CN104140616A - High-elasticity environment-friendly PVC modified material and preparation method thereof - Google Patents
High-elasticity environment-friendly PVC modified material and preparation method thereof Download PDFInfo
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- CN104140616A CN104140616A CN201410374008.4A CN201410374008A CN104140616A CN 104140616 A CN104140616 A CN 104140616A CN 201410374008 A CN201410374008 A CN 201410374008A CN 104140616 A CN104140616 A CN 104140616A
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Abstract
The invention relates to the technical field of PVC modified materials, in particular to a high-elasticity environment-friendly PVC modified material and a preparation method of the high-elasticity environment-friendly PVC modified material. The high-elasticity environment-friendly PVC modified material comprises 80-120 parts of PVC resin, 10-15 parts of filler agents, 40-60 parts of plasticizers, 2-6 parts of heat stabilizers, 10-15 parts of impact modifiers and 15-35 parts of elasticity modifiers, wherein the plasticizers are a mixture composed of diisononyl phthalate and epoxidized soybean oil according to the weight ratio of 8-10:1, the elasticity modifiers are expanded polystyrene, the glass transition temperature of the expanded polystyrene ranges from 80 DEG C to 90 DEG C, and the density of the expanded polystyrene ranges from 1.04 g/cm<3> to 1.06 g/cm<3>. All properties of the prepared high-elasticity environment-friendly PVC modified material exceed national standards, elasticity is high, the maximum tensile strength is 24.6 MPa, and the maximum elongation at break is 567 percent, and the PVC modified material is environmentally friendly. The preparation method of the high-elasticity environment-friendly PVC modified material is simple in process, convenient to implement and control, stable in quality, high in production efficiency and applicable 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 snappiness environment-friendly 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 200910116208.9 to disclose a kind of PVC material and preparation method thereof, and described PVC material comprises following material and weight part: 100 parts of PVC, 2-8 part stablizer, 2-6 part processing aid, 1.5-2.5 lubricant, 4-12 part filler, 0.05-1 part tinting material.
Application number is 201110306510.8 to disclose a kind of proprietary material of pvc pipe material, by forming according to the component of weight part as follows: 100 parts of polyvinyl chloride resins, nitrile rubber/nano-calcium carbonate composite powder rubber 4-16 part, chlorinatedpolyethylene 2.5-7 part, thermo-stabilizer 0.4-6 part, lubricant 1.1-3.5 part and tinting material 0.3-3.8 part.
Application number is 201110427270.7 to disclose a kind of antistatic PVC particulate material and preparation method thereof, raw material by following weight proportioning is prepared from: PVC SG-3 90-100 part, plasticizer DOP 70-85 part, one package stabilizer 4-5.5 part, stearate 1-3 part, weighting agent 35-48 part, initiator DCP 0.2-0.5 part, reactive monomer TAIC 3-5 part, oxyethane 4-6 part, ethylene oxide 1-3 part.
The performance index of existing most of PVC material are all to meet the basic demand of national standard, and the elasticity of current PVC material is not good enough, and therefore, the elasticity 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, researches and develops that a kind of PVC of environmental protection is material modified also seems particularly important.
Summary of the invention
In order to overcome the shortcoming and defect existing in prior art, the object of the present invention is to provide a kind of snappiness environment-friendly PVC material modified, this material modified good springiness, 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 a kind of snappiness environment-friendly PVC material modified preparation method, 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 snappiness environment-friendly PVC is material modified, comprises the raw material of following weight part:
Polyvinyl chloride resin 80-120 part
Weighting agent 10-15 part
Softening agent 40-60 part
Thermo-stabilizer 2-6 part
Impact modifier 10-15 part
Elastomeric modification agent 15-35 part;
The mixture that described softening agent is comprised of with weight ratio 8-10:1 diisononyl phthalate and epoxy soybean oil.
Diisononyl phthalate (DINP), colourless oil liquid, molecular formula is C
26h
42o
4, molecular weight is 418.6, and density is 0.973-0.977, belongs to nontoxic epoxy plasticiser, is a kind of universal primary plasticizer of excellent property, and DINP can be used as vinyl resin plasticizer, paracril tenderizer, the tensile strength auxiliary agent of celluloid lacquer etc.DINP compares with o-phthalic acid dibutyl ester (DOP), and more greatly, carbochain is longer for molecular weight, so have better aging resistance, ability of resisting to migration, anti-extraction ability, higher resistance to elevated temperatures, accordingly, under equal conditions, the plasticizing effect of DINP is slightly poorer than DOP.DINP, than more environmental protection of DOP, is 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 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 diisononyl phthalate 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.
Described elastomeric modification agent is second-order transition temperature at 80-90 ℃, density at 1.04-1.06g/cm
3polystyrene foamed.
Polystyrene foamed (EPS) claim again Expandable Polystyrene (EPS), is by styrene suspension polymerization, then add whipping agent and make.EPS is the hard honeycomb shape foam thing of polystyrene (PS), has good thermal insulation and shock absorbing effect, high compression-strength, and very light weight, polystyrene foamed joins in PVC, can improve the elasticity of material.The present invention is controlled at 1.04-1.06g/cm by the second-order transition temperature of polystyrene foamed being controlled to 80-90 ℃, density
3, the elastic properties of materials making is good, tensile strength and elongation are large, the elasticity of material be improved significantly.
Preferably, also comprise lubricant 1-2 part, the mixture that described lubricant is comprised of with weight ratio 1.2-1.8:1 PE wax and pentaerythritol stearate.
The present invention adopts PE wax as external lubricant, can reduce the friction of PVC melt and mould, machine barrel; Adopt pentaerythritol stearate 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.
Preferably, described polyvinyl chloride resin be the polymerization degree in 1000-1200, density at 1.35-1.45g/cm
3polyvinyl chloride resin.
The physical and mechanical properties of the molecular weight of polyvinyl chloride resin (polymerization degree) and goods is relevant, and molecular weight is higher, and the tensile strength of goods, shock strength, Young's modulus are higher; The present invention, can be so that goods have higher intensity by the polymerization degree of polyvinyl chloride resin is controlled to 1000-1200.
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 is by being controlled at 1.35-1.45g/cm by the density of polyvinyl chloride resin
3, make material plasticizing rate fast, easily processing.
Preferably, described weighting agent is particle diameter at 2-20nm and the nm-class active calcium carbonate processed through maleic anhydride graft polyvinyl chloride.
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 super nm-class active 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 nm-class active calcium carbonate of processing through compatilizer maleic anhydride graft polyvinyl chloride, can improve the consistency of nm-class active 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 6-8:1.5-2.5:1 hydrotalcite, calcium stearate and Zinic stearas; 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 N.F,USP MANNITOL form with weight ratio 1.8-2.6:1.
The present invention adopts hydrotalcite, calcium stearate and Zinic stearas as main body thermo-stabilizer, and to control its weight ratio be 6-8:1.5-2.5:1, 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 N.F,USP MANNITOL are as auxiliary heat stabilizer, and to control its weight ratio be 1.8-2.6:1, 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; Described defoamer is by tributyl phosphate and a kind of mixture forming than 1:1.6-2.4 of 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 styrene-butadiene-styrene block copolymer, and wherein, the content of styrene units is 10-30%, and the content of butadiene unit is 70-90%.
The kind that styrene-butadiene-styrene block copolymer (SBS) is output maximum (accounting for more than 70%) in styrene series thermoplastic elastomer (being called again styrene block copolymer), cost is minimum, application is wider, to take the triblock copolymer that vinylbenzene, divinyl is monomer, have the characteristic of plastics and rubber concurrently, be called as " third generation synthetic rubber ".Similar to styrene-butadiene rubber(SBR), the characteristic such as SBS can contact with water, weak acid, alkali etc., has good tensile strength, and skin friction coefficient is large, and low-temperature performance is good, and electrical property is good, good processability, becomes the thermoplastic elastomer of current consumption maximum.The present invention is by selecting styrene-butadiene-styrene block copolymer as impact modifier, and the content of controlling styrene units is at 10-30%, and the content of butadiene unit is at 70-90%, and the material shock resistance making is good, and the elasticity of material is better.
Another object of the present invention is achieved through the following technical solutions: the material modified preparation method of a kind of snappiness environment-friendly 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 snappiness environment-friendly 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 diisononyl phthalate 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 is controlled at 1.04-1.06g/cm by the second-order transition temperature of polystyrene foamed being controlled to 80-90 ℃, density
3, the elastic properties of materials making is good, tensile strength and elongation are large, the elasticity of material be improved significantly.
The present invention adopts PE wax as external lubricant, can reduce the friction of PVC melt and mould, machine barrel; Adopt pentaerythritol stearate 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 present invention, can be so that goods have higher intensity by the polymerization degree of polyvinyl chloride resin is controlled to 1000-1200.The present invention is by being controlled at 1.35-1.45g/cm by the density of polyvinyl chloride resin
3, make material plasticizing rate fast, easily processing.
The present invention adopts the nm-class active calcium carbonate of processing through compatilizer maleic anhydride graft polyvinyl chloride, can improve the consistency of nm-class active calcium carbonate and polyvinyl chloride resin, thereby improves 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 hydrotalcite, calcium stearate and Zinic stearas as main body thermo-stabilizer, and to control its weight ratio be 6-8:1.5-2.5:1, 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 N.F,USP MANNITOL are as auxiliary heat stabilizer, and to control its weight ratio be 1.8-2.6:1, 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 is by selecting styrene-butadiene-styrene block copolymer as impact modifier, and the content of controlling styrene units is at 10-30%, and the content of butadiene unit is at 70-90%, and the material shock resistance making is good, and the elasticity of material is better.
The material modified properties of snappiness environment-friendly PVC that the present invention makes has all exceeded national standard, good springiness, 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 snappiness environment-friendly PVC is material modified, comprises the raw material of following weight part:
80 parts of polyvinyl chloride resins
10 parts of weighting agents
40 parts, softening agent
2 parts of thermo-stabilizers
10 parts of impact modifiers
15 parts of elastomeric modification agent
1 part of lubricant;
The mixture that described softening agent is comprised of with weight ratio 8:1 diisononyl phthalate and epoxy soybean oil; Described elastomeric modification agent is second-order transition temperature at 80 ℃, density at 1.04g/cm
3polystyrene foamed; The mixture that described lubricant is comprised of with weight ratio 1.2:1 PE wax and pentaerythritol stearate; Described polyvinyl chloride resin is the polymerization degree 1000, density is at 1.35g/cm
3polyvinyl chloride resin; Described weighting agent is particle diameter at 2nm and the nm-class active calcium carbonate processed through maleic anhydride graft polyvinyl chloride; 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 6:1.5:1 hydrotalcite, calcium stearate and Zinic stearas; 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 N.F,USP MANNITOL form with weight ratio 1.8:1; 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; Described defoamer is by tributyl phosphate and a kind of mixture forming than 1:1.6 of polydimethylsiloxane; Described impact modifier is styrene-butadiene-styrene block copolymer, and wherein, the content of styrene units is 10%, and the content of butadiene unit is 90%.
The preparation method that snappiness environment-friendly 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 snappiness 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 four district's temperature 132 ℃He five district's temperature.
Embodiment 2
A kind of snappiness environment-friendly PVC is material modified, comprises the raw material of following weight part:
90 parts of polyvinyl chloride resins
11 parts of weighting agents
45 parts, softening agent
3 parts of thermo-stabilizers
11 parts of impact modifiers
20 parts of elastomeric modification agent
1.2 parts of lubricants;
The mixture that described softening agent is comprised of with weight ratio 8.5:1 diisononyl phthalate and epoxy soybean oil; Described elastomeric modification agent is second-order transition temperature at 82 ℃, density at 1.05g/cm
3polystyrene foamed; The mixture that described lubricant is comprised of with weight ratio 1.3:1 PE wax and pentaerythritol stearate; Described polyvinyl chloride resin is the polymerization degree 1030, density is at 1.38g/cm
3polyvinyl chloride resin; Described weighting agent is particle diameter at 5nm and the nm-class active calcium carbonate processed through maleic anhydride graft polyvinyl chloride; 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 6.5:1.8:1 hydrotalcite, calcium stearate and Zinic stearas; 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 N.F,USP MANNITOL form with weight ratio 2.0:1; 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; Described defoamer is by tributyl phosphate and a kind of mixture forming than 1:1.8 of polydimethylsiloxane; Described impact modifier is styrene-butadiene-styrene block copolymer, and wherein, the content of styrene units is 15%, and the content of butadiene unit is 85%.
The preparation method that snappiness environment-friendly 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 snappiness environment-friendly 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 snappiness environment-friendly PVC is material modified, comprises the raw material of following weight part:
100 parts of polyvinyl chloride resins
12 parts of weighting agents
50 parts, softening agent
4 parts of thermo-stabilizers
12 parts of impact modifiers
25 parts of elastomeric modification agent
1.5 parts of lubricants;
The mixture that described softening agent is comprised of with weight ratio 9:1 diisononyl phthalate and epoxy soybean oil; Described elastomeric modification agent is second-order transition temperature at 85 ℃, density at 1.06g/cm
3polystyrene foamed; The mixture that described lubricant is comprised of with weight ratio 1.5:1 PE wax and pentaerythritol stearate; Described polyvinyl chloride resin is the polymerization degree 1100, density is at 1.40g/cm
3polyvinyl chloride resin; Described weighting agent is particle diameter at 10nm and the nm-class active calcium carbonate processed through maleic anhydride graft polyvinyl chloride; 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 7:2:1 hydrotalcite, calcium stearate and Zinic stearas; 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 N.F,USP MANNITOL form with weight ratio 2.2:1; 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; Described defoamer is by tributyl phosphate and a kind of mixture forming than 1:2.0 of polydimethylsiloxane; Described impact modifier is styrene-butadiene-styrene block copolymer, and wherein, the content of styrene units is 20%, and the content of butadiene unit is 80%.
The preparation method that snappiness environment-friendly 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 snappiness environment-friendly 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 snappiness environment-friendly PVC is material modified, comprises the raw material of following weight part:
110 parts of polyvinyl chloride resins
13 parts of weighting agents
55 parts, softening agent
5 parts of thermo-stabilizers
13 parts of impact modifiers
30 parts of elastomeric modification agent
1.8 parts of lubricants;
The mixture that described softening agent is comprised of with weight ratio 9.5:1 diisononyl phthalate and epoxy soybean oil; Described elastomeric modification agent is second-order transition temperature at 88 ℃, density at 1.05g/cm
3polystyrene foamed; The mixture that described lubricant is comprised of with weight ratio 1.7:1 PE wax and pentaerythritol stearate; Described polyvinyl chloride resin is the polymerization degree 1150, density is at 1.42g/cm
3polyvinyl chloride resin; Described weighting agent is particle diameter at 15nm and the nm-class active calcium carbonate processed through maleic anhydride graft polyvinyl chloride; 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 7.5:2.2:1 hydrotalcite, calcium stearate and Zinic stearas; 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 N.F,USP MANNITOL form with weight ratio 2.4:1; 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 3.0:2.2:1 potassium oleate, potassium stearate and potassium rosinate; Described defoamer is by tributyl phosphate and a kind of mixture forming than 1:1.6 of polydimethylsiloxane; Described impact modifier is styrene-butadiene-styrene block copolymer, and wherein, the content of styrene units is 25%, and the content of butadiene unit is 75%.
The preparation method that snappiness environment-friendly 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 snappiness environment-friendly 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 snappiness environment-friendly PVC is material modified, comprises the raw material of following weight part:
120 parts of polyvinyl chloride resins
15 parts of weighting agents
60 parts, softening agent
6 parts of thermo-stabilizers
15 parts of impact modifiers
35 parts of elastomeric modification agent
2 parts of lubricants;
The mixture that described softening agent is comprised of with weight ratio 10:1 diisononyl phthalate and epoxy soybean oil; Described elastomeric modification agent is second-order transition temperature at 90 ℃, density at 1.06g/cm
3polystyrene foamed; The mixture that described lubricant is comprised of with weight ratio 1.8:1 PE wax and pentaerythritol stearate; Described polyvinyl chloride resin is the polymerization degree 1200, density is at 1.45g/cm
3polyvinyl chloride resin; Described weighting agent is particle diameter at 20nm and the nm-class active calcium carbonate processed through maleic anhydride graft polyvinyl chloride; 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 8:12.5:1 hydrotalcite, calcium stearate and Zinic stearas; 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 N.F,USP MANNITOL form with weight ratio 2.6:1; 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; Described defoamer is by tributyl phosphate and a kind of mixture forming than 1:2.4 of polydimethylsiloxane; Described impact modifier is styrene-butadiene-styrene block copolymer, and wherein, the content of styrene units is 30%, and the content of butadiene unit is 70%.
The preparation method that snappiness environment-friendly 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 snappiness 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 four district's temperature 150 ℃He five district's temperature.
The material modified mechanical and physical performance of snappiness environment-friendly 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 |
| Tensile strength (MPa) | ≥15.0 | 21.2 | 23.3 | 24.6 | 24.1 | 22.1 |
| Flexural strength (MPa) | ≥15.0 | 45.7 | 47.5 | 50.6 | 53.4 | 44.2 |
| Elongation at break (%) | ≥150 | 544 | 548 | 556 | 567 | 546 |
| Heat-drawn wire (℃) | ≥50.0 | 114.1 | 117.2 | 118.2 | 120.8 | 114.9 |
| Impact embrittlement temperature (℃) | ≤-20 | -25 | -25 | -30 | -30 | -25 |
| Heat-stable time in the time of 200 ℃ (min) | ≥60 | 90 | 110 | 120 | 120 | 100 |
| Hardness/Shore D | ≥50 | 81 | 84 | 86 | 87 | 82 |
| Fire-retardant | V0 | V0 | V0 | V0 | V0 | V0 |
As can be seen from Table 1, the material modified properties of snappiness environment-friendly PVC that the present invention makes has all exceeded national standard, good springiness, and tensile strength is 24.6 MPa to the maximum, and elongation at break maximum reaches 567%, 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.
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 snappiness environment-friendly 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 10-15 part
Softening agent 40-60 part
Thermo-stabilizer 2-6 part
Impact modifier 10-15 part
Elastomeric modification agent 15-35 part;
The mixture that described softening agent is comprised of with weight ratio 8-10:1 diisononyl phthalate and epoxy soybean oil;
Described elastomeric modification agent is second-order transition temperature at 80-90 ℃, density at 1.04-1.06g/cm
3polystyrene foamed.
2. a kind of snappiness environment-friendly PVC according to claim 1 is material modified, it is characterized in that: also comprise lubricant 1-2 part, the mixture that described lubricant is comprised of with weight ratio 1.2-1.8:1 PE wax and pentaerythritol stearate.
3. a kind of snappiness environment-friendly PVC according to claim 1 is material modified, it is characterized in that: described polyvinyl chloride resin be the polymerization degree in 1000-1200, density at 1.35-1.45g/cm
3polyvinyl chloride resin.
4. a kind of snappiness environment-friendly PVC according to claim 1 is material modified, it is characterized in that: described weighting agent is particle diameter at 2-20nm and the nm-class active calcium carbonate processed through maleic anhydride graft polyvinyl chloride.
5. a kind of snappiness environment-friendly 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.
6. a kind of snappiness environment-friendly PVC according to claim 5 is material modified, it is characterized in that: the mixture that described main body thermo-stabilizer is comprised of with weight ratio 6-8:1.5-2.5:1 hydrotalcite, calcium stearate and Zinic stearas; 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 N.F,USP MANNITOL form with weight ratio 1.8-2.6:1.
7. a kind of snappiness environment-friendly PVC according to claim 5 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; Described defoamer is by tributyl phosphate and a kind of mixture forming than 1:1.6-2.4 of polydimethylsiloxane.
8. a kind of snappiness environment-friendly PVC according to claim 1 is material modified, it is characterized in that: described impact modifier is styrene-butadiene-styrene block copolymer, wherein, the content of styrene units is 10-30%, and the content of butadiene unit is 70-90%.
9. the material modified preparation method of a kind of snappiness environment-friendly 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 snappiness environment-friendly PVC material modified.
10. the material modified preparation method of a kind of snappiness environment-friendly 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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