CN104109325A - Waterproof and environment-friendly PVC modified material and preparation method thereof - Google Patents
Waterproof and environment-friendly PVC modified material and preparation method thereof Download PDFInfo
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- CN104109325A CN104109325A CN201410374023.9A CN201410374023A CN104109325A CN 104109325 A CN104109325 A CN 104109325A CN 201410374023 A CN201410374023 A CN 201410374023A CN 104109325 A CN104109325 A CN 104109325A
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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
- B29C2948/92676—Weight
-
- 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 invention relates to the technical field of PVC modified materials and particularly relates to a waterproof and environment-friendly PVC modified material and a preparation method thereof. The waterproof and environment-friendly PVC modified material is prepared from the following raw materials: 80-120 parts of PVC resin, 20-30 parts of bulking agent, 50-70 parts of plasticizer, 4-8 parts of heat stabilizer, 10-15 parts of impact modifier, 4-8 parts of modified rubber and 1-2 parts of lubricant, wherein the plasticizer is a mixture prepared from trioctyl trimellitate and epoxidized soybean oil which are in the weight ratio of (8-10): 1; the modified rubber is a mixture prepared from butyl rubber, nitrile-butadiene rubber and ethylene propylene terpolymer rubber which are in the weight ratio of (1.2-1.8): (1.6-2.4): 1. According to the waterproof and environment-friendly PVC modified material prepared by the preparation method, all properties exceed the national standards, the waterproof effect is good, and the PVC modified material is environment-friendly; the preparation method disclosed by the invention is simple in process, convenient in operation and control, stable in quality and high in production efficiency and can be applied to 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 water-proof environmental protection PVC material modified and preparation method thereof.
Background technology
Polyvinyl chloride (PVC) is one of industrialization the earliest, 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, very easily embrittlement while being hit, therefore 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 starts to decomposite HCl in the time of 100 ℃, decomposes rapidlyer during higher than 150 ℃, and the melt temperature of PVC is about 210 ℃; 3, the viscosity of PVC is high, and mobility 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 200910155137.3 to disclose a kind of PVC elastomer material, this material is prepared from by each component of following weight part: PVC 95～105 weight parts, calcium stearate 1.5～3 weight parts, Zinic stearas 0.5～2 weight part, lubricant 0.5～2 weight part, vinyl chloride-vinyl acetate resin 8～16 weight parts, thermoplastic styrene butadiene rubber 15～25 weight parts, weighting agent 60～100 weight parts.
Application number is 201010198789.8 to disclose a kind of hard PVC injectable plastic material, and by weight percentage, it forms and content is: 800 type resins 45～75, calcium carbonate 5～15; Dibutyl ester 1～3, stablizer 2～5, chlorinatedpolyethylene (CPE) 1～5, industrial paraffin 0.5～10, titanium dioxide 0.5～10, softening agent 0.5～1.
The performance index of existing most of PVC material are all to meet the basic demand of national standard, for a lot of particular surroundingss as under wet environment, current PVC material property still can not meet the demand of life-time service under wet condition reliably, therefore, the water resistance of PVC material also needs further to optimize improvement; In addition, all there is quite serious pollution in existing PVC jacketed cable, PVC plug, PVC film and pvc pipe, can cause certain harm to HUMAN HEALTH, and the PVC material of researching and developing a kind of environmental protection also seems particularly important.
Summary of the invention
In order to overcome the shortcoming and defect existing in prior art, the object of the present invention is to provide a kind of water-proof environmental protection PVC material modified, this material modified good waterproof performance, environmental protection, and heatproof and weather resistance good, excellent shock resistance, good flame retardation effect, processing characteristics is good, excellent combination property.
Another object of the present invention is to provide the material modified preparation method of a kind of water-proof environmental protection PVC, this preparation method's technique is simple, convenient operation and control, and steady quality, production efficiency is high, can large-scale industrial production.
Object of the present invention is achieved through the following technical solutions: a kind of water-proof environmental protection PVC is material modified, comprises the raw material of following weight part:
Polyvinyl chloride resin 80-120 part
Weighting agent 20-30 part
Softening agent 50-70 part
Thermo-stabilizer 4-8 part
Impact modifier 10-15 part
Modified rubber 4-8 part
Lubricant 1-2 part;
The mixture that described softening agent is comprised of with weight ratio 8-10:1 trioctyl trimellitate and epoxy soybean oil.
Trioctyl trimellitate (TOTM), molecular formula is C
33h
54o
6molecular weight is 546.78, and density is 0.988 ± 0.003g/mL, has thermotolerance, weather resistance and transport property good, intermiscibility and winter hardiness all can, mainly for the production of 105 ℃ of level heatproof wire CABLE MATERIALS and other, require the heat-resisting and goods such as sheet material, sheet material and gasket weather resistance.
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 the physical strength that goods are good, weathering resistance and electrical property, and nontoxicity are the chemical technology auxiliary agents for packaging material for food of international endorsement, all polrvinyl chloride products be can be widely used in, special ink, paint, coating, synthetic rubber and liquid composite stabilizing agent etc. also can be used for.
The present invention adopts the mixture of trioctyl trimellitate and epoxy soybean oil as softening agent, two kinds of softening agent are environment-friendly plasticizer, can reduce the reactive force between PVC molecular chain, the fusing point of second-order transition temperature, yield temperature and the contained crystallite of PVC plastics is all reduced, softening agent can improve the plasticity-of resin, makes that goods are soft, resistance to low temperature is good; When two kinds of softening agent are during with the composite use of weight ratio 8-10:1, can improve flexibility and the resistance to low temperature of goods.
The mixture that described modified rubber is comprised of with weight ratio 1.2-1.8:1.6-2.4:1 isoprene-isobutylene rubber, nitrile rubber and terpolymer EP rubber.
The present invention adopts isoprene-isobutylene rubber, nitrile rubber and terpolymer EP rubber as modified rubber, and three kinds of rubber all have good water tolerance, and when three kinds of rubber are during with the composite use of weight ratio 1.2-1.8:1.6-2.4:1, the material waterproofing making is effective, good weatherability.
Preferably, described polyvinyl chloride resin is that particle diameter is at the polyvinyl chloride resin of 0.1-0.2mm.
The polyvinyl chloride resin that the present invention adopts is the loose type resin that suspension method makes, surface imperfection, and porous, is cotton spherical, easily absorbs softening agent; The present invention, by the particle diameter of polyvinyl chloride resin is controlled to 0.1-0.2mm, makes material plasticizing rate fast, easily processing.
Preferably, described weighting agent is particle diameter at 2-20nm and the ultramicrofine light calcium carbonate processed through titante coupling agent.
The particle diameter of weighting agent is less, more useful to the tensile strength of packing material and shock strength, and the present invention, by selecting ultramicrofine light calcium carbonate as weighting agent and controlling its particle diameter at 2-20nm, can improve the intensity of material; The consistency that weighting agent and resin are good is its effect of performance and the key of controlling addition, the present invention adopts the ultramicrofine light calcium carbonate of processing through titante coupling agent, can improve the consistency of ultramicrofine light calcium carbonate and polyvinyl chloride resin, thereby improve the intensity of material.
Preferably, described thermo-stabilizer is the mixture being comprised of with weight ratio 20-40:4-8:1 Soil stability agent, auxiliary stabilizer and auxiliary agent.
The present invention is by mixing Soil stability agent, auxiliary stabilizer and auxiliary agent to make thermo-stabilizer with weight ratio 20-40:4-8:1, and its thermostable effect is good.
Preferably, the mixture that described main body thermo-stabilizer is comprised of with weight ratio 1.6-2.4:1:1.8-2.6 Zinic stearas, calcium stearate and zinc laurate; Described auxiliary heat stabilizer is by carbon back-4, the mixture that 4-bis-different fork-fatty alcohol-phosphorous acid chelating chemical combination polymkeric substance and tetramethylolmethane form with weight ratio 1.5-2.5:1.
The present invention adopts Zinic stearas, calcium stearate and zinc laurate as main body thermo-stabilizer, and to control its weight ratio be 1.6-2.4:1:1.8-2.6, make material in the course of processing, have good dispersiveness, consistency and processing fluidity, make material good heat stability, there is efficient weathering resistance.
The present invention adopts carbon back-4,4-bis-different fork-fatty alcohol-phosphorous acid chelating chemical combination polymkeric substance and tetramethylolmethane are as auxiliary heat stabilizer, and to control its weight ratio be 1.5-2.5:1, can improve the stability of main body thermo-stabilizer, make material in the course of processing, have good dispersiveness, consistency and processing fluidity, make material good heat stability, there is efficient weathering resistance.
Preferably, the mixture that described auxiliary agent is comprised of with weight ratio 4-8:1 emulsifying agent and defoamer; The mixture that described emulsifying agent is comprised 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 comprised of with weight ratio 1:1.6-2.4 tributyl phosphate and polydimethylsiloxane.
It is emulsifying agent that the present invention adopts potassium oleate, potassium stearate and potassium rosinate, and to control its weight ratio be 2.4-3.2:1.6-2.4:1, emulsify well; The present invention adopts tributyl phosphate and polydimethylsiloxane as defoamer, and to control its weight ratio be 1:1.6-2.4, and foaming effect is good; The present invention is by adopting emulsifying agent and defoamer, and to control its weight ratio be 4-8:1, can improve the stability of the thermo-stabilizer making, make material in the course of processing, have good dispersiveness, consistency and processing fluidity, make material good heat stability, there is efficient weathering resistance.
Preferably, described impact modifier is that chlorinity is at the chlorinatedpolyethylene of 25-45%.
Chlorinatedpolyethylene (CPE) is a kind of properties-correcting agent of thermoplastics, has good over-all properties.In polyvinyl chloride resin, add appropriate CPE, can reduce resin melt viscosity, improve mobility, improve the processing characteristics of plastics; Can also improve PVC shock strength, resistance to low temperature, weather resisteant energy, extend work-ing life of goods.CPE is added in calcic-plastic composite material, not only can replace Plasticizer DBP, also contributes to the dispersed of ultramicrofine light calcium carbonate and polyvinyl chloride resin.The application has also carried out large quantity research to the cl content of chlorinatedpolyethylene, and research shows, when the chlorinity of chlorinatedpolyethylene is 25-45%, the material shock resistance making is good, and good weatherability.
Preferably, the mixture that described lubricant is comprised of with weight ratio 1.2-1.8:1 native paraffin and methylene-bis stearylamide.
The present invention adopts native paraffin as external lubricant, can reduce the friction of PVC melt and mould, machine barrel; Adopt methylene-bis stearylamide as internal lubricant, can reduce the intermolecular friction of PVC melt; Two kinds of lubricants mix to use with weight ratio 1.2-1.8:1 can make material in the course of processing, improve the mobility of material and the release property of goods.
Another object of the present invention is achieved through the following technical solutions: the material modified preparation method of a kind of water-proof environmental protection PVC, comprises the steps:
(1) by the weight part of constitutive material, take above-mentioned raw materials, mix;
(2) mixed raw material is put into high speed blender, at 100-140 ℃ of temperature, stir 15-25min;
(3) raw material after stirring is passed through to twin screw extruder extruding pelletization, make water-proof environmental protection PVC material modified.
Preferably, the extruder temperature of described twin screw extruder is: a district temperature 138-160 ℃, two district temperature 135-160 ℃, three district temperature 135-155 ℃, four district temperature 132-150 ℃He five district temperature 130-148 ℃
Beneficial effect of the present invention is: the present invention adopts trioctyl trimellitate and epoxy soybean oil as softening agent, two kinds of softening agent are environment-friendly plasticizer, can reduce the reactive force between PVC molecular chain, the fusing point of second-order transition temperature, yield temperature and the contained crystallite of PVC plastics is all reduced, softening agent can improve the plasticity-of resin, makes that goods are soft, resistance to low temperature is good; When two kinds of softening agent are during with the composite use of weight ratio 8-10:1, can improve flexibility and the resistance to low temperature of goods.
The present invention adopts isoprene-isobutylene rubber, nitrile rubber and terpolymer EP rubber as modified rubber, and three kinds of rubber all have good water tolerance, and when three kinds of rubber are during with the composite use of weight ratio 1.2-1.8:1.6-2.4:1, the material waterproofing making is effective, good weatherability.
The present invention, by the particle diameter of polyvinyl chloride resin is controlled to 0.1-0.2mm, makes material plasticizing rate fast, easily processing.
The present invention, by selecting ultramicrofine light calcium carbonate as weighting agent and controlling its particle diameter at 2-20nm, can improve the intensity of material; The consistency that additive and resin are good is its effect of performance and the key of controlling addition, the present invention adopts the ultramicrofine light calcium carbonate of processing through titante coupling agent, can improve the consistency of ultramicrofine light calcium carbonate and polyvinyl chloride resin, thereby improve the intensity of material.
The present invention is by mixing Soil stability agent, auxiliary stabilizer and auxiliary agent to make thermo-stabilizer with weight ratio 20-40:4-8:1, and its thermostable effect is good.
The present invention adopts Zinic stearas, calcium stearate and zinc laurate as main body thermo-stabilizer, and to control its weight ratio be 1.6-2.4:1:1.8-2.6, make material in the course of processing, have good dispersiveness, consistency and processing fluidity, make material good heat stability, there is efficient weathering resistance.
The present invention adopts carbon back-4,4-bis-different fork-fatty alcohol-phosphorous acid chelating chemical combination polymkeric substance and tetramethylolmethane are as auxiliary heat stabilizer, and to control its weight ratio be 1.5-2.5:1, can improve the stability of main body thermo-stabilizer, make material in the course of processing, have good dispersiveness, consistency and processing fluidity, make material good heat stability, there is efficient weathering resistance.
The present invention adopt chlorinity at the chlorinatedpolyethylene of 25-45% as impact modifier, the material shock resistance making is good, and good weatherability.
The present invention adopts native paraffin as external lubricant, can reduce the friction of PVC melt and mould, machine barrel; Adopt methylene-bis stearylamide as internal lubricant, can reduce the intermolecular friction of PVC melt; Two kinds of lubricants mix to use with weight ratio 1.2-1.8:1 can make material in the course of processing, improve the mobility of material and the release property of goods.
The material modified properties of water-proof environmental protection PVC that the present invention makes has all exceeded national standard, good water-proof effect, and environmental protection, and resistance to elevated temperatures is good, and intensity is high, good flame retardation effect, compression performance and toughness are strong, and processing characteristics is good, excellent combination property.Product of the present invention meets the international standards such as REACH, ROHS, PAHS, N-P, 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, can large-scale industrial production.
Embodiment
For the ease of those skilled in the art's understanding, below in conjunction with embodiment, the present invention is further illustrated, and the content that embodiment is mentioned not is limitation of the invention.
Embodiment 1
A kind of water-proof environmental protection PVC is material modified, comprises the raw material of following weight part:
80 parts of polyvinyl chloride resins
20 parts of weighting agents
50 parts, softening agent
4 parts of thermo-stabilizers
10 parts of impact modifiers
4 parts of modified rubbers
1 part of lubricant;
The mixture that described softening agent is comprised of with weight ratio 8:1 trioctyl trimellitate and epoxy soybean oil; The mixture that described modified rubber is comprised of with weight ratio 1.2:1.6:1 isoprene-isobutylene rubber, nitrile rubber and terpolymer EP rubber; Described polyvinyl chloride resin is that particle diameter is at the polyvinyl chloride resin of 0.1mm; Described weighting agent is particle diameter at 2nm and the ultramicrofine light calcium carbonate processed through titante coupling agent; Described thermo-stabilizer is the mixture being comprised of with weight ratio 20:4:1 Soil stability agent, auxiliary stabilizer and auxiliary agent; The mixture that described main body thermo-stabilizer is comprised of with weight ratio 1.6:1:1.8 Zinic stearas, calcium stearate and zinc laurate; Described auxiliary heat stabilizer is by carbon back-4, the mixture that 4-bis-different fork-fatty alcohol-phosphorous acid chelating chemical combination polymkeric substance and tetramethylolmethane form with weight ratio 1.5:1; The mixture that described auxiliary agent is comprised of with weight ratio 4:1 emulsifying agent and defoamer; The mixture that described emulsifying agent is comprised of with weight ratio 2.4:1.6:1 potassium oleate, potassium stearate and potassium rosinate; The mixture that described defoamer is comprised of with weight ratio 1:1.6 tributyl phosphate and polydimethylsiloxane; Described impact modifier is chlorinity at 25% chlorinatedpolyethylene; The mixture that described lubricant is comprised of with weight ratio 1.2:1 native paraffin and methylene-bis stearylamide.
The preparation method that water-proof environmental protection PVC is material modified, comprises the steps:
(1) by the weight part of constitutive material, take above-mentioned raw materials, mix;
(2) mixed raw material is put into high speed blender, at 100 ℃ of temperature, stir 15min;
(3) raw material after stirring is passed through to twin screw extruder extruding pelletization, make water-proof environmental protection 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 four district's temperature 132 ℃He five district's temperature.
Embodiment 2
A kind of water-proof environmental protection PVC is material modified, comprises the raw material of following weight part:
90 parts of polyvinyl chloride resins
22 parts of weighting agents
55 parts, softening agent
5 parts of thermo-stabilizers
11 parts of impact modifiers
5 parts of modified rubbers
1.5 parts of lubricants;
The mixture that described softening agent is comprised of with weight ratio 8.5:1 trioctyl trimellitate and epoxy soybean oil; The mixture that described modified rubber is comprised of with weight ratio 1.4:1.8:1 isoprene-isobutylene rubber, nitrile rubber and terpolymer EP rubber; Described polyvinyl chloride resin is that particle diameter is at the polyvinyl chloride resin of 0.12mm; Described weighting agent is particle diameter at 5nm and the ultramicrofine light calcium carbonate processed through titante coupling agent; Described thermo-stabilizer is the mixture being comprised of with weight ratio 25:5:1 Soil stability agent, auxiliary stabilizer and auxiliary agent; The mixture that described main body thermo-stabilizer is comprised of with weight ratio 1.8:1:2.0 Zinic stearas, calcium stearate and zinc laurate; Described auxiliary heat stabilizer is by carbon back-4, the mixture that 4-bis-different fork-fatty alcohol-phosphorous acid chelating chemical combination polymkeric substance and tetramethylolmethane form with weight ratio 1.8:1; The mixture that described auxiliary agent is comprised of with weight ratio 5:1 emulsifying agent and defoamer; The mixture that described emulsifying agent is comprised of with weight ratio 2.6:1.8:1 potassium oleate, potassium stearate and potassium rosinate; The mixture that described defoamer is comprised of with weight ratio 1:1.8 tributyl phosphate and polydimethylsiloxane; Described impact modifier is chlorinity at 30% chlorinatedpolyethylene; The mixture that described lubricant is comprised of with weight ratio 1.4:1 native paraffin and methylene-bis stearylamide.
The preparation method that water-proof environmental protection PVC is material modified, comprises the steps:
1) by the weight part of constitutive material, take above-mentioned raw materials, mix;
(2) mixed raw material is put into high speed blender, at 110 ℃ of temperature, stir 18min;
(3) raw material after stirring is passed through to twin screw extruder extruding pelletization, make water-proof environmental protection PVC material modified; The extruder temperature of described twin screw extruder is: 144 ℃ of district's temperature, 141 ℃ of two district's temperature, 140 ℃ of three district's temperature, 135 ℃ of four district's temperature 136 ℃He five district's temperature.
Embodiment 3
A kind of water-proof environmental protection PVC is material modified, comprises the raw material of following weight part:
100 parts of polyvinyl chloride resins
5 parts of weighting agents
60 parts, softening agent
6 parts of thermo-stabilizers
12 parts of impact modifiers
6 parts of modified rubbers
2 parts of lubricants;
The mixture that described softening agent is comprised of with weight ratio 9:1 trioctyl trimellitate and epoxy soybean oil; The mixture that described modified rubber is comprised of with weight ratio 1.5:2.0:1 isoprene-isobutylene rubber, nitrile rubber and terpolymer EP rubber; Described polyvinyl chloride resin is that particle diameter is at the polyvinyl chloride resin of 0.15mm; Described weighting agent is particle diameter at 10nm and the ultramicrofine light calcium carbonate processed through titante coupling agent; Described thermo-stabilizer is the mixture being comprised of with weight ratio 30:6:1 Soil stability agent, auxiliary stabilizer and auxiliary agent; The mixture that described main body thermo-stabilizer is comprised of with weight ratio 2.0:1:2.2 Zinic stearas, calcium stearate and zinc laurate; Described auxiliary heat stabilizer is by carbon back-4, the mixture that 4-bis-different fork-fatty alcohol-phosphorous acid chelating chemical combination polymkeric substance and tetramethylolmethane form with weight ratio 2:1; The mixture that described auxiliary agent is comprised of with weight ratio 6:1 emulsifying agent and defoamer; The mixture that described emulsifying agent is comprised of with weight ratio 2.8:2.0:1 potassium oleate, potassium stearate and potassium rosinate; The mixture that described defoamer is comprised of with weight ratio 1:2.0 tributyl phosphate and polydimethylsiloxane; Described impact modifier is chlorinity at 35% chlorinatedpolyethylene; The mixture that described lubricant is comprised of with weight ratio 1.5:1 native paraffin and methylene-bis stearylamide.
The preparation method that water-proof environmental protection PVC is material modified, comprises the steps:
(1) by the weight part of constitutive material, take above-mentioned raw materials, mix;
(2) mixed raw material is put into high speed blender, at 120 ℃ of temperature, stir 20min;
(3) raw material after stirring is passed through to twin screw extruder extruding pelletization, make water-proof environmental protection PVC material modified; The extruder temperature of described twin screw extruder is: 149 ℃ of district's temperature, 147 ℃ of two district's temperature, 145 ℃ of three district's temperature, 139 ℃ of four district's temperature 141 ℃He five district's temperature.
Embodiment 4
A kind of water-proof environmental protection PVC is material modified, comprises the raw material of following weight part:
110 parts of polyvinyl chloride resins
28 parts of weighting agents
65 parts, softening agent
7 parts of thermo-stabilizers
13 parts of impact modifiers
7 parts of modified rubbers
1.5 parts of lubricants;
The mixture that described softening agent is comprised of with weight ratio 9.5:1 trioctyl trimellitate and epoxy soybean oil; The mixture that described modified rubber is comprised of with weight ratio 1.6:2.2:1 isoprene-isobutylene rubber, nitrile rubber and terpolymer EP rubber; Described polyvinyl chloride resin is that particle diameter is at the polyvinyl chloride resin of 0.18mm; Described weighting agent is particle diameter at 15nm and the ultramicrofine light calcium carbonate processed through titante coupling agent; Described thermo-stabilizer is the mixture being comprised of with weight ratio 35:7:1 Soil stability agent, auxiliary stabilizer and auxiliary agent; The mixture that described main body thermo-stabilizer is comprised of with weight ratio 2.2:1:2.4 Zinic stearas, calcium stearate and zinc laurate; Described auxiliary heat stabilizer is by carbon back-4, the mixture that 4-bis-different fork-fatty alcohol-phosphorous acid chelating chemical combination polymkeric substance and tetramethylolmethane form with weight ratio 2.2:1; The mixture that described auxiliary agent is comprised of with weight ratio 7:1 emulsifying agent and defoamer; The mixture that described emulsifying agent is comprised of with weight ratio 3:2.2:1 potassium oleate, potassium stearate and potassium rosinate; The mixture that described defoamer is comprised of with weight ratio 1:2.2 tributyl phosphate and polydimethylsiloxane; Described impact modifier is chlorinity at 40% chlorinatedpolyethylene; The mixture that described lubricant is comprised of with weight ratio 1.6:1 native paraffin and methylene-bis stearylamide.
The preparation method that water-proof environmental protection PVC is material modified, comprises the steps:
1) by the weight part of constitutive material, take above-mentioned raw materials, mix;
(2) mixed raw material is put into high speed blender, at 130 ℃ of temperature, stir 22min;
(3) raw material after stirring is passed through to twin screw extruder extruding pelletization, make water-proof environmental protection PVC material modified; The extruder temperature of described twin screw extruder is: 155 ℃ of district's temperature, 153 ℃ of two district's temperature, 150 ℃ of three district's temperature, 144 ℃ of four district's temperature 145 ℃He five district's temperature.
Embodiment 5
A kind of water-proof environmental protection PVC is material modified, comprises the raw material of following weight part:
120 parts of polyvinyl chloride resins
30 parts of weighting agents
70 parts, softening agent
8 parts of thermo-stabilizers
15 parts of impact modifiers
8 parts of modified rubbers
1 part of lubricant;
The mixture that described softening agent is comprised of with weight ratio 10:1 trioctyl trimellitate and epoxy soybean oil; The mixture that described modified rubber is comprised of with weight ratio 1.8:2.4:1 isoprene-isobutylene rubber, nitrile rubber and terpolymer EP rubber; Described polyvinyl chloride resin is that particle diameter is at the polyvinyl chloride resin of 0.2mm; Described weighting agent is particle diameter at 20nm and the ultramicrofine light calcium carbonate processed through titante coupling agent; Described thermo-stabilizer is the mixture being comprised of with weight ratio 40:8:1 Soil stability agent, auxiliary stabilizer and auxiliary agent; The mixture that described main body thermo-stabilizer is comprised of with weight ratio 2.4:1:2.6 Zinic stearas, calcium stearate and zinc laurate; Described auxiliary heat stabilizer is by carbon back-4, the mixture that 4-bis-different fork-fatty alcohol-phosphorous acid chelating chemical combination polymkeric substance and tetramethylolmethane form with weight ratio 2.5:1; The mixture that described auxiliary agent is comprised of with weight ratio 8:1 emulsifying agent and defoamer; The mixture that described emulsifying agent is comprised of with weight ratio 3.2:2.4:1 potassium oleate, potassium stearate and potassium rosinate; The mixture that described defoamer is comprised of with weight ratio 1:2.4 tributyl phosphate and polydimethylsiloxane; Described impact modifier is chlorinity at 45% chlorinatedpolyethylene; The mixture that described lubricant is comprised of with weight ratio 1.8:1 native paraffin and methylene-bis stearylamide.
The preparation method that water-proof environmental protection PVC is material modified, comprises the steps:
(1) by the weight part of constitutive material, take above-mentioned raw materials, mix;
(2) mixed raw material is put into high speed blender, at 140 ℃ of temperature, stir 25min;
(3) raw material after stirring is passed through to twin screw extruder extruding pelletization, make water-proof environmental protection 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 four district's temperature 150 ℃He five district's temperature.
The material modified mechanical and physical performance of water-proof environmental protection PVC that embodiments of the invention 1-5 makes is as shown in table 1.
Table 1
| Test event | Standard value | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Water-repellancy | Well | Good | Good | Good | Good | Good |
| Tensile strength (MPa) | ≥15.0 | 22.3 | 24.4 | 25.6 | 26.1 | 23.2 |
| Flexural strength (MPa) | ≥15.0 | 46.8 | 48.7 | 51.6 | 54.4 | 45.2 |
| Elongation at break (%) | ≥150 | 299 | 304 | 311 | 322 | 302 |
| Heat-drawn wire (℃) | ≥50.0 | 115.4 | 118.2 | 120.5 | 122.4 | 116.2 |
| Impact embrittlement temperature (℃) | ≤-20 | -35 | -35 | -40 | -40 | -35 |
| Heat-stable time in the time of 200 ℃ (min) | ≥60 | 90 | 110 | 120 | 120 | 100 |
| Hardness/Shore D | ≥50 | 79 | 82 | 84 | 85 | 80 |
| Fire-retardant | V0 | V0 | V0 | V0 | V0 | V0 |
As can be seen from Table 1, the material modified properties of water-proof environmental protection PVC that the present invention makes has all exceeded national standard, good water-proof effect, environmental protection, and resistance to elevated temperatures is good, intensity is high, good flame retardation effect, compression performance and toughness are strong, and processing characteristics is good, excellent combination property.Product of the present invention meets the international standards such as REACH, ROHS, PAHS, N-P, can be widely used in the industrial circles such as automobile, electronic apparatus, instrument, weaving and building.
Above-described embodiment is preferably implementation of the present invention, and in addition, the present invention can also realize by alternate manner, and any apparent replacement is all within protection scope of the present invention without departing from the inventive concept of the premise.
Claims (10)
1. a water-proof environmental protection PVC is material modified, it is characterized in that: the raw material that comprises following weight part:
Polyvinyl chloride resin 80-120 part
Weighting agent 20-30 part
Softening agent 50-70 part
Thermo-stabilizer 4-8 part
Impact modifier 10-15 part
Modified rubber 4-8 part
Lubricant 1-2 part;
The mixture that described softening agent is comprised of with weight ratio 8-10:1 trioctyl trimellitate and epoxy soybean oil;
The mixture that described modified rubber is comprised of with weight ratio 1.2-1.8:1.6-2.4:1 isoprene-isobutylene rubber, nitrile rubber and terpolymer EP rubber.
2. a kind of water-proof environmental protection PVC according to claim 1 is material modified, it is characterized in that: described polyvinyl chloride resin is that particle diameter is at the polyvinyl chloride resin of 0.1-0.2mm.
3. a kind of water-proof environmental protection PVC according to claim 1 is material modified, it is characterized in that: described weighting agent is particle diameter at 2-20nm and the ultramicrofine light calcium carbonate processed through titante coupling agent.
4. a kind of water-proof environmental protection PVC according to claim 1 is material modified, it is characterized in that: described thermo-stabilizer is the mixture being comprised of with weight ratio 20-40:4-8:1 Soil stability agent, auxiliary stabilizer and auxiliary agent.
5. a kind of water-proof environmental protection PVC according to claim 4 is material modified, it is characterized in that: the mixture that described main body thermo-stabilizer is comprised of with weight ratio 1.6-2.4:1:1.8-2.6 Zinic stearas, calcium stearate and zinc laurate; Described auxiliary heat stabilizer is by carbon back-4, the mixture that 4-bis-different fork-fatty alcohol-phosphorous acid chelating chemical combination polymkeric substance and tetramethylolmethane form with weight ratio 1.5-2.5:1.
6. a kind of water-proof environmental protection PVC according to claim 4 is material modified, it is characterized in that: the mixture that described auxiliary agent is comprised of with weight ratio 4-8:1 emulsifying agent and defoamer; The mixture that described emulsifying agent is comprised 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 comprised of with weight ratio 1:1.6-2.4 tributyl phosphate and polydimethylsiloxane.
7. a kind of water-proof environmental protection PVC according to claim 1 is material modified, it is characterized in that: described impact modifier is that chlorinity is at the chlorinatedpolyethylene of 25-45%.
8. a kind of water-proof environmental protection PVC according to claim 1 is material modified, it is characterized in that: the mixture that described lubricant is comprised of with weight ratio 1.2-1.8:1 native paraffin and methylene-bis stearylamide.
9. the material modified preparation method of a kind of water-proof environmental protection PVC as described in claim 1-8 any one, is characterized in that: comprise the steps:
(1) by the weight part of constitutive material, take above-mentioned raw materials, mix;
(2) mixed raw material is put into high speed blender, at 100-140 ℃ of temperature, stir 15-25min;
(3) raw material after stirring is passed through to twin screw extruder extruding pelletization, make water-proof environmental protection PVC material modified.
10. the material modified preparation method of a kind of water-proof environmental protection PVC according to claim 9, is characterized in that: the extruder temperature of described twin screw extruder is: a district temperature 138-160 ℃, two district temperature 135-160 ℃, three district temperature 135-155 ℃, four district temperature 132-150 ℃He five district temperature 130-148 ℃.
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