physical performance of the antiultraviolet environment-friendly PVC that the present embodiment makes is as shown in table 1.
Embodiment 5
Take by weighing 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 40% chlorinatedpolyethylene 7Kg, the butyl acrylate of butyl acrylate units content 70%-methylmethacrylate copolymer 6Kg, native paraffin 0.9Kg, stearic acid 0.7Kg, Octabenzone 0.2Kg, 2-(2 '-hydroxyl-3 ', 5 '-two uncle's 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 the high speed blender, under 100 ℃ of temperature, stir 25min; Raw material after stirring by the twin screw extruder extruding pelletization, is made the antiultraviolet environment-friendly PVC material modified; The extruder temperature of described twin screw extruder is: 150 ℃ of district's temperature, 150 ℃ of two district's temperature, 145 ℃ of three district's temperature, 140 ℃ of 140 ℃ of He Wu districts of four district's temperature temperature.The material modified mechanical and physical performance of the antiultraviolet environment-friendly PVC that the present embodiment makes is as shown in table 1.
Embodiment 6
Take by weighing 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 45% chlorinatedpolyethylene 8Kg, the butyl acrylate of butyl acrylate units content 75%-methylmethacrylate copolymer 7Kg, microcrystalline wax 1.2Kg, stearic acid 0.8Kg, Octabenzone 0.3Kg, 2-(2 '-hydroxyl-3 ', 5 '-two uncle's 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 the high speed blender, under 140 ℃ of temperature, stir 15min; Raw material after stirring by the twin screw extruder extruding pelletization, is made the antiultraviolet environment-friendly PVC material modified; The extruder temperature of described twin screw extruder is: 145 ℃ of district's temperature, 145 ℃ of two district's temperature, 140 ℃ of three district's temperature, 135 ℃ of 135 ℃ of He Wu districts of four district's temperature temperature.The material modified mechanical and physical performance of the antiultraviolet environment-friendly PVC that the present embodiment makes is as shown in table 1.
The material modified mechanical and physical performance of antiultraviolet environment-friendly PVC that table 1 embodiment 1 ~ 6 makes
As can be seen from Table 1, the antiultraviolet environment-friendly PVC that the present invention makes is material modified owing to having adopted 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-methylmethacrylate copolymer are as the composite use of impact modifier, rare-earth stabilizer and metal soap stablizer are as stablizer, so that this material modifiedly has stronger antiultraviolet and a resistance of oxidation, greatly improved the work-ing life of PVC material in exposure air, and this is material modified behind accumulation sun exposure 240h, and property indices is still better; The material modified properties of the antiultraviolet environment-friendly PVC that the present invention makes has all exceeded national standard, and intensity is high, good flame retardation effect, and compression performance and toughness are strong, and processing characteristics is good, excellent combination property; The material modified smooth in appearance of antiultraviolet environment-friendly PVC that the present invention adopts multiple high-environmental material to make, do not contain phthalate, do not contain polycyclic aromatic hydrocarbons, do not contain free phenol, halogen-containing flame retardant not, without boron compound, environmental protection is better than the international standards such as the ROHS of European Union, 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, convenient operation and control, and steady quality, production efficiency is high, but large-scale industrial production.
Above-described embodiment is the better implementation of the present invention, in addition, all right alternate manner realization of the present invention, any apparent replacement is all within protection scope of the present invention without departing from the inventive concept of the premise.
Claims (10)
1. an antiultraviolet environment-friendly PVC is material modified, it is characterized in that: it is comprised of the raw material of following weight part:
80 ~ 120 parts of polyvinyl chloride resins
30 ~ 70 parts of weighting agents
41 ~ 80 parts in softening agent
1 ~ 10 part of fire retardant
1 ~ 10 part of stablizer
5 ~ 15 parts of impact modifiers
0.2 ~ 2 part of lubricant
0.5 ~ 1.5 part of photostabilizer
0.2 ~ 1 part in oxidation inhibitor.
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 softening agent is comprised of 1 ~ 10 part of 40 ~ 70 parts of Octyl adipates and epoxy soybean oil; Described fire retardant is comprised of 0.5 ~ 6 part of 0.5 ~ 4 part of antimonous oxide and magnesium hydroxide.
4. a kind of antiultraviolet environment-friendly PVC according to claim 1 is material modified, it is characterized in that: described stablizer is comprised of 0.5 ~ 5 part of 0.5 ~ 5 part of rare-earth stabilizer and metal soap stablizer.
5. a kind of antiultraviolet environment-friendly PVC according to claim 1 is material modified, it is characterized in that: described impact modifier is that 2 ~ 7 parts of the butyl acrylate-methylmethacrylate copolymers of 3 ~ 8 parts of 25% ~ 45% chlorinatedpolyethylenees and butyl acrylate units content 50% ~ 75% form by chlorinity.
6. a kind of antiultraviolet environment-friendly PVC according to claim 1 is material modified, it is characterized in that: described lubricant is comprised of 0.1 ~ 0.8 part of 0.1 ~ 1.2 part of saturated hydrocarbons lubricant and fatty acid lubricant.
7. a kind of antiultraviolet environment-friendly PVC according to claim 1 is material modified, it is characterized in that: described photostabilizer is comprised of 744 0.2 ~ 0.6 part of 0.2 ~ 0.6 part of 0.1 ~ 0.3 part of ultraviolet absorbent UV-531, UV light absorber UV-327 and photostabilizer.
8. a kind of antiultraviolet environment-friendly PVC according to claim 1 is material modified, it is characterized in that: described oxidation inhibitor is comprised of 0.1 ~ 0.4 part of 0.1 ~ 0.6 part of antioxidant 1010 and irgasfos 168.
9. the material modified preparation method of each described a kind of antiultraviolet environment-friendly PVC of claim 1 ~ 8 is characterized in that: comprise the steps:
(1) weight part by constitutive material takes by weighing polyvinyl chloride resin, weighting agent, softening agent, fire retardant, stablizer, impact modifier, lubricant, UV light absorber and oxidation inhibitor mixing;
(2) mixed raw material is put into the high speed blender, under 100 ~ 140 ℃ of temperature, stir 15 ~ 25min;
(3) raw material after will stirring makes the antiultraviolet environment-friendly PVC material modified by the twin screw extruder extruding pelletization.
10. the material modified preparation method of a kind of antiultraviolet environment-friendly PVC according to claim 9, it is characterized in that: the extruder temperature of described twin screw extruder is: 138 ~ 160 ℃ of district's temperature, 135 ~ 160 ℃ of two district's temperature, 135 ~ 155 ℃ of three district's temperature, 130 ~ 148 ℃ of 132 ~ 150 ℃ of He Wu districts of four district's temperature temperature.
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Address after: Ye Wu industrial zone Dalingshan Meilin Village 523000 Guangdong city of Dongguan Province Patentee after: Guangdong Qi Long Technology Co., Ltd. Address before: Ye Wu industrial zone Dalingshan Meilin Village 523820 Guangdong city of Dongguan Province Patentee before: Dongguan Qilong Electricity Co., Ltd. |