CN104109324B - A kind of insulating environment-friendly PVC is material modified and preparation method thereof - Google Patents
A kind of insulating environment-friendly PVC is material modified and preparation method thereof Download PDFInfo
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- CN104109324B CN104109324B CN201410374022.4A CN201410374022A CN104109324B CN 104109324 B CN104109324 B CN 104109324B CN 201410374022 A CN201410374022 A CN 201410374022A CN 104109324 B CN104109324 B CN 104109324B
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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
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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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
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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
- B29C48/92—Measuring, controlling or regulating
-
- 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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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Abstract
The present invention relates to the material modified technical field of PVC, it is specifically related to a kind of insulating environment-friendly PVC material modified and preparation method thereof, polyvinyl chloride resin 80 120 parts, filler 40 60 parts, 40 60 parts of plasticizer, insulation modifying agent 10 15 parts, heat stabilizer 37 parts, lubricant 0.5 1.5 parts；The mixture that described plasticizer is made up of with weight ratio 5 7:1 DOTP and tri-n-butyl citrate；The mixture that described insulation modifying agent is made up of with weight ratio 2 4:1.5 2.5:1 kaolin, titanium dioxide and glass microballoon, wherein, the particle diameter of described glass microballoon is less than 20 μm.This material modified properties is all beyond national standard, good insulation preformance, and resistivity is up to 5.1 × 1014Ω, environmental protection.The preparation method technique of the present invention is simple, convenient operation and control, steady quality, and production efficiency is high, can large-scale industrial production.
Description
Technical field
The present invention relates to the material modified technical field of PVC, be specifically related to a kind of insulating environment-friendly PVC material modified and preparation method thereof.
Background technology
Polyvinyl chloride (PVC) is industrialization, one of broad-spectrum general-purpose thermoplastic plastic the earliest, it has, and light weight, intensity is high, insulation, fire-retardant, corrosion-resistant, high comprehensive performance, the cheap and raw material sources advantage such as extensively；But there is also following shortcoming: 1, poor toughness, easily embrittlement when being hit, therefore cannot act as structural material, it addition, the fragility of polyvinyl chloride is greatly influenced by temperature, 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 begins to decomposite HCl when 100 DEG C, decomposes more rapid, and the melt temperature of PVC is about 210 DEG C during higher than 150 DEG C；3, the viscosity of PVC is high, mobility extreme difference, limits it to a certain extent and uses.People improve the performance of PVC frequently with methods such as adding filler, elastomer, plasticizer, heat stabilizer, processing aid, heat-proof modifier and flow ability modifying agent.
Application No. 201110428758.1 discloses a kind of high-hydroscopicity PVC granule material and preparation method thereof, it is prepared from by the raw material of following portions by weight: PVC SG～3:90～100, carboxymethylcellulose calcium: 35～46, initiator DCP: 0.2～0.4, Third monomer TMPTMA:3～5, antioxidant 1010: 0.3～0.5, plasticizer DOP: 75～86, compound stabilizer: 4～6.
Application No. 200810218876.8 discloses a kind of PVC plastic glue encapsulant, it is made up of the component of following parts by weight: polyvinyl chloride resin 100 parts, plasticizer 55～85 parts, calcium-zinc composite stabilizing agent 0.8～5 parts, filler 30～70 parts, thermoplastic elastomer (TPE) 0～25 parts, antiseptic 0.01～0.05 part, toner 0.5～1.5 parts, composite synergist 0.5～2 parts.
It is material modified and preparation method thereof that Application No. 200710029001.9 discloses a kind of PVC, it is made up of following component and parts by weight: PVC 100, SAN 2～100, bulking agent 0.2～30, modifier 1～10, inorganic filler 5～80, heat stabilizer 0～10, lubricant 0～10, antioxidant 0～10, foaming agent 0～5.
The performance indications of existing major part PVC material are all to meet the basic demand of national standard, and the insulating properties of current PVC material is not good enough, and therefore, the insulating properties of PVC material also needs to optimize improvement further；Additionally, existing PVC sheath cable, PVC plug, PVC film and pvc pipe all exist the most serious pollution, health can be caused certain harm, research and develop that the PVC of a kind of environmental protection is material modified to be also particularly important.
Summary of the invention
In order to overcome shortcoming and defect present in prior art, it is an object of the invention to provide a kind of insulating environment-friendly PVC material modified, this material modified good insulating, environmental protection, and resistance to gentle weather resistance is excellent, excellent shock resistance, good flame retardation effect, processing characteristics is excellent, excellent combination property.
Another object of the present invention is to provide a kind of preparation method material modified for insulating environment-friendly PVC, this preparation method technique is simple, convenient operation and control, steady quality, and production efficiency is high, can large-scale industrial production.
The purpose of the present invention is achieved through the following technical solutions: a kind of insulating environment-friendly PVC is material modified, including the raw material of following weight portion:
Polyvinyl chloride resin 80-120 part
Filler 40-60 part
Plasticizer 40-60 part
Insulation modifying agent 10-15 part
Heat stabilizer 3-7 part
Lubricant 0.5-1.5 part；
The mixture that described plasticizer is made up of with weight ratio 5-7:1 DOTP and tri-n-butyl citrate.
DOTP (DOTP), the low-viscosity (mobile) liquid of near colorless, molecular formula is C24H38O4, molecular weight is 390.30, and density is 0.981-0.986g/mL, is the primary plasticizer of a kind of function admirable of polyvinyl chloride (PVC) plastics.It is compared with at present conventional diisooctyl phthalate (DOP), has the advantages such as heat-resisting, cold-resistant, difficulty volatilization, anti-extraction, flexibility and electrical insulation capability are good, demonstrates that excellent persistence, resistance to soap is aqueous and low-temperature pliability in goods.
Tri-n-butyl citrate (TBC) is a kind of good environment-friendly plasticizer, under normal temperature for nontoxic, have fruital taste, colourless transparent oil liquid, boiling point 170 DEG C (133.3Pa), flash-point (opening cup) 185 DEG C, be dissolved in most organic solvent.Volatility is little, good with the compatibility of resin, and plasticizing efficiency is high, is allowed for the industries such as packaging for foodstuff and health care goods, and the soft toy of children, pharmacy, medical product, essence and flavoring agent, cosmetics manufacture in countries such as America and Europes.The good cold resistance of goods, resistance to water and fungus resistance can be given.Resin presents the good transparency and low temperature warpage performance after this product plasticising, and has low volatility and low extractable, Heat stability is good, heat nondiscolouring in different medium.The lubricating oil prepared by this product has good greasy property.
The present invention uses DOTP and tri-n-butyl citrate as plasticizer, two kinds of plasticizer are environment-friendly plasticizer, the active force of PVC molecule interchain can be reduced, the vitrification point of PVC plastic, flowing temperature is made all to reduce with the fusing point of contained crystallite, plasticizer can improve the plasticity of resin, makes goods softness, resistance to low temperature good；When two kinds of plasticizer use so that weight ratio 5-7:1 is compounding, flexibility and the resistance to low temperature of goods can be improved.
The mixture that described insulation modifying agent is made up of with weight ratio 2-4:1.5-2.5:1 kaolin, titanium dioxide and glass microballoon, wherein, the particle diameter of described glass microballoon is less than 20 μm.
The present invention uses kaolin, titanium dioxide and glass microballoon as insulation modifying agent, kaolin, titanium dioxide filled PVC, can make the insulation effect of raising goods；Due to the high resistivity characteristic of glass microballoon, use the specific insulation of the goods of glass microballoon filled PVC can meet and exceed 1 × 1013, when kaolin, titanium dioxide and glass microballoon use so that weight ratio 2-4:1.5-2.5:1 is compounding, prepared PVC material has preferable insulating properties.
Preferably, also including impact modifier 5-15 part, described impact modifier is acrylonitrile-butadiene-styrene terpolymer, and wherein, the content of acrylonitrile unit is 25-35%, and the content of butadiene unit is 15-25%, and the content of styrene units is 40-60%.
Acrylonitrile-butadiene-styrene terpolymer (ABS), it is a kind of impact modifier, there is excellent combination property, have fabulous heat resistance, impact strength, good stability of the dimension, electrical property, wearability, chemical proof, dyeability, processing and forming and machining are preferable.PVC/ABS alloy material had both had the advantages such as the corrosion resistance of PVC, high rigidity, fire-retardant and electrical insulating property be good, has again the advantages such as the heat resistance of ABS, molding processibility, good impact resistance concurrently, is a kind of ideal material.The present invention is by selecting acrylonitrile-butadiene-styrene terpolymer as impact modifier, and control the content of acrylonitrile unit at 15-35%, the content of butadiene unit is at 5-30%, the content of styrene units is at 40-60%, prepare material good impact resistance, and heat resistance and processing characteristics excellent.
Preferably, described polyvinyl chloride resin be particle diameter in 0.1-0.2mm, apparent density at 0.4-0.5g/cm3Polyvinyl chloride resin.
The polyvinyl chloride resin that the present invention uses is the loose type resin that suspension method prepares, surface imperfection, and porous is spherical in cotton, easily absorbs plasticizer；The present invention by by the size controlling of polyvinyl chloride resin at 0.1-0.2mm, the apparent density of polyvinyl chloride resin is controlled at 0.4-0.5g/cm3So that material plasticizing rate is fast, is easily worked.
Preferably, described filler is particle diameter at 20-200nm and the nm-class active calcium carbonate that processed through maleic anhydride graft phenylethene-isoprene-styrene block copolymer.
The particle diameter of filler is the least, and hot strength and impact strength to packing material are the most useful, and the present invention, by selecting super nm-class active calcium carbonate as filler and to control its particle diameter at 20-200nm, can improve the intensity of material；The compatibility that filler is good with resin is to play its effect and control the key of addition, the present invention uses the nm-class active calcium carbonate processed through compatilizer maleic anhydride graft phenylethene-isoprene-styrene block copolymer, the compatibility of nm-class active calcium carbonate and polyvinyl chloride resin can be improved, thus improve the intensity of material.
Preferably, described heat stabilizer is the mixture being made up of with weight ratio 20-40:4-8:1 Soil stability agent, auxiliary stabilizer and auxiliary agent；The mixture that described main body heat stabilizer is made up of with weight ratio 2.2-2.8:1 organo-tin compound and rare-earth compounds；The mixture that described auxiliary heat stabilizer is made up of with weight ratio 1.5-2.5:1.8-2.6:1 phosphite ester compound, epoxidized soybean oil and beta-diketone compounds；The mixture that described auxiliary agent is made up of with weight ratio 4-8:1 emulsifying agent and defoamer.
The present invention is by being mixed to prepare heat stabilizer by Soil stability agent, auxiliary stabilizer and auxiliary agent with weight ratio 20-40:4-8:1, and its thermostable effect is good.
The present invention, by introducing rare earth compound in Soil stability agent, is greatly improved the thermal stability in goods process, and does not affect the properties of transparency of PVC product.The present invention uses organo-tin compound and rare-earth compounds as main body heat stabilizer, and to control its weight ratio be 20-40:4-8:1, make material have good dispersiveness, compatibility and processing fluidity in process, make material good heat stability, there is efficient weatherability.
The present invention uses phosphite ester compound, epoxidized soybean oil and beta-diketone compounds as auxiliary heat stabilizer, and to control its weight ratio be 1.5-2.5:1.8-2.6:1, the stability of main body heat stabilizer can be improved, material is made to have good dispersiveness, compatibility and processing fluidity in process, make material good heat stability, there is efficient weatherability.
Preferably, the mixture that described organo-tin compound is made up of with weight ratio 2-4:1 thiol-butyl tin and dibutyl tin laurate；The mixture that described rare-earth compounds is Lanthanum Stearate and cerium stearate forms with weight ratio 0.8-1.2:1；The mixture that described phosphite ester compound is made up of with weight ratio 1:1.5-2.5 the different monooctyl ester of phosphorous acid hexichol one and triphenyl phosphite；The mixture that described beta-diketone compounds is made up of with weight ratio 1:2-4 stearoyl benzoyl methane and dibenzoyl methane.
The present invention is organo-tin compound by using thiol-butyl tin and dibutyl tin laurate, and to control its weight ratio be 2-4:1, it is rare-earth compounds by using Lanthanum Stearate and cerium stearate, and to control its weight ratio be 0.8-1.2:1, material is made to have good dispersiveness, compatibility and processing fluidity in process, make material good heat stability, there is efficient weatherability.
The present invention is by using the different monooctyl ester of phosphorous acid hexichol one and triphenyl phosphite as phosphite ester compound, and to control its weight ratio be 1:1.5-2.5, it is beta-diketone compounds by using stearoyl benzoyl methane and dibenzoyl methane, and to control its weight ratio be 1:2-4, the stability of main body heat stabilizer can be improved, make material have good dispersiveness, compatibility and processing fluidity in process, make material good heat stability, there is efficient weatherability.
Preferably, the mixture that described emulsifying agent is made up of with weight ratio 2.4-3.2:1.6-2.4:1 potassium oleate, potassium stearate and potassium rosinate；The mixture that described defoamer is made up of with weight ratio 1:1.6-2.4 tributyl phosphate and dimethyl silicone polymer.
The present invention uses potassium oleate, potassium stearate and potassium rosinate to be emulsifying agent, and to control its weight ratio be 2.4-3.2:1.6-2.4:1, and emulsifying effectiveness is good；The present invention uses tributyl phosphate and dimethyl silicone polymer as defoamer, and to control its weight ratio be 1:1.6-2.4, and foaming effect is good；The present invention is by using emulsifying agent and defoamer, and to control its weight ratio be 4-8:1, the stability of the heat stabilizer prepared can be improved, make material have good dispersiveness, compatibility and processing fluidity in process, make material good heat stability, there is efficient weatherability.
Preferably, the mixture that described lubricant is made up of with weight ratio 1.2-1.8:1 chlorinated paraffin and stearyl alcohol.
The present invention uses chlorinated paraffin as external lubricant, can reduce PVC melt and mould, the friction of machine barrel；Use stearyl alcohol as in-lubricant, the intermolecular friction of PVC melt can be reduced；Two kinds of lubricants are used in mixed way the mobility that material can be made to improve material in process and the release property of goods with weight ratio 1.2-1.8:1.
Another object of the present invention is achieved through the following technical solutions: a kind of preparation method material modified for insulating environment-friendly PVC, comprises the steps:
(1) above-mentioned raw materials is weighed by the weight portion of constitutive material, mixing；
(2) mixed raw material is put in high speed blender, at a temperature of 100-140 DEG C, stir 15-25min；
(3) by the raw material after stirring by double screw extruder extruding pelletization, insulating environment-friendly PVC is prepared material modified.
Preferably, the extruder temperature of described double 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 temperature 132-150 DEG CHe five district of district temperature 130-148 DEG C.
The beneficial effects of the present invention is: the present invention uses DOTP and tri-n-butyl citrate as plasticizer, two kinds of plasticizer are environment-friendly plasticizer, the active force of PVC molecule interchain can be reduced, the vitrification point of PVC plastic, flowing temperature is made all to reduce with the fusing point of contained crystallite, plasticizer can improve the plasticity of resin, makes goods softness, resistance to low temperature good；When two kinds of plasticizer use so that weight ratio 5-7:1 is compounding, flexibility and the resistance to low temperature of goods can be improved.
The present invention uses kaolin, titanium dioxide and glass microballoon as insulation modifying agent, kaolin, titanium dioxide filled PVC, can make the insulation effect of raising goods；Due to the high resistivity characteristic of glass microballoon, use the specific insulation of the goods of glass microballoon filled PVC can meet and exceed 1 × 1013, when kaolin, titanium dioxide and glass microballoon use so that weight ratio 2-4:1.5-2.5:1 is compounding, prepared PVC material has preferable insulating properties.
The present invention is by selecting acrylonitrile-butadiene-styrene terpolymer as impact modifier, and control the content of acrylonitrile unit at 15-35%, the content of butadiene unit is at 5-30%, the content of styrene units is at 40-60%, prepare material good impact resistance, and heat resistance and processing characteristics excellent.
The present invention by by the size controlling of polyvinyl chloride resin at 0.1-0.2mm, the apparent density of polyvinyl chloride resin is controlled at 0.4-0.5g/cm3So that material plasticizing rate is fast, is easily worked.
The present invention uses the nm-class active calcium carbonate processed through compatilizer maleic anhydride graft phenylethene-isoprene-styrene block copolymer, can improve the compatibility of nm-class active calcium carbonate and polyvinyl chloride resin, thus improve the intensity of material.
The present invention is by being mixed to prepare heat stabilizer by Soil stability agent, auxiliary stabilizer and auxiliary agent with weight ratio 20-40:4-8:1, and its thermostable effect is good.
The present invention, by introducing rare earth compound in Soil stability agent, is greatly improved the thermal stability in goods process, and does not affect the properties of transparency of PVC product.The present invention uses organo-tin compound and rare-earth compounds as main body heat stabilizer, and to control its weight ratio be 20-40:4-8:1, make material have good dispersiveness, compatibility and processing fluidity in process, make material good heat stability, there is efficient weatherability.
The present invention uses phosphite ester compound, epoxidized soybean oil and beta-diketone compounds as auxiliary heat stabilizer, and to control its weight ratio be 1.5-2.5:1.8-2.6:1, the stability of main body heat stabilizer can be improved, material is made to have good dispersiveness, compatibility and processing fluidity in process, make material good heat stability, there is efficient weatherability.
The present invention uses chlorinated paraffin as external lubricant, can reduce PVC melt and mould, the friction of machine barrel；Use stearyl alcohol as in-lubricant, the intermolecular friction of PVC melt can be reduced；Two kinds of lubricants are used in mixed way the mobility that material can be made to improve material in process and the release property of goods with weight ratio 1.2-1.8:1.
The properties material modified for insulating environment-friendly PVC that the present invention prepares is all excellent beyond national standard, good insulation preformance, environmental protection, and resistance to elevated temperatures, and intensity is high, good flame retardation effect, and compression performance and toughness are strong, and processing characteristics is excellent, excellent combination property.The product of the present invention meets the international standards such as REACH, ROHS, PAHS, N-P, can be widely applied to automobile, electronic apparatus, instrument and meter, weaves and the industrial circle such as building.
The preparation method technique of the present invention is simple, convenient operation and control, steady quality, and production efficiency is high, can large-scale industrial production.
Detailed description of the invention
For the ease of the understanding of those skilled in the art, below in conjunction with embodiment, the present invention is further illustrated, the content that embodiment is mentioned not limitation of the invention.
Embodiment 1
A kind of insulating environment-friendly PVC is material modified, including the raw material of following weight portion:
Polyvinyl chloride resin 80 parts
Filler 40 parts
40 parts of plasticizer
Insulation modifying agent 10 parts
Heat stabilizer 3 parts
Lubricant 0.5 part
Impact modifier 5 parts；
The mixture that described plasticizer is made up of with weight ratio 5:1 DOTP and tri-n-butyl citrate；The mixture that described insulation modifying agent is made up of with weight ratio 2:1.5:1 kaolin, titanium dioxide and glass microballoon, wherein, the particle diameter of described glass microballoon is 11 μm；Described impact modifier is acrylonitrile-butadiene-styrene terpolymer, and wherein, the content of acrylonitrile unit is 35%, and the content of butadiene unit is 25%, and the content of styrene units is 40%；Described polyvinyl chloride resin be particle diameter in 0.1mm, apparent density at 0.4g/cm3Polyvinyl chloride resin；Described filler is particle diameter at 20nm and the nm-class active calcium carbonate that processed through maleic anhydride graft phenylethene-isoprene-styrene block copolymer；Described heat stabilizer is the mixture being made up of with weight ratio 20:4:1 Soil stability agent, auxiliary stabilizer and auxiliary agent；The mixture that described main body heat stabilizer is made up of with weight ratio 2.2:1 organo-tin compound and rare-earth compounds；The mixture that described auxiliary heat stabilizer is made up of with weight ratio 1.5:1.8:1 phosphite ester compound, epoxidized soybean oil and beta-diketone compounds；The mixture that described auxiliary agent is made up of with weight ratio 4:1 emulsifying agent and defoamer；The mixture that described organo-tin compound is made up of with weight ratio 2:1 thiol-butyl tin and dibutyl tin laurate；The mixture that described rare-earth compounds is Lanthanum Stearate and cerium stearate forms with weight ratio 0.8:1；The mixture that described phosphite ester compound is made up of with weight ratio 1:1.5 the different monooctyl ester of phosphorous acid hexichol one and triphenyl phosphite；The mixture that described beta-diketone compounds is made up of with weight ratio 1:2 stearoyl benzoyl methane and dibenzoyl methane；The mixture that described emulsifying agent is made up of with weight ratio 2.4:1.6:1 potassium oleate, potassium stearate and potassium rosinate；The mixture that described defoamer is made up of with weight ratio 1:1.6 tributyl phosphate and dimethyl silicone polymer；The mixture that described lubricant is made up of with weight ratio 1.2:1 chlorinated paraffin and stearyl alcohol.
A kind of preparation method material modified for insulating environment-friendly PVC, comprises the steps:
(1) above-mentioned raw materials is weighed by the weight portion of constitutive material, mixing；
(2) mixed raw material is put in high speed blender, at a temperature of 100 DEG C, stir 15min；
(3) by the raw material after stirring by double screw extruder extruding pelletization, insulating environment-friendly PVC is prepared material modified；The extruder temperature of described double 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.
Embodiment 2
A kind of insulating environment-friendly PVC is material modified, including the raw material of following weight portion:
Polyvinyl chloride resin 90 parts
Filler 45 parts
45 parts of plasticizer
Insulation modifying agent 11 parts
Heat stabilizer 4 parts
Lubricant 0.8 part
Impact modifier 8 parts；
The mixture that described plasticizer is made up of with weight ratio 5.5:1 DOTP and tri-n-butyl citrate；The mixture that described insulation modifying agent is made up of with weight ratio 2.5:1.8:1 kaolin, titanium dioxide and glass microballoon, wherein, the particle diameter of described glass microballoon is 13 μm；Described impact modifier is acrylonitrile-butadiene-styrene terpolymer, and wherein, the content of acrylonitrile unit is 32.5%, and the content of butadiene unit is 22.5%, and the content of styrene units is 45%；Described polyvinyl chloride resin be particle diameter in 0.12mm, apparent density at 0.42g/cm3Polyvinyl chloride resin；Described filler is particle diameter at 50nm and the nm-class active calcium carbonate that processed through maleic anhydride graft phenylethene-isoprene-styrene block copolymer；Described heat stabilizer is the mixture being made up of with weight ratio 25:5:1 Soil stability agent, auxiliary stabilizer and auxiliary agent；The mixture that described main body heat stabilizer is made up of with weight ratio 2.3:1 organo-tin compound and rare-earth compounds；The mixture that described auxiliary heat stabilizer is made up of with weight ratio 1.8:2.0:1 phosphite ester compound, epoxidized soybean oil and beta-diketone compounds；The mixture that described auxiliary agent is made up of with weight ratio 5:1 emulsifying agent and defoamer；The mixture that described organo-tin compound is made up of with weight ratio 2.5:1 thiol-butyl tin and dibutyl tin laurate；The mixture that described rare-earth compounds is Lanthanum Stearate and cerium stearate forms with weight ratio 0.9:1；The mixture that described phosphite ester compound is made up of with weight ratio 1:1.8 the different monooctyl ester of phosphorous acid hexichol one and triphenyl phosphite；The mixture that described beta-diketone compounds is made up of with weight ratio 1:2.5 stearoyl benzoyl methane and dibenzoyl methane；The mixture that described emulsifying agent is made up of with weight ratio 2.6:1.8:1 potassium oleate, potassium stearate and potassium rosinate；The mixture that described defoamer is made up of with weight ratio 1:1.8 tributyl phosphate and dimethyl silicone polymer；The mixture that described lubricant is made up of with weight ratio 1.3:1 chlorinated paraffin and stearyl alcohol.
A kind of preparation method material modified for insulating environment-friendly PVC, comprises the steps:
(1) above-mentioned raw materials is weighed by the weight portion of constitutive material, mixing；
(2) mixed raw material is put in high speed blender, at a temperature of 110 DEG C, stir 18min；
(3) by the raw material after stirring by double screw extruder extruding pelletization, insulating environment-friendly PVC is prepared material modified；The extruder temperature of described double screw extruder is: district's temperature 144 DEG C, two district's temperature 141 DEG C, three district's temperature 140 DEG C, four district's temperature 136 DEG CHe five district temperature 135 DEG C.
Embodiment 3
A kind of insulating environment-friendly PVC is material modified, including the raw material of following weight portion:
Polyvinyl chloride resin 100 parts
Filler 50 parts
50 parts of plasticizer
Insulation modifying agent 13 parts
Heat stabilizer 5 parts
Lubricant 1 part
Impact modifier 10 parts；
The mixture that described plasticizer is made up of with weight ratio 6:1 DOTP and tri-n-butyl citrate；The mixture that described insulation modifying agent is made up of with weight ratio 3:2:1 kaolin, titanium dioxide and glass microballoon, wherein, the particle diameter of described glass microballoon is 15 μm；Described impact modifier is acrylonitrile-butadiene-styrene terpolymer, and wherein, the content of acrylonitrile unit is 30%, and the content of butadiene unit is 20%, and the content of styrene units is 50%；Described polyvinyl chloride resin be particle diameter in 0.15mm, apparent density at 0.45g/cm3Polyvinyl chloride resin；Described filler is particle diameter at 100nm and the nm-class active calcium carbonate that processed through maleic anhydride graft phenylethene-isoprene-styrene block copolymer；Described heat stabilizer is the mixture being made up of with weight ratio 30:6:1 Soil stability agent, auxiliary stabilizer and auxiliary agent；The mixture that described main body heat stabilizer is made up of with weight ratio 2.5:1 organo-tin compound and rare-earth compounds；The mixture that described auxiliary heat stabilizer is made up of with weight ratio 2.0:2.2:1 phosphite ester compound, epoxidized soybean oil and beta-diketone compounds；The mixture that described auxiliary agent is made up of with weight ratio 6:1 emulsifying agent and defoamer；The mixture that described organo-tin compound is made up of with weight ratio 3:1 thiol-butyl tin and dibutyl tin laurate；The mixture that described rare-earth compounds is Lanthanum Stearate and cerium stearate forms with weight ratio 1:1；The mixture that described phosphite ester compound is made up of with weight ratio 1:2 the different monooctyl ester of phosphorous acid hexichol one and triphenyl phosphite；The mixture that described beta-diketone compounds is made up of with weight ratio 1:3 stearoyl benzoyl methane and dibenzoyl methane；The mixture that described emulsifying agent is made up of with weight ratio 2.8:2.0:1 potassium oleate, potassium stearate and potassium rosinate；The mixture that described defoamer is made up of with weight ratio 1:2.0 tributyl phosphate and dimethyl silicone polymer；The mixture that described lubricant is made up of with weight ratio 1.5:1 chlorinated paraffin and stearyl alcohol.
A kind of preparation method material modified for insulating environment-friendly PVC, comprises the steps:
(1) above-mentioned raw materials is weighed by the weight portion of constitutive material, mixing；
(2) mixed raw material is put in high speed blender, at a temperature of 120 DEG C, stir 20min；
(3) by the raw material after stirring by double screw extruder extruding pelletization, insulating environment-friendly PVC is prepared material modified；The extruder temperature of described double screw extruder is: district's temperature 149 DEG C, two district's temperature 147 DEG C, three district's temperature 145 DEG C, four district's temperature 141 DEG CHe five district temperature 139 DEG C.
Embodiment 4
A kind of insulating environment-friendly PVC is material modified, including the raw material of following weight portion:
Polyvinyl chloride resin 110 parts
Filler 55 parts
55 parts of plasticizer
Insulation modifying agent 14 parts
Heat stabilizer 6 parts
Lubricant 1.2 parts
Impact modifier 12 parts；
The mixture that described plasticizer is made up of with weight ratio 6.5:1 DOTP and tri-n-butyl citrate；The mixture that described insulation modifying agent is made up of with weight ratio 3.5:2.2:1 kaolin, titanium dioxide and glass microballoon, wherein, the particle diameter of described glass microballoon is 17 μm；Described impact modifier is acrylonitrile-butadiene-styrene terpolymer, and wherein, the content of acrylonitrile unit is 27.5%, and the content of butadiene unit is 17.5%, and the content of styrene units is 55%；Described polyvinyl chloride resin be particle diameter in 0.18mm, apparent density at 0.48g/cm3Polyvinyl chloride resin；Described filler is particle diameter at 150nm and the nm-class active calcium carbonate that processed through maleic anhydride graft phenylethene-isoprene-styrene block copolymer；Described heat stabilizer is the mixture being made up of with weight ratio 35:7:1 Soil stability agent, auxiliary stabilizer and auxiliary agent；The mixture that described main body heat stabilizer is made up of with weight ratio 2.6:1 organo-tin compound and rare-earth compounds；The mixture that described auxiliary heat stabilizer is made up of with weight ratio 2.2:2.4:1 phosphite ester compound, epoxidized soybean oil and beta-diketone compounds；The mixture that described auxiliary agent is made up of with weight ratio 7:1 emulsifying agent and defoamer；The mixture that described organo-tin compound is made up of with weight ratio 3.5:1 thiol-butyl tin and dibutyl tin laurate；The mixture that described rare-earth compounds is Lanthanum Stearate and cerium stearate forms with weight ratio 1.1:1；The mixture that described phosphite ester compound is made up of with weight ratio 1:2.2 the different monooctyl ester of phosphorous acid hexichol one and triphenyl phosphite；The mixture that described beta-diketone compounds is made up of with weight ratio 1:3.5 stearoyl benzoyl methane and dibenzoyl methane；The mixture that described emulsifying agent is made up of with weight ratio 3.0:2.2:1 potassium oleate, potassium stearate and potassium rosinate；The mixture that described defoamer is made up of with weight ratio 1:2.2 tributyl phosphate and dimethyl silicone polymer；The mixture that described lubricant is made up of with weight ratio 1.6:1 chlorinated paraffin and stearyl alcohol.
A kind of preparation method material modified for insulating environment-friendly PVC, comprises the steps:
(1) above-mentioned raw materials is weighed by the weight portion of constitutive material, mixing；
(2) mixed raw material is put in high speed blender, at a temperature of 130 DEG C, stir 22min；
(3) by the raw material after stirring by double screw extruder extruding pelletization, insulating environment-friendly PVC is prepared material modified；The extruder temperature of described double screw extruder is: district's temperature 155 DEG C, two district's temperature 153 DEG C, three district's temperature 150 DEG C, four district's temperature 145 DEG CHe five district temperature 144 DEG C.
Embodiment 5
A kind of insulating environment-friendly PVC is material modified, including the raw material of following weight portion:
Polyvinyl chloride resin 120 parts
Filler 60 parts
60 parts of plasticizer
Insulation modifying agent 15 parts
Heat stabilizer 7 parts
Lubricant 1.5 parts
Impact modifier 15 parts；
The mixture that described plasticizer is made up of with weight ratio 7:1 DOTP and tri-n-butyl citrate；The mixture that described insulation modifying agent is made up of with weight ratio 4:2.5:1 kaolin, titanium dioxide and glass microballoon, wherein, the particle diameter of described glass microballoon is 19 μm；Described impact modifier is acrylonitrile-butadiene-styrene terpolymer, and wherein, the content of acrylonitrile unit is 25%, and the content of butadiene unit is 15%, and the content of styrene units is 60%；Described polyvinyl chloride resin be particle diameter in 0.2mm, apparent density at 0.5g/cm3Polyvinyl chloride resin；Described filler is particle diameter at 200nm and the nm-class active calcium carbonate that processed through maleic anhydride graft phenylethene-isoprene-styrene block copolymer；Described heat stabilizer is the mixture being made up of with weight ratio 40:8:1 Soil stability agent, auxiliary stabilizer and auxiliary agent；The mixture that described main body heat stabilizer is made up of with weight ratio 2.8:1 organo-tin compound and rare-earth compounds；The mixture that described auxiliary heat stabilizer is made up of with weight ratio 2.5:2.6:1 phosphite ester compound, epoxidized soybean oil and beta-diketone compounds；The mixture that described auxiliary agent is made up of with weight ratio 8:1 emulsifying agent and defoamer；The mixture that described organo-tin compound is made up of with weight ratio 4:1 thiol-butyl tin and dibutyl tin laurate；The mixture that described rare-earth compounds is Lanthanum Stearate and cerium stearate forms with weight ratio 1.2:1；The mixture that described phosphite ester compound is made up of with weight ratio 1:2.5 the different monooctyl ester of phosphorous acid hexichol one and triphenyl phosphite；The mixture that described beta-diketone compounds is made up of with weight ratio 1:4 stearoyl benzoyl methane and dibenzoyl methane；The mixture that described emulsifying agent is made up of with weight ratio 3.2:2.4:1 potassium oleate, potassium stearate and potassium rosinate；The mixture that described defoamer is made up of with weight ratio 1:2.4 tributyl phosphate and dimethyl silicone polymer；The mixture that described lubricant is made up of with weight ratio 1.8:1 chlorinated paraffin and stearyl alcohol.
A kind of preparation method material modified for insulating environment-friendly PVC, comprises the steps:
(1) above-mentioned raw materials is weighed by the weight portion of constitutive material, mixing；
(2) mixed raw material is put in high speed blender, at a temperature of 140 DEG C, stir 25min；
(3) by the raw material after stirring by double screw extruder extruding pelletization, insulating environment-friendly PVC is prepared material modified；The extruder temperature of described double 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.
Material modified for the insulating environment-friendly PVC mechanical and physical performance that embodiments of the invention 1-5 prepares is as shown in table 1.
Table 1
| Test event | Standard value | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Resistivity (Ω) | ≥1.0×109 | 4.9×1013 | 3.2×1014 | 5.1×1014 | 6.7×1013 | 8.5×1013 |
| Hot strength (MPa) | ≥15.0 | 23.2 | 25.3 | 26.6 | 27.1 | 24.2 |
| Bending strength (MPa) | ≥15.0 | 46.2 | 48.1 | 51.2 | 53.8 | 44.6 |
| Elongation at break (%) | ≥150 | 297 | 302 | 309 | 320 | 299 |
| Heat distortion temperature (DEG C) | ≥50.0 | 115.6 | 118.5 | 120.7 | 123.3 | 116.4 |
| Impact brittle temperature (DEG C) | ≤-20 | -25 | -25 | -30 | -30 | -25 |
| Heat-stable time (min) when 200 DEG C | ≥60 | 90 | 110 | 120 | 120 | 100 |
| Hardness/Shore D | ≥50 | 80 | 83 | 85 | 86 | 81 |
| Fire-retardant | V0 | V0 | V0 | V0 | V0 | V0 |
The properties material modified for insulating environment-friendly PVC that the present invention prepares is all beyond national standard, good insulation preformance, and resistivity is up to 5.1 × 1014Ω, environmental protection, and resistance to elevated temperatures are excellent, and intensity is high, good flame retardation effect, and compression performance and toughness are strong, and processing characteristics is excellent, excellent combination property.The product of the present invention meets the international standards such as REACH, ROHS, PAHS, N-P, can be widely applied to automobile, electronic apparatus, instrument and meter, weaves and the industrial circle such as building.
Above-described embodiment is the present invention preferably implementation, and in addition, the present invention can realize with alternate manner, and the most any obvious replacement is all within protection scope of the present invention.
Claims (5)
1. an insulating environment-friendly PVC is material modified, it is characterised in that: include the raw material of following weight portion:
Polyvinyl chloride resin
80-120 part
Filler
40-60 part
Plasticizer
40-60 part
Insulation modifying agent 10-15 part
Heat stabilizer
3-7 part
Lubricant
0.5-1.5 part；
The mixture that described plasticizer is made up of with weight ratio 5-7:1 DOTP and tri-n-butyl citrate；
The mixture that described insulation modifying agent is made up of with weight ratio 2-4:1.5-2.5:1 kaolin, titanium dioxide and glass microballoon, wherein, the particle diameter of described glass microballoon is less than 20 μm；
Also including impact modifier 5-15 part, described impact modifier is acrylonitrile-butadiene-styrene terpolymer, and wherein, the content of acrylonitrile unit is 25-35%, and the content of butadiene unit is 15-25%, and the content of styrene units is 40-60%；
Described polyvinyl chloride resin be particle diameter in 0.1-0.2mm, apparent density at 0.4-0.5g/cm3Polyvinyl chloride resin；
Described filler is particle diameter at 20-200nm and the nm-class active calcium carbonate that processed through maleic anhydride graft phenylethene-isoprene-styrene block copolymer；
The mixture that described lubricant is made up of with weight ratio 1.2-1.8:1 chlorinated paraffin and stearyl alcohol.
A kind of insulating environment-friendly PVC the most according to claim 1 is material modified, it is characterised in that: described heat stabilizer is the mixture being made up of with weight ratio 20-40:4-8:1 Soil stability agent, auxiliary stabilizer and auxiliary agent；The mixture that described main body heat stabilizer is made up of with weight ratio 2.2-2.8:1 organo-tin compound and rare-earth compounds；The mixture that described auxiliary heat stabilizer is made up of with weight ratio 1.5-2.5:1.8-2.6:1 phosphite ester compound, epoxidized soybean oil and beta-diketone compounds；The mixture that described auxiliary agent is made up of with weight ratio 4-8:1 emulsifying agent and defoamer.
A kind of insulating environment-friendly PVC the most according to claim 2 is material modified, it is characterised in that: the mixture that described organo-tin compound is made up of with weight ratio 2-4:1 thiol-butyl tin and dibutyl tin laurate；The mixture that described rare-earth compounds is Lanthanum Stearate and cerium stearate forms with weight ratio 0.8-1.2:1；The mixture that described phosphite ester compound is made up of with weight ratio 1:1.5-2.5 the different monooctyl ester of phosphorous acid hexichol one and triphenyl phosphite；The mixture that described beta-diketone compounds is made up of with weight ratio 1:2-4 stearoyl benzoyl methane and dibenzoyl methane.
A kind of insulating environment-friendly PVC the most according to claim 2 is material modified, it is characterised in that: the mixture that described emulsifying agent is made up of with weight ratio 2.4-3.2:1.6-2.4:1 potassium oleate, potassium stearate and potassium rosinate；The mixture that described defoamer is made up of with weight ratio 1:1.6-2.4 tributyl phosphate and dimethyl silicone polymer.
5. a kind of preparation method material modified for insulating environment-friendly PVC as described in any one of claim 1-4, it is characterised in that: comprise the steps:
(1) above-mentioned raw materials is weighed by the weight portion of constitutive material, mixing；
(2) mixed raw material is put in high speed blender, at a temperature of 100-140 DEG C, stir 15-25min；
(3) by the raw material after stirring by double screw extruder extruding pelletization, insulating environment-friendly PVC is prepared material modified；
The extruder temperature of described double 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 temperature 132-150 DEG CHe five district of district temperature 130-148 DEG C.
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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. |
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