CN103059468A - Low temperature resistant environment-friendly polyvinyl chloride (PVC) modified material and preparing method thereof - Google Patents
Low temperature resistant environment-friendly polyvinyl chloride (PVC) modified material and preparing method thereof Download PDFInfo
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- CN103059468A CN103059468A CN2012105694166A CN201210569416A CN103059468A CN 103059468 A CN103059468 A CN 103059468A CN 2012105694166 A CN2012105694166 A CN 2012105694166A CN 201210569416 A CN201210569416 A CN 201210569416A CN 103059468 A CN103059468 A CN 103059468A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
Abstract
The invention relates to the technical field of polyvinyl chloride composite materials, in particular to a low temperature resistant environment-friendly polyvinyl chloride (PVC) modified material and a preparing method thereof. The modified material comprises by weight, 80-120 parts of PVC resin, 20-45 parts of filling agent, 41-80 parts of plasticizer, 1-10 parts of cold-resistant modifying agent, 1-10 parts of fire retardant, 1-10 parts of stabilizing agent, 5-15 parts of impact modifier and 0.2-2 parts of lubricating agent. Each raw material is weighed by weight and mixed, after being stirred; the raw material is squeezed out of prilling through a double-screw extruder and the modified material is available. The low temperature resistant performance of the modified material manufactured by the preparing method is fine; the minimum usage temperature can reach below 65 DEG C. The modified material is environment-friendly and has the advantages of high intensity, good flame retardant effects, strong compression performance and toughness, excellent processing performance and better comprehensive performance. The preparing method of the low temperature resistant environment-friendly polyvinyl chloride (PVC) modified material has the advantages of being simple in technology, convenient to control and operate, stable in quality, high in production efficiency. In addition, the preparation method of the low temperature resistant environment-friendly polyvinyl chloride (PVC) modified material can be used for a large scale industrial production.
Description
Technical field
The present invention relates to the polyvinyl chloride composite materials technical field, be specifically related to a kind of low temperature resistant 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 201210199487.1 to disclose a kind of PVC thermoplastic elastic material, the polychloroethylene with high polymerization degree that comprises 100 weight parts, the softening agent of 50 to 80 weight parts, the snappiness properties-correcting agent of 30 to 50 weight parts, the thermo-stabilizer of 4 to 6 weight parts, the lubricant of 0.3 to 0.6 weight part, the processing aid of 1 to 3 weight part, 0.2 to the oxidation inhibitor of 0.5 weight part, the weighting agent of 5 to 10 weight parts.
Application number is 201110132493.0 to disclose a kind of automotive interior material PVC prescription, comprise polyvinyl chloride (PVC) RESINS, softening agent, tranquilizer, wherein, described polyvinyl chloride (PVC) RESINS is got 50～60 weight parts, described softening agent is got 40～50 weight parts, described tranquilizer is got 1.5～2.0 weight parts, described polyvinyl chloride (PVC) RESINS be for the K value be 70～80, viscosity is 1500～4500cps, and VCM content＜10ppm sieves residual＜1, number of impurity particles＜10, whiteness〉85 outward appearance is the polyvinyl chloride of white powder, and described softening agent is ester plasticizer, and described tranquilizer is the tranquilizer of organic tin.
The performance index of existing most of PVC material all are to satisfy the basic demand of national standard, under a lot of particular surroundingss such as low temperature environment, low temperature oil product or gas such as low temperature processed oil, natural gas liquids, oxyethane, liquid carbon dioxide and compressed natural gas etc. all require to use low temperature resistant PVC material in storage and use procedure, present PVC material property still can not satisfy the demand of life-time service under the cold condition reliably, minimum temperature also can only reach-30 ℃, and the resistance to low temperature of PVC material also needs further to optimize improvement; In addition, all there are quite serious pollution in existing PVC jacketed cable, PVC plug, PVC film and pvc pipe, can cause certain harm to HUMAN HEALTH, research and develop 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 low temperature resistant environment-friendly PVC material modified, the material modified resistance to low temperature that the present invention makes is good, minimum reaching-65 ℃, 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 low temperature resistant 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 low temperature resistant 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
20 ~ 45 parts of weighting agents
41 ~ 80 parts in softening agent
1 ~ 10 part of cold-resistant properties-correcting agent
1 ~ 10 part of fire retardant
1 ~ 10 part of stablizer
5 ~ 15 parts of impact modifiers
0.2 ~ 2 part of lubricant.
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 comprised of 10 ~ 20 parts of 10 ~ 25 parts of water-ground limestones and calcenes.
Water-ground limestone is 1250 orders, white powder, powdery mineral filler commonly used, have that chemical purity is high, inertia large, be difficult for chemical reaction, Heat stability is good, can not decompose below 400 ℃, whiteness is high, oil absorbency is low, refractive index is low, matter is soft, dry, do not contain crystal water, hardness is hanged down the advantages such as wear(ing)value is little, nontoxic, tasteless, odorless, good dispersity.
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.
Composite use can improve hardness and the thermotolerance of material as weighting agent for water-ground limestone and calcene, can also improve surface luster and the profile pattern of material.
Preferably, described softening agent is comprised of 1 ~ 10 part of 10 ~ 20 parts of 30 ~ 50 parts of diisononyl phthalate, Octyl adipate and epoxy soybean oil.
Octyl adipate (DOA), colourless transparent liquid, molecular formula is C
22H
42O
4, relative molecular mass is 370.24, relative density is 0.922, is a kind of cold-resistant plasticizer.The DOA plasticizing efficiency is high, and heated discoloration is little, and has certain photo and thermal stability and water tolerance, can give the good low-temperature pliability of goods and photostabilization; DOA is during as the good cold resistant plasticizer of polyvinyl chloride, give goods good low-temperature pliability, in plastisol, initial stage viscosity is low, viscosity stability is good, is used for the packaging film of cold-resistant agricultural film, electric wire, thin plate, leatheroid, outdoor water pipe and frozen product.
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 composite stabilizing agent etc. also can be used for.
The composite use of diisononyl phthalate, Octyl adipate 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 cold-resistant properties-correcting agent is comprised of 0.5 ~ 5 part of 0.5 ~ 5 part of paracril and cis-1,4-polybutadiene rubber.
Paracril (NBR) is the random copolymers that divinyl and vinyl cyanide obtain through letex polymerization, has good resistance to low temperature, the flexible PVC of its modification has the advantages such as low temperature elasticity is good, complete processing is good, and it also has good water tolerance, resistance to air loss and good adhesive property.Be widely used in the various oil resisting rubber goods of system, multiple oil seat gasket, pad, sleeve pipe, soft packaging, flexible rubber hose, printer's roll, cable gum material etc., in the industries such as automobile, aviation, oil, duplicating, become requisite resilient material.The polarity of paracril is very strong, and is generally not so good with the consistency of other polymkeric substance, but and cis-1,4-polybutadiene rubber, modified phenolic resins, polymkeric substance that the polyvinyl chloride isopolarity is strong, particularly have preferably consistency with chloride polymkeric substance.Described paracril is the paracril of the fine unit of propylene content 15% ~ 25%, and acrylonitrile content is higher, and oil-proofness is better, but then corresponding decline of winter hardiness.
Cis-1,4-polybutadiene rubber (BR) intermolecular forces is little, and molecular weight is high, thereby Chain Flexibility is large, and second-order transition temperature is low, is amorphous state when normal temperature is zero load, and very high deformability is arranged when bearing external force, is the best synthetic rubber of elasticity and winter hardiness.And because molecular chain is more regular, can obtain the crystallization reinforcement during stretching, add carbon black and can obtain again significant black-reinforced effect, be preferably conventional rubber of a kind of over-all properties.Cis-1,4-polybutadiene rubber is particularly suitable for doughnut processed and cold-resistant goods, can also make cushioning material and various rubber overshoes, adhesive plaster, adhesive tape and gelatin sponge etc.
Paracril and cis-1,4-polybutadiene rubber can improve the resistance to low temperature of material as the cold-resistant composite use of properties-correcting agent, can also improve consistency, impact and the processibility of material.
Preferably, described fire retardant is comprised of 0.5 ~ 6 part of 0.5 ~ 4 part of antimony peroxide and magnesium hydroxide.
Antimony peroxide is a kind of Sb system fire retardant, be applicable to Resins, epoxy, urethane, cis-1,4-polybutadiene 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.
Antimony peroxide 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 metal soap stablizer and organic tin stablizer.At least a in metal soap stablizer barium stearate, barium laurate, calcium stearate, calcium laurate, Zinc Stearate and the zinc laurate; The organic tin stablizer is at least a in dibutyl tin laurate, Bis(lauroyloxy)dioctyltin, dimethyl dimercapto 2-ethyl hexyl ethanoate tin, dimercapto 2-ethyl hexyl ethanoate dioctyltin, toxilic acid dioctyltin and the butyl maleate dibutyl tin.
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.
The organic tin stablizer is the most effective in the thermo-stabilizer, a most widely used class in transparent and nontoxic goods, and its outstanding advantages is: Heat stability is good, the transparency is good, most of nontoxic.
Metal soap stablizer and organic tin 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 chlorinity is 25 ~ 45% chlorinatedpolyethylene.
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.
Preferably, described lubricant is comprised of 0.1 ~ 0.8 part of 0.1 ~ 1.2 part of saturated hydrocarbons lubricant and aliphatic amide series lubricant agent.The saturated hydrocarbons lubricant is at least a in paraffin, oxidized petroleum wax, whiteruss, polyethylene wax, native paraffin and the microcrystalline wax; The aliphatic amide series lubricant agent is that stearic amide, fatty acid alkyl amide, erucicamide, palm fibre are put at least a of sour acid amides, methylene-bis stearylamide and ethylene bis stearic acid amide.
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.
The saturated hydrocarbons lubricant is external lubricant, can reduce the friction of PVC melt and mould, machine barrel; The aliphatic amide series lubricant agent 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.
The material modified preparation method of a kind of low temperature resistant environment-friendly PVC comprises the steps:
(1) weight part by constitutive material takes by weighing polyvinyl chloride resin, weighting agent, softening agent, cold-resistant properties-correcting agent, fire retardant, stablizer, impact modifier and mix lubricant;
(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 low temperature resistant 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 Octyl adipate of the low temperature resistant environment-friendly PVC that the present invention makes can improve the resistance to low temperature of material as cold resistant plasticizer, and composite use can also make material have the advantages such as heat-resisting, difficult volatilization, anti-extraction, flexibility and electrical insulation capability are good as softening agent for diisononyl phthalate, Octyl adipate and epoxy soybean oil; Employing paracril and cis-1,4-polybutadiene rubber can improve the resistance to low temperature of material as the cold-resistant composite use of properties-correcting agent, can also improve consistency, impact and the processibility of material; Simultaneously, adopt chlorinatedpolyethylene also can improve the resistance to low temperature of material as impact modifier, can also reduce material melt viscosity, improve processing characteristics mobile, that improve plastics, improve material shock strength, weather resisteant energy, prolong work-ing life of goods; Composite use can improve hardness and the thermotolerance of material as weighting agent to adopt water-ground limestone and calcene, can also improve surface luster and the profile pattern of material; Adopt metal soap stablizer and organic tin compound stabilizer to use and to 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; Composite use can reach good flame retardant effect as fire retardant to adopt antimony peroxide and magnesium hydroxide, can also improve Drawing abillity and mechanical property; Adopt saturated hydrocarbons lubricant and the composite use of aliphatic amide series lubricant agent 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 low temperature resistant environment-friendly PVC that the present invention makes has all exceeded national standard, and resistance to low temperature is good, and minimum use temperature reaches-65 ℃, environmental protection, and intensity is high, good flame retardation effect, compression performance and toughness are strong, and processing characteristics is good, excellent combination property; The material modified smooth in appearance of low temperature resistant 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, water-ground limestone 10Kg, calcene 10Kg, diisononyl phthalate 30Kg, Octyl adipate 10Kg, epoxy soybean oil 1Kg, paracril 0.5Kg, cis-1,4-polybutadiene rubber 0.5Kg, antimony peroxide 0.5Kg, magnesium hydroxide 0.5Kg, barium stearate 0.5Kg, dibutyl tin laurate 0.5Kg, chlorinity is 25% chlorinatedpolyethylene 5Kg, paraffin 0.1Kg, stearic amide 0.1Kg mix; 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 low temperature resistant 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 low temperature resistant 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, water-ground limestone 13Kg, calcene 12Kg, diisononyl phthalate 34Kg, Octyl adipate 12Kg, epoxy soybean oil 2Kg, paracril 1Kg, cis-1,4-polybutadiene rubber 1Kg, antimony peroxide 1Kg, magnesium hydroxide 2Kg, barium laurate 1Kg, Bis(lauroyloxy)dioctyltin 1Kg, chlorinity is 30% chlorinatedpolyethylene 7Kg, oxidized petroleum wax 0.3Kg, fatty acid alkyl amide 0.2Kg mix; 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 low temperature resistant 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 low temperature resistant 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, water-ground limestone 16Kg, calcene 14Kg, diisononyl phthalate 38Kg, Octyl adipate 14Kg, epoxy soybean oil 4Kg, paracril 2Kg, cis-1,4-polybutadiene rubber 2Kg, antimony peroxide 2Kg, magnesium hydroxide 3Kg, calcium stearate 2Kg, dimethyl dimercapto 2-ethyl hexyl ethanoate tin 2Kg, chlorinity is 30% chlorinatedpolyethylene 9Kg, whiteruss 0.5Kg, erucicamide 0.4Kg mix; 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 low temperature resistant 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 low temperature resistant 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, water-ground limestone 19Kg, calcene 16Kg, diisononyl phthalate 42Kg, Octyl adipate 16Kg, epoxy soybean oil 6Kg, paracril 3Kg, cis-1,4-polybutadiene rubber 3Kg, antimony peroxide 2.5Kg, magnesium hydroxide 4Kg, calcium laurate 3Kg, dimercapto 2-ethyl hexyl ethanoate dioctyltin 3Kg, chlorinity is 35% chlorinatedpolyethylene 11Kg, polyethylene wax 0.7Kg, palm fibre are put sour acid amides 0.4Kg and mix; 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 low temperature resistant 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 low temperature resistant 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, water-ground limestone 22Kg, calcene 18Kg, diisononyl phthalate 46Kg, Octyl adipate 18Kg, epoxy soybean oil 8Kg, paracril 4Kg, cis-1,4-polybutadiene rubber 4Kg, antimony peroxide 3Kg, magnesium hydroxide 5Kg, Zinc Stearate 4Kg, toxilic acid dioctyltin 4Kg, chlorinity is 40% chlorinatedpolyethylene 13Kg, native paraffin 0.9Kg, methylene-bis stearylamide 0.7Kg mix; 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 low temperature resistant 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 low temperature resistant 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, water-ground limestone 25Kg, calcene 20Kg, diisononyl phthalate 50Kg, Octyl adipate 20Kg, epoxy soybean oil 10Kg, paracril 5Kg, cis-1,4-polybutadiene rubber 5Kg, antimony peroxide 4Kg, magnesium hydroxide 6Kg, zinc laurate 5Kg, butyl maleate dibutyl tin 5Kg, chlorinity is 45% chlorinatedpolyethylene 15Kg, microcrystalline wax 1.2Kg, ethylene bis stearic acid amide 0.8Kg mix; 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 low temperature resistant 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 low temperature resistant environment-friendly PVC that the present embodiment makes is as shown in table 1.
The material modified mechanical and physical performance of low temperature resistant environment-friendly PVC that table 1 embodiment 1 ~ 6 makes
As can be seen from Table 1, the low temperature resistant environment-friendly PVC that the present invention makes is material modified owing to having adopted Octyl adipate to resist cold properties-correcting agent, chlorinatedpolyethylene as impact modifier as cold resistant plasticizer, paracril and cis-1,4-polybutadiene rubber conduct, so that this material modified resistance to low temperature is good, minimum use temperature reaches-65 ℃; The material modified properties of the low temperature resistant 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 low temperature resistant 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. a low temperature resistant 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
20 ~ 45 parts of weighting agents
41 ~ 80 parts in softening agent
1 ~ 10 part of cold-resistant properties-correcting agent
1 ~ 10 part of fire retardant
1 ~ 10 part of stablizer
5 ~ 15 parts of impact modifiers
0.2 ~ 2 part of lubricant.
2. a kind of low temperature resistant 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 comprised of 10 ~ 20 parts of 10 ~ 25 parts of water-ground limestones and calcenes.
3. a kind of low temperature resistant 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 10 ~ 20 parts of 30 ~ 50 parts of diisononyl phthalate, Octyl adipate and epoxy soybean oil.
4. a kind of low temperature resistant environment-friendly PVC according to claim 1 is material modified, it is characterized in that: described cold-resistant properties-correcting agent is comprised of 0.5 ~ 5 part of 0.5 ~ 5 part of paracril and cis-1,4-polybutadiene rubber.
5. a kind of low temperature resistant environment-friendly PVC according to claim 1 is material modified, it is characterized in that: described fire retardant is comprised of 0.5 ~ 6 part of 0.5 ~ 4 part of antimony peroxide and magnesium hydroxide.
6. a kind of low temperature resistant 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 metal soap stablizer and organic tin stablizer.
7. a kind of low temperature resistant environment-friendly PVC according to claim 1 is material modified, it is characterized in that: described impact modifier is that chlorinity is 25 ~ 45% chlorinatedpolyethylene.
8. a kind of low temperature resistant 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 aliphatic amide series lubricant agent.
9. the material modified preparation method of each described a kind of low temperature resistant 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, cold-resistant properties-correcting agent, fire retardant, stablizer, impact modifier and mix lubricant;
(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 low temperature resistant environment-friendly PVC material modified by the twin screw extruder extruding pelletization.
10. the material modified preparation method of a kind of low temperature resistant 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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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704977A (en) * | 2009-11-13 | 2010-05-12 | 江苏恒峰线缆有限公司 | Polyvinyl chloride/sulfonated cis-butadiene rubber and preparation method thereof |
| CN102731929A (en) * | 2012-06-18 | 2012-10-17 | 成都新兴富皇高分子材料科技有限公司 | PVC thermoplastic elastomer material and preparation method thereof |
-
2012
- 2012-12-25 CN CN201210569416.6A patent/CN103059468B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704977A (en) * | 2009-11-13 | 2010-05-12 | 江苏恒峰线缆有限公司 | Polyvinyl chloride/sulfonated cis-butadiene rubber and preparation method thereof |
| CN102731929A (en) * | 2012-06-18 | 2012-10-17 | 成都新兴富皇高分子材料科技有限公司 | PVC thermoplastic elastomer material and preparation method thereof |
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