CN105482309A - Radiation-proofing PVC modified material and preparation method thereof - Google Patents
Radiation-proofing PVC modified material and preparation method thereof Download PDFInfo
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- CN105482309A CN105482309A CN201511015850.XA CN201511015850A CN105482309A CN 105482309 A CN105482309 A CN 105482309A CN 201511015850 A CN201511015850 A CN 201511015850A CN 105482309 A CN105482309 A CN 105482309A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Abstract
The invention relates to the technical field of PVC materials, and particularly relates to a radiation-proofing PVC modified material and a preparation method thereof. The radiation-proofing PVC modified material is prepared from the following raw materials in parts by weight: 80-120 parts of PVC resin, 45-65 parts of plasticizer, 10-15 parts of an anti-gamma-ray agent, 3-7 parts of thermal stabilizer, 2-4 parts of toughening modifier and 0.4-0.8 part of an anti-ultraviolet agent. By adopting the raw materials and strictly controlling the weight proportion of the raw materials, each performance of the radiation-proofing PVC modified material is superior to the national standard, and the radiation-proofing PVC modified material has the advantages of good radiation proofing effect, environmental friendliness, excellent temperature resistance, excellent weather resistance, high strength, excellent impact resistance, good flame retardant performance, excellent processing performance and excellent comprehensive performance.
Description
Technical field
The present invention relates to PVC material technical field, it is material modified and preparation method thereof to be specifically related to a kind of radioprotective PVC.
Background technology
The advantages such as polyvinyl chloride (PVC) is one of industrialization the earliest, broad-spectrum general-purpose thermoplastic plastic, and it has, and quality is light, intensity is high, insulation, fire-retardant, corrosion-resistant, high comprehensive performance, cheap and raw material sources are extensive; But also there is following shortcoming: 1, poor toughness, very easily embrittlement when being hit, therefore can not be used as structured material, in addition, the fragility temperature influence of polyvinyl chloride is very large, and 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 just starts to decomposite HCl 100 DEG C time, more rapid higher than decomposing when 150 DEG C, and the melt temperature of PVC is about 210 DEG C; 3, the viscosity of PVC is high, mobility extreme difference, limits it to a certain extent and uses.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 200810218876.8 disclose a kind of PVC plastic glue sealing material, be made up of the component of following parts by weight: polyvinyl chloride resin 100 parts, 55 ~ 85 parts, softening agent, calcium-zinc composite stabilizing agent 0.8 ~ 5 part, weighting agent 30 ~ 70 parts, thermoplastic elastomer 0 ~ 25 part, antiseptic-germicide 0.01 ~ 0.05 part, toner 0.5 ~ 1.5 part, composite synergist 0.5 ~ 2 part.
Application number is that 200710029001.9 to disclose a kind of PVC material modified and preparation method thereof, it is made up of following component and parts by weight: PVC100 part, SAN2 ~ 100 part, expanding material 0.2 ~ 30 part, modifier 1 ~ 10 part, mineral filler 5 ~ 80 parts, thermo-stabilizer 0 ~ 10 part, lubricant 0 ~ 10 part, 0 ~ 10 part, oxidation inhibitor, whipping agent 0 ~ 5 part.
The harm of Radiation On Human body is very large, and the ray discharged when gamma ray is atomic energy order transition transformation, has very strong penetration power, have lethality to cell, therefore, researches and develops a kind of radiation-resistant PVC material and seems particularly necessary.
Summary of the invention
In order to overcome the shortcoming and defect existed in prior art, the object of the present invention is to provide a kind of radioprotective PVC material modified, this material modified radiation-proof effect is good, environmental protection, and resistance to gentle weather resistance is excellent, intensity is high, excellent shock resistance, good flame retardation effect, processing characteristics is excellent, excellent combination property.
Another object of the present invention is to the preparation method providing a kind of radioprotective PVC material modified, this preparation method's technique is simple, and convenient operation and control, steady quality, production efficiency is high, and production cost is low, can large-scale industrial production.
Object of the present invention is achieved through the following technical solutions: a kind of radioprotective PVC is material modified, the material modified raw material comprising following weight part of described radioprotective PVC:
Polyvinyl chloride resin 80-120 part
Softening agent 45-65 part
Anti-gamma ray agent 10-15 part
Thermo-stabilizer 3-7 part
Plasticized modifier 2-4 part
Anti UV agent 0.4-0.8 part.
Radioprotective PVC of the present invention is material modified by adopting above-mentioned raw materials, and the strict weight proportion controlling each raw material, the material modified properties of obtained radioprotective PVC is all beyond national standard, and radiation-proof effect is good, environmental protection, and resistance to gentle weather resistance is excellent, intensity is high, excellent shock resistance, good flame retardation effect, processing characteristics is excellent, excellent combination property.
Preferably, the mixture that is made up of with weight ratio 2-4:1 calcium carbide process PVC resin and ethylene process polyvinyl chloride resin of described polyvinyl chloride resin.
The present invention is by adopting calcium carbide process PVC resin and ethylene process polyvinyl chloride resin as the composite use of polyvinyl chloride resin, and to control its weight ratio be 2-4:1, makes plasticize speed fast, easily processes.
Preferably, described softening agent is the mixture be made up of with weight ratio 1.5-2.5:0.8-1.2:1 hexanaphthene 1,2-dioctyl phthalate diisononyl esters, triethyl citrate and epoxy soybean oil.
The present invention adopts 1,2-dioctyl phthalate diisononyl esters, triethyl citrate and epoxy soybean oil are as the composite use of softening agent, and to control its weight ratio be 1.5-2.5:0.8-1.2:1, three kinds of softening agent are environment-friendly plasticizer, the reactive force between PVC molecular chain can be reduced, the fusing point of the second-order transition temperature of PVC plastic, yield temperature and contained crystallite is all reduced, improves the plasticity-of resin, make goods softness, resistance to low temperature good.
Preferably, the mixture that is made up of with weight ratio 2-4:1 polysulfones and barium sulfate of described anti-gamma ray agent.
The present invention is by adopting polysulfones and barium sulfate as the composite use of anti-gamma ray agent, and to control its weight ratio be 2-4:1, the anti-gamma radiation of obtained material and anti-electromagnetic radiation effective.
Preferably, the mixture that is made up of with weight ratio 0.8-1.2:1 Ca-Zn composite heat stabilizer and hydrotalcite thermal stabilizer of described thermo-stabilizer.
Ca-Zn composite heat stabilizer not only can replace the poisonous stablizers such as plumbous cadmium salt class and organic tin, and has goodish thermostability, light stability and the transparency and tinting strength.Facts have proved, in polyvinyl chloride resin goods, good processability, heat stabilization is equivalent to lead salt stabilizer, is a kind of good non-toxic stabilizer.
Hydrotalcite stablizer has high thermal stability: distinctive sour absorption mechanism, result in its thermostability of thermostability higher than lead base; High transparent: have identical specific refractory power with PVC; High-insulativity: by anion exchange reaction, absorbed muriate can not discharge, and insulativity is splendid; High security: hydrotalcite can be applicable in the food pack of polymer materials; Good weathering resistance (environmental compatibility is strong), can not produce sulfide staining: can with various thermo-stabilizer with the use of.
The present invention is by adopting Ca-Zn composite heat stabilizer and hydrotalcite thermal stabilizer as the composite use of thermo-stabilizer, and to control its weight ratio be 0.8-1.2:1, can 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 mixture that described Ca-Zn composite heat stabilizer is made up of with weight ratio 0.5-1.5:1:0.5-1.5:0.8-1.2 calcium stearate, ricinolic acid calcium, Zinic stearas and zinc ricinate.
The present invention is by adopting calcium stearate, ricinolic acid calcium, Zinic stearas and zinc ricinate as Ca-Zn composite heat stabilizer, and to control its weight ratio be 0.5-1.5:1:0.5-1.5:0.8-1.2, there is goodish thermostability, light stability and the transparency and tinting strength, and good processability.
Preferably, the mixture that is made up of with weight ratio 8-12:1.5-2.5:1 high-density low pressure polyethylene, chlorinatedpolyethylene and titanate coupling agent of described plasticized modifier.
The present invention, by adopting the mixture of high-density low pressure polyethylene, chlorinatedpolyethylene and titanate coupling agent as plasticized modifier, can improve toughness and the processing characteristics of material.
Preferably, described anti UV agent is the mixture be made up of with weight ratio 1.5-2.5:1 4-benzoyloxy-2,2,6,6-tetramethyl piperidine and Octabenzone.
The present invention is by adopting 4-benzoyloxy-2,2,6,6-tetramethyl piperidine and Octabenzone are as the composite use of anti UV agent, and to control its weight ratio be 1.5-2.5:1, energy strong absorption ultraviolet, has excellent synergistic effect, makes material antiageing effect better.
Preferably, described radioprotective PVC is material modified also comprises weighting agent 5-10 part and lubricant 0.4-0.8 part, the mixture that described weighting agent is made up of with weight ratio 1-2:0.8-1.2:1 water-ground limestone, light calcium carbonate and kaolin.
The present invention is by adopting water-ground limestone, light calcium carbonate and kaolin as the composite use of weighting agent, and to control its weight ratio be 1-2:0.8-1.2:1, good with the consistency of polyvinyl chloride resin, thus improves intensity and the shock resistance of material.
The mixture that described lubricant is made up of with weight ratio 1.5-2.5:0.8-1.2:1 oxidized polyethlene wax, pentaerythritol stearate and ethylene bis stearic acid amide.
The present invention adopts oxidized polyethlene wax as external lubricant, can reduce the friction of PVC melt and mould, machine barrel; Adopt pentaerythritol stearate and ethylene bis stearic acid amide as internal lubricant, the intermolecular friction of PVC melt can be reduced; Three kinds of lubricants can make material in the course of processing, improve the mobility of material and the release property of goods with the composite use of weight ratio 1.5-2.5:0.8-1.2:1.
Preferably, described radioprotective PVC is material modified also comprises impact modifier 5-10 part, and described impact modifier is the mixture that the chlorinatedpolyethylene of 25%-45% and the ethylene-vinyl acetate copolymer of vinyl acetate between to for plastic unit content 5%-25% form with weight ratio 1.5-2.5:1 by chlorinity.
Chlorinatedpolyethylene (CPE) is a kind of properties-correcting agent of thermoplastics, has good over-all properties.Appropriate CPE is added, the processing characteristics that can reduce the melt viscosity of resin, improve mobility, improve plastics in polyvinyl chloride (PVC) resin; The work-ing life of the shock strength of PVC, resistance to low temperature, weathering performance, prolongation goods can also be improved.CPE also contributes to the dispersed of calcium carbonate and polyvinyl chloride resin; And when the chlorinity (weight content) of chlorinatedpolyethylene is for 25%-45%, make the resistance to impact shock of material best.
Ethylene-vinyl acetate copolymer (EVA) can be used as the impact modifying agent of PVC, has good flexibility, obdurability, lower temperature resistance (-58 DEG C still have pliability), weathering resistance, stress cracking resistance, heat sealer, agglutinating value(of coal), the transparency and glossiness; Also there is the elasticity as rubber simultaneously, excellent chemical stability, thermostability (heat decomposition temperature 229 ~ 230 DEG C), ozone resistance, nontoxicity, good processibility and dyeability; Fine with the miscibility of filler, even if fill more filler, also unlikelyly have a strong impact on its physical and mechanical property.
EVA is as the impact modifying agent of PVC, its effect is different with the content of vinyl acetate between to for plastic in multipolymer, when the content of vinyl acetate between to for plastic is low, with the poor compatibility of PVC, reinforced effects is poor, and goods are opaque, along with the increase of vinyl acetate between to for plastic unit content, the consistency of multipolymer and PVC improves, and reinforced effects improves, and the goods transparency is also better; But the content of vinyl acetate between to for plastic also can not be too high, during vinyl acetate between to for plastic unit content 5%-25%, obviously can improve the shock strength of PVC, compared with the impact modifying agent containing carbon-carbon double bond, also there is the good advantage of ageing resistance.
The present invention is by adopting chlorinatedpolyethylene and ethylene-vinyl acetate copolymer as the composite use of impact modifier, and to control its weight ratio be 1.5-2.5:1, the high temperature resistant of material and resistance to low temperature can be improved, the processing characteristics that can also reduce the melt viscosity of material, improve mobility, improve plastics, improves the work-ing life of the shock strength of material, weathering performance, prolongation goods.
Described radioprotective PVC is material modified also comprises fire retardant 1-5 part, slipping agent 0.05-0.15 part and pigment powder 0.01-0.05 part; The mixture that described fire retardant is made up of with weight ratio 0.5-1.5:1 antimonous oxide and zinc borate.
Antimonous oxide and lime borate are inorganic environment-friendly fire retardant, the present invention is by adopting antimonous oxide and zinc borate as the composite use of fire retardant, and to control its weight ratio be 0.5-1.5:1, good flame retardant effect can be reached, Drawing abillity and mechanical property can also be improved.
Described slipping agent is the mixture be made up of with weight ratio 1.5-2.5:0.8-1.2:1 erucicamide, amine hydroxybenzene and N, N'-ethylene bis stearamide.
The present invention is by adopting erucicamide, amine hydroxybenzene and N, N'-ethylene bis stearamide is as slipping agent and to control its weight ratio be 1.5-2.5:0.8-1.2:1, mechanical resistant stirring capacity and fingerprinting stress can be strengthened, finished product good forming effect, any surface finish, the extensibility of finished product can also be strengthened, easy-to-draw not easily broken.
Described pigment powder is particle diameter at the titanium dioxide of 1-5 μm; The mixture that described titanium dioxide is made up of with weight ratio 1:1.5-2.5 Rutile type Titanium Dioxide and anatase thpe white powder.
The present invention adopts particle diameter at the titanium dioxide of 1-5 μm as pigment powder, further employing Rutile type Titanium Dioxide and the composite use of anatase thpe white powder, and to control its weight ratio be 1:1.5-2.5, there is superior whiteness, tinting strength, opacifying power, weathering resistance, thermotolerance and chemical stability, particularly there is no toxicity.
Another object of the present invention is achieved through the following technical solutions: the preparation method that a kind of radioprotective PVC is material modified, comprises the steps:
(1) take above-mentioned raw materials mixing by weight ratio, put into high speed blender, at 100-140 DEG C of temperature, stir 15-25min;
(2) raw material after stirring is passed through twin screw extruder extruding pelletization, obtained radioprotective PVC is material modified.
Preparation method's technique of the present invention is simple, and convenient operation and control, steady quality, production efficiency is high, and production cost is low, can large-scale industrial production.
Preferably, in described step (2), the extruder temperature of twin screw extruder is: a district temperature 138-160 DEG C, two district temperature 135-160 DEG C, three district temperature 135-155 DEG C, four district temperature 132-150 DEG CHe five district temperature 130-148 DEG C.
Beneficial effect of the present invention is: the material modified properties of radioprotective PVC of the present invention is all beyond national standard, and radiation-proof effect is good, environmental protection, and resistance to gentle weather resistance is excellent, intensity is high, excellent shock resistance, good flame retardation effect, processing characteristics is excellent, excellent combination property.Radioprotective PVC of the present invention is material modified meets the International Environmental Protection standards such as REACH, ROHS, PAHS, N-P, can be widely used in the field that medical treatment etc. can produce radiation.
Preparation method's technique of the present invention is simple, and convenient operation and control, steady quality, production efficiency is high, and production cost is low, can large-scale industrial production.
Embodiment
For the ease of the understanding of those skilled in the art, 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 radioprotective PVC is material modified, the material modified raw material comprising following weight part of described radioprotective PVC:
Polyvinyl chloride resin 80 parts
45 parts, softening agent
Anti-gamma ray agent 10 parts
Thermo-stabilizer 3 parts
Plasticized modifier 2 parts
Anti UV agent 0.4 part.
The mixture that described polyvinyl chloride resin is made up of with weight ratio 2:1 calcium carbide process PVC resin and ethylene process polyvinyl chloride resin.
Described softening agent is the mixture be made up of with weight ratio 1.5:0.8:1 hexanaphthene 1,2-dioctyl phthalate diisononyl esters, triethyl citrate and epoxy soybean oil.
The mixture that described anti-gamma ray agent is made up of with weight ratio 2:1 polysulfones and barium sulfate.
The mixture that described thermo-stabilizer is made up of with weight ratio 0.8-1.2:1 Ca-Zn composite heat stabilizer and hydrotalcite thermal stabilizer; The mixture that described Ca-Zn composite heat stabilizer is made up of with weight ratio 0.5:1:0.5:0.8 calcium stearate, ricinolic acid calcium, Zinic stearas and zinc ricinate.
The mixture that described plasticized modifier is made up of with weight ratio 8:1.5:1 high-density low pressure polyethylene, chlorinatedpolyethylene and titanate coupling agent.
Described anti UV agent is the mixture be made up of with weight ratio 1.5:1 4-benzoyloxy-2,2,6,6-tetramethyl piperidine and Octabenzone.
Described radioprotective PVC is material modified also comprises weighting agent 5 parts and lubricant 0.4 part, the mixture that described weighting agent is made up of with weight ratio 1-2:0.8:1 water-ground limestone, light calcium carbonate and kaolin; The mixture that described lubricant is made up of with weight ratio 1.5:0.8:1 oxidized polyethlene wax, pentaerythritol stearate and ethylene bis stearic acid amide.
Described radioprotective PVC is material modified also comprises impact modifier 5 parts, and described impact modifier is the mixture that the chlorinatedpolyethylene of 45% and the ethylene-vinyl acetate copolymer of vinyl acetate between to for plastic unit content 5%% form with weight ratio 1.5:1 by chlorinity.
Described radioprotective PVC is material modified also comprises fire retardant 1 part, slipping agent 0.05 part and 0.01 part, pigment powder; The mixture that described fire retardant is made up of with weight ratio 1.1:1 antimonous oxide and zinc borate; Described slipping agent is the mixture be made up of with weight ratio 1.5:0.8:1 erucicamide, amine hydroxybenzene and N, N'-ethylene bis stearamide; Described pigment powder is particle diameter at the titanium dioxide of 1 μm; The mixture that described titanium dioxide is made up of with weight ratio 1:1.5 Rutile type Titanium Dioxide and anatase thpe white powder.
The preparation method that radioprotective PVC is material modified, comprises the steps:
(1) take above-mentioned raw materials mixing by weight ratio, put into high speed blender, at 100 DEG C of temperature, stir 25min;
(2) raw material after stirring is passed through twin screw extruder extruding pelletization, obtained radioprotective PVC is material modified.
In described step (2), the extruder temperature of twin 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 radioprotective PVC is material modified, the material modified raw material comprising following weight part of described radioprotective PVC:
Polyvinyl chloride resin 90 parts
50 parts, softening agent
Anti-gamma ray agent 11 parts
Thermo-stabilizer 5 parts
Plasticized modifier 2.5 parts
Anti UV agent 0.5 part.
The mixture that described polyvinyl chloride resin is made up of with weight ratio 2.5:1 calcium carbide process PVC resin and ethylene process polyvinyl chloride resin.
Described softening agent is the mixture be made up of with weight ratio 1.8:0.9:1 hexanaphthene 1,2-dioctyl phthalate diisononyl esters, triethyl citrate and epoxy soybean oil.
The mixture that described anti-gamma ray agent is made up of with weight ratio 2.5:1 polysulfones and barium sulfate.
The mixture that described thermo-stabilizer is made up of with weight ratio 0.9:1 Ca-Zn composite heat stabilizer and hydrotalcite thermal stabilizer; The mixture that described Ca-Zn composite heat stabilizer is made up of with weight ratio 0.8:1:0.8:0.9 calcium stearate, ricinolic acid calcium, Zinic stearas and zinc ricinate.
The mixture that described plasticized modifier is made up of with weight ratio 9:1.8:1 high-density low pressure polyethylene, chlorinatedpolyethylene and titanate coupling agent.
Described anti UV agent is the mixture be made up of with weight ratio 1.8:1 4-benzoyloxy-2,2,6,6-tetramethyl piperidine and Octabenzone.
Described radioprotective PVC is material modified also comprises weighting agent 6 parts and lubricant 0.5 part, the mixture that described weighting agent is made up of with weight ratio 1.2:0.9:1 water-ground limestone, light calcium carbonate and kaolin; The mixture that described lubricant is made up of with weight ratio 2.2:0.9:1 oxidized polyethlene wax, pentaerythritol stearate and ethylene bis stearic acid amide.
Described radioprotective PVC is material modified also comprises impact modifier 6 parts, and described impact modifier is the mixture that the chlorinatedpolyethylene of 30% and the ethylene-vinyl acetate copolymer of vinyl acetate between to for plastic unit content 10% form with weight ratio 1.8:1 by chlorinity.
Described radioprotective PVC is material modified also comprises fire retardant 2 parts, slipping agent 0.08 part and 0.02 part, pigment powder; The mixture that described fire retardant is made up of with weight ratio 1.2:1 antimonous oxide and zinc borate; Described slipping agent is the mixture be made up of with weight ratio 1.8:0.9:1 erucicamide, amine hydroxybenzene and N, N'-ethylene bis stearamide; Described pigment powder is particle diameter at the titanium dioxide of 2 μm; The mixture that described titanium dioxide is made up of with weight ratio 1:1.8 Rutile type Titanium Dioxide and anatase thpe white powder.
The preparation method that radioprotective PVC is material modified, comprises the steps:
(1) take above-mentioned raw materials mixing by weight ratio, put into high speed blender, at 110 DEG C of temperature, stir 22min;
(2) raw material after stirring is passed through twin screw extruder extruding pelletization, obtained radioprotective PVC is material modified.
In described step (2), the extruder temperature of twin screw extruder is: district's temperature 140 DEG C, two district's temperature 140 DEG C, three district's temperature 135 DEG C, four district's temperature 135 DEG CHe five district temperature 135 DEG C.
Embodiment 3
A kind of radioprotective PVC is material modified, the material modified raw material comprising following weight part of described radioprotective PVC:
Polyvinyl chloride resin 100 parts
55 parts, softening agent
Anti-gamma ray agent 12 parts
Thermo-stabilizer 5 parts
Plasticized modifier 3 parts
Anti UV agent 0.6 part.
The mixture that described polyvinyl chloride resin is made up of with weight ratio 3:1 calcium carbide process PVC resin and ethylene process polyvinyl chloride resin.
Described softening agent is the mixture be made up of with weight ratio 2:1:1 hexanaphthene 1,2-dioctyl phthalate diisononyl esters, triethyl citrate and epoxy soybean oil.
The mixture that described anti-gamma ray agent is made up of with weight ratio 3:1 polysulfones and barium sulfate.
The mixture that described thermo-stabilizer is made up of with weight ratio 1:1 Ca-Zn composite heat stabilizer and hydrotalcite thermal stabilizer; The mixture that described Ca-Zn composite heat stabilizer is made up of with weight ratio 1:1:1:1 calcium stearate, ricinolic acid calcium, Zinic stearas and zinc ricinate.
The mixture that described plasticized modifier is made up of with weight ratio 10:2:1 high-density low pressure polyethylene, chlorinatedpolyethylene and titanate coupling agent.
Described anti UV agent is the mixture be made up of with weight ratio 2:1 4-benzoyloxy-2,2,6,6-tetramethyl piperidine and Octabenzone.
Described radioprotective PVC is material modified also comprises weighting agent 8 parts and lubricant 0.6 part, the mixture that described weighting agent is made up of with weight ratio 1.5:1:1 water-ground limestone, light calcium carbonate and kaolin; The mixture that described lubricant is made up of with weight ratio 2:1:1 oxidized polyethlene wax, pentaerythritol stearate and ethylene bis stearic acid amide.
Described radioprotective PVC is material modified also comprises impact modifier 8 parts, and described impact modifier is the mixture that the chlorinatedpolyethylene of 35% and the ethylene-vinyl acetate copolymer of vinyl acetate between to for plastic unit content 15% form with weight ratio 2:1 by chlorinity.
Described radioprotective PVC is material modified also comprises fire retardant 3 parts, slipping agent 0.1 part and 0.03 part, pigment powder; The mixture that described fire retardant is made up of with weight ratio 1.3:1 antimonous oxide and zinc borate; Described slipping agent is the mixture be made up of with weight ratio 2:1:1 erucicamide, amine hydroxybenzene and N, N'-ethylene bis stearamide; Described pigment powder is particle diameter at the titanium dioxide of 3 μm; The mixture that described titanium dioxide is made up of with weight ratio 1:2 Rutile type Titanium Dioxide and anatase thpe white powder.
The preparation method that radioprotective PVC is material modified, comprises the steps:
(1) take above-mentioned raw materials mixing by weight ratio, put into high speed blender, at 120 DEG C of temperature, stir 20min;
(2) raw material after stirring is passed through twin screw extruder extruding pelletization, obtained radioprotective PVC is material modified.
In described step (2), the extruder temperature of twin 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.
Embodiment 4
A kind of radioprotective PVC is material modified, the material modified raw material comprising following weight part of described radioprotective PVC:
Polyvinyl chloride resin 110 parts
60 parts, softening agent
Anti-gamma ray agent 14 parts
Thermo-stabilizer 6 parts
Plasticized modifier 3.5 parts
Anti UV agent 0.7 part.
The mixture that described polyvinyl chloride resin is made up of with weight ratio 3.5:1 calcium carbide process PVC resin and ethylene process polyvinyl chloride resin.
Described softening agent is the mixture be made up of with weight ratio 2.2:1.1:1 hexanaphthene 1,2-dioctyl phthalate diisononyl esters, triethyl citrate and epoxy soybean oil.
The mixture that described anti-gamma ray agent is made up of with weight ratio 3.5:1 polysulfones and barium sulfate.
The mixture that described thermo-stabilizer is made up of with weight ratio 0.8-1.2:1 Ca-Zn composite heat stabilizer and hydrotalcite thermal stabilizer; The mixture that described Ca-Zn composite heat stabilizer is made up of with weight ratio 1.2:1:1.2:1.1 calcium stearate, ricinolic acid calcium, Zinic stearas and zinc ricinate.
The mixture that described plasticized modifier is made up of with weight ratio 11:2.2:1 high-density low pressure polyethylene, chlorinatedpolyethylene and titanate coupling agent.
Described anti UV agent is the mixture be made up of with weight ratio 2.2:1 4-benzoyloxy-2,2,6,6-tetramethyl piperidine and Octabenzone.
Described radioprotective PVC is material modified also comprises weighting agent 9 parts and lubricant 0.7 part, the mixture that described weighting agent is made up of with weight ratio 1.8:1.1:1 water-ground limestone, light calcium carbonate and kaolin; The mixture that described lubricant is made up of with weight ratio 2.2:1.1:1 oxidized polyethlene wax, pentaerythritol stearate and ethylene bis stearic acid amide.
Described radioprotective PVC is material modified also comprises impact modifier 9 parts, and described impact modifier is the mixture that the chlorinatedpolyethylene of 40% and the ethylene-vinyl acetate copolymer of vinyl acetate between to for plastic unit content 20% form with weight ratio 2.2:1 by chlorinity.
Described radioprotective PVC is material modified also comprises fire retardant 4 parts, slipping agent 0.12 part and 0.04 part, pigment powder; The mixture that described fire retardant is made up of with weight ratio 1.4:1 antimonous oxide and zinc borate; Described slipping agent is the mixture be made up of with weight ratio 2.2:1.1:1 erucicamide, amine hydroxybenzene and N, N'-ethylene bis stearamide; Described pigment powder is particle diameter at the titanium dioxide of 4 μm; The mixture that described titanium dioxide is made up of with weight ratio 1:2.2 Rutile type Titanium Dioxide and anatase thpe white powder.
The preparation method that radioprotective PVC is material modified, comprises the steps:
(1) take above-mentioned raw materials mixing by weight ratio, put into high speed blender, at 130 DEG C of temperature, stir 18min;
(2) raw material after stirring is passed through twin screw extruder extruding pelletization, obtained radioprotective PVC is material modified.
In described step (2), the extruder temperature of twin screw extruder is: district's temperature 155 DEG C, two district's temperature 155 DEG C, three district's temperature 150 DEG C, four district's temperature 148 DEG CHe five district temperature 145 DEG C.
Embodiment 5
A kind of radioprotective PVC is material modified, the material modified raw material comprising following weight part of described radioprotective PVC:
Polyvinyl chloride resin 120 parts
65 parts, softening agent
Anti-gamma ray agent 15 parts
Thermo-stabilizer 7 parts
Plasticized modifier 4 parts
Anti UV agent 0.8 part.
The mixture that described polyvinyl chloride resin is made up of with weight ratio 4:1 calcium carbide process PVC resin and ethylene process polyvinyl chloride resin.
Described softening agent is the mixture be made up of with weight ratio 2.5:1.2:1 hexanaphthene 1,2-dioctyl phthalate diisononyl esters, triethyl citrate and epoxy soybean oil.
The mixture that described anti-gamma ray agent is made up of with weight ratio 4:1 polysulfones and barium sulfate.
The mixture that described thermo-stabilizer is made up of with weight ratio 1.2:1 Ca-Zn composite heat stabilizer and hydrotalcite thermal stabilizer; The mixture that described Ca-Zn composite heat stabilizer is made up of with weight ratio 1.5:1:1.5:1.2 calcium stearate, ricinolic acid calcium, Zinic stearas and zinc ricinate.
The mixture that described plasticized modifier is made up of with weight ratio 12:2.5:1 high-density low pressure polyethylene, chlorinatedpolyethylene and titanate coupling agent.
Described anti UV agent is the mixture be made up of with weight ratio 2.5:1 4-benzoyloxy-2,2,6,6-tetramethyl piperidine and Octabenzone.
Described radioprotective PVC is material modified also comprises weighting agent 10 parts and lubricant 0.8 part, the mixture that described weighting agent is made up of with weight ratio 2:1.2:1 water-ground limestone, light calcium carbonate and kaolin; The mixture that described lubricant is made up of with weight ratio 2.5:1.2:1 oxidized polyethlene wax, pentaerythritol stearate and ethylene bis stearic acid amide.
Described radioprotective PVC is material modified also comprises impact modifier 10 parts, and described impact modifier is the mixture that the chlorinatedpolyethylene of 45% and the ethylene-vinyl acetate copolymer of vinyl acetate between to for plastic unit content 25% form with weight ratio 2.5:1 by chlorinity.
Described radioprotective PVC is material modified also comprises fire retardant 5 parts, slipping agent 0.15 part and 0.05 part, pigment powder; The mixture that described fire retardant is made up of with weight ratio 1.5:1 antimonous oxide and zinc borate; Described slipping agent is the mixture be made up of with weight ratio 2.5:1.2:1 erucicamide, amine hydroxybenzene and N, N'-ethylene bis stearamide; Described pigment powder is particle diameter at the titanium dioxide of 5 μm; The mixture that described titanium dioxide is made up of with weight ratio 1:2.5 Rutile type Titanium Dioxide and anatase thpe white powder.
The preparation method that radioprotective PVC is material modified, comprises the steps:
(1) take above-mentioned raw materials mixing by weight ratio, put into high speed blender, at 140 DEG C of temperature, stir 15min;
(2) raw material after stirring is passed through twin screw extruder extruding pelletization, obtained radioprotective PVC is material modified.
In described step (2), the extruder temperature of twin 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.
The material modified mechanical and physical performance of the radioprotective PVC that embodiment 1-5 obtains 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 | 23.8 | 25.9 | 27.2 | 27.6 | 24.7 |
| Flexural strength (MPa) | ≥15.0 | 48.4 | 50.3 | 52.2 | 55.8 | 46.8 |
| Elongation at break (%) | ≥150 | 293 | 298 | 303 | 316 | 295 |
| Heat-drawn wire (DEG C) | ≥50.0 | 118.3 | 120.9 | 123.4 | 125.1 | 119.1 |
| Impact embrittlement temperature (DEG C) | ≤-20 | -35 | -35 | -40 | -40 | -35 |
| Heat-stable time (min) when 200 DEG C | ≥60 | 100 | 120 | 130 | 130 | 110 |
| Hardness/Shore D | ≥50 | 82 | 85 | 87 | 88 | 83 |
| Fire-retardant | V0 | V0 | V0 | V0 | V0 | V0 |
| Anti-gamma radiation | ≥80% | 95% | 96% | 98% | 97% | 94% |
| Anti-electromagnetic radiation | ≥70% | 88% | 90% | 92% | 87% | 85% |
As can be seen from Table 1, the present invention obtain the material modified properties of radioprotective PVC all beyond national standard, radiation-proof effect is good, environmental protection, and resistance to gentle weather resistance is excellent, intensity is high, excellent shock resistance, good flame retardation effect, processing characteristics is excellent, excellent combination property.
Above-described embodiment is the present invention's preferably implementation, 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 radioprotective PVC is material modified, it is characterized in that: the material modified raw material comprising following weight part of described radioprotective PVC:
Polyvinyl chloride resin 80-120 part
Softening agent 45-65 part
Anti-gamma ray agent 10-15 part
Thermo-stabilizer 3-7 part
Plasticized modifier 2-4 part
Anti UV agent 0.4-0.8 part.
2. a kind of radioprotective PVC according to claim 1 is material modified, it is characterized in that: the mixture that described polyvinyl chloride resin is made up of with weight ratio 2-4:1 calcium carbide process PVC resin and ethylene process polyvinyl chloride resin.
3. a kind of radioprotective PVC according to claim 1 is material modified, it is characterized in that: described softening agent is the mixture be made up of with weight ratio 1.5-2.5:0.8-1.2:1 hexanaphthene 1,2-dioctyl phthalate diisononyl esters, triethyl citrate and epoxy soybean oil.
4. a kind of radioprotective PVC according to claim 1 is material modified, it is characterized in that: the mixture that described anti-gamma ray agent is made up of with weight ratio 2-4:1 polysulfones and barium sulfate.
5. a kind of radioprotective PVC according to claim 1 is material modified, it is characterized in that: the mixture that described thermo-stabilizer is made up of with weight ratio 0.8-1.2:1 Ca-Zn composite heat stabilizer and hydrotalcite thermal stabilizer; The mixture that described Ca-Zn composite heat stabilizer is made up of with weight ratio 0.5-1.5:1:0.5-1.5:0.8-1.2 calcium stearate, ricinolic acid calcium, Zinic stearas and zinc ricinate.
6. a kind of radioprotective PVC according to claim 1 is material modified, it is characterized in that: the mixture that described plasticized modifier is made up of with weight ratio 8-12:1.5-2.5:1 high-density low pressure polyethylene, chlorinatedpolyethylene and titanate coupling agent.
7. a kind of radioprotective PVC according to claim 1 is material modified, it is characterized in that: described anti UV agent is by 4-benzoyloxy-2, the mixture that 2,6,6-tetramethyl piperidine and Octabenzone form with weight ratio 1.5-2.5:1.
8. a kind of radioprotective PVC according to claim 1 is material modified, it is characterized in that: described radioprotective PVC is material modified also comprises weighting agent 5-10 part and lubricant 0.4-0.8 part, the mixture that described weighting agent is made up of with weight ratio 1-2:0.8-1.2:1 water-ground limestone, light calcium carbonate and kaolin; The mixture that described lubricant is made up of with weight ratio 1.5-2.5:0.8-1.2:1 oxidized polyethlene wax, pentaerythritol stearate and ethylene bis stearic acid amide.
9. the preparation method that a kind of radioprotective PVC as described in any one of claim 1-8 is material modified, is characterized in that: comprise the steps:
(1) take above-mentioned raw materials mixing by weight ratio, put into high speed blender, at 100-140 DEG C of temperature, stir 15-25min;
(2) raw material after stirring is passed through twin screw extruder extruding pelletization, obtained radioprotective PVC is material modified.
10. the preparation method that a kind of radioprotective PVC according to claim 9 is material modified, it is characterized in that: in described step (2), the extruder temperature of twin screw extruder is: a district temperature 138-160 DEG C, two district temperature 135-160 DEG C, three district temperature 135-155 DEG C, four district temperature 132-150 DEG CHe five district temperature 130-148 DEG C.
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| CN107266826A (en) * | 2017-07-31 | 2017-10-20 | 广东祺龙科技有限公司 | One kind rope skipping is material modified and preparation method thereof with PVC |
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| CN116333432A (en) * | 2023-03-10 | 2023-06-27 | 湖北省疾病预防控制中心（湖北省预防医学科学院） | Anti-radiation protective material and preparation method and application thereof |
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| CN106905641A (en) * | 2017-04-18 | 2017-06-30 | 东莞市祺龙电业有限公司 | A kind of wallpaper cloth is material modified and preparation method thereof with PVC |
| CN106916394A (en) * | 2017-04-18 | 2017-07-04 | 东莞市祺龙电业有限公司 | A kind of anti-slip carpet is material modified and preparation method thereof with PVC |
| CN107266826A (en) * | 2017-07-31 | 2017-10-20 | 广东祺龙科技有限公司 | One kind rope skipping is material modified and preparation method thereof with PVC |
| CN107603151A (en) * | 2017-09-01 | 2018-01-19 | 张峰 | A kind of encapsulating material and its preparation method and application of radiation-screening, high rigidity |
| CN107629363A (en) * | 2017-10-31 | 2018-01-26 | 桂林市漓江机电制造有限公司 | A kind of radiation proof is material modified and preparation method thereof |
| CN109593291A (en) * | 2018-10-29 | 2019-04-09 | 赵顺全 | A kind of preparation method of the medicinal stiff sheet of thermostabilization PVC |
| CN111925610A (en) * | 2020-08-25 | 2020-11-13 | 海宁市宏鹰装饰材料有限公司 | Novel PVC (polyvinyl chloride) plate and manufacturing method thereof |
| CN116333432A (en) * | 2023-03-10 | 2023-06-27 | 湖北省疾病预防控制中心（湖北省预防医学科学院） | Anti-radiation protective material and preparation method and application thereof |
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Address after: Ye Wu industrial zone Dalingshan Meilin Village 523000 Guangdong city of Dongguan Province Applicant after: Guangdong Qi Long Technology Co., Ltd. Address before: Ye Wu industrial zone Dalingshan Meilin Village 523820 Guangdong city of Dongguan Province Applicant before: Dongguan Qilong Electricity Co., Ltd. |
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Application publication date: 20160413 |