CN105419167A - Carpet environmental protection PVC modified material and preparation method therefor - Google Patents
Carpet environmental protection PVC modified material and preparation method therefor Download PDFInfo
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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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- 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
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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
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/011—Nanostructured additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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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Abstract
The invention relates to the PVC material technology field, and concretely relates to a carpet environmental protection PVC modified material and a preparation method therefor. The modified material comprises the following raw materials, by weight, 80-120 parts of PVC resin, 40-56 parts of plasticizer, 20-30 parts of filler, 8-12 parts of copolymerization resin, 3-7 parts of wear resistant modifier, 2-6 parts of heat stabilizer, 0.8-1.6 parts of antilubricant and 0.4-0.8 part of lubricant. The provided modified material employs the above raw materials, the weight ratios of the raw materials are controlled strictly, various performances of the prepared modified material exceed the national standard, environmental protection is achieved, temperature resistance and weather resistance are excellent, the intensity is high, the shock resistance is excellent, the flame retardant effects are good, the processing property is excellent, and the comprehensive properties are excellent.
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 carpet environment-friendly 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 201210199487.1 disclose a kind of PVC thermoplastic elastomer material, comprise the polychloroethylene with high polymerization degree of 100 weight parts, the softening agent of 50 to 80 weight parts, the snappiness properties-correcting agent of 30 to 50 weight parts, the thermo-stabilizer of 4 to 6 weight parts, the lubricant of 0.3 to 0.6 weight part, the processing aid of 1 to 3 weight part, the oxidation inhibitor of 0.2 to 0.5 weight part, the weighting agent of 5 to 10 weight parts.
Application number is 201110132493.0 disclose a kind of automotive interior material PVC and fill a prescription, comprise polyvinyl chloride (PVC) RESINS, softening agent, tranquilizer, wherein, described polyvinyl chloride (PVC) RESINS gets 50 ~ 60 weight parts, 40 ~ 50 weight parts got by described softening agent, described tranquilizer gets 1.5 ~ 2.0 weight parts, described polyvinyl chloride (PVC) RESINS is for K value is 70 ~ 80, viscosity is 1500 ~ 4500cps, VCM content <10ppm, the residual <1 of sieve, number of impurity particles <10, the outward appearance of whiteness >85 is the polyvinyl chloride of white powder, described softening agent is ester plasticizer, described tranquilizer is the tranquilizer of organic tin.
The performance index of above-mentioned existing PVC material are all meeting the basic demand of national standard, as higher in the wear-resisting antiskid performance requriements of carpet to PVC material for a lot of particular surroundings, and current PVC material performance still reliably can not meet the demand of life-time service under wear-resisting antiskid condition, therefore, the wear-resisting antiskid performance of PVC material also needs to optimize improvement further.
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 carpet environment-friendly PVC material modified, this material modified wear resisting property and non-skid property better, 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 carpet environment-friendly 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 carpet environment-friendly PVC is material modified, the material modified raw material comprising following weight part of described carpet environment-friendly PVC:
Polyvinyl chloride resin 80-120 part
Softening agent 40-56 part
Weighting agent 20-30 part
Copolymer resins 8-12 part
Abrasion resistance modifier 3-7 part
Thermo-stabilizer 2-6 part
Slipproofing agent 0.8-1.6 part
Lubricant 0.4-0.8 part.
Carpet environment-friendly 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 carpet environment-friendly PVC all beyond national standard, wear resisting property and non-skid property better, 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, described polyvinyl chloride resin is the ethylene process polyvinyl chloride resin of the polymerization degree at 1600-2000.
The present invention passes through the ethylene process polyvinyl chloride resin of the employing polymerization degree at 1600-2000 as polyvinyl chloride resin, makes plasticize speed fast, easily processes.
Preferably, described softening agent is the mixture be made up of with weight ratio 10-12:1 hexanaphthene 1,2-dioctyl phthalate diisononyl esters and epoxy soybean oil.
The present invention adopts 1,2-dioctyl phthalate diisononyl esters and epoxy soybean oil are as the composite use of softening agent, and to control its weight ratio be 10-12:1, two all 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, described weighting agent is the nm-class active calcium carbonate of particle diameter at 10-100nm.
The present invention is by adopting particle diameter at the nm-class active calcium carbonate of 10-100nm as weighting agent, good with the consistency of polyvinyl chloride resin, thus improves intensity and the shock resistance of material.
Preferably, the mixture that is made up of with weight ratio 0.8-1.2:1 acrylic resin copolymer and copolymerized panlite of described copolymer resins.
The present invention is by adopting acrylic resin copolymer and copolymerized panlite as the composite use of copolymer resins, and to control its weight ratio be 0.8-1.2:1, the obtained material modified resistance to gentle weather resistance of carpet environment-friendly PVC 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 1.8-2.6:1 styrene-butadiene rubber(SBR) and natural rubber of described abrasion resistance modifier.
The present invention is by adopting styrene-butadiene rubber(SBR) and natural rubber as the composite use of abrasion resistance modifier, and to control its weight ratio be 1.8-2.6:1, can improve the wear resisting property of material, can also improve the thermotolerance of material, drought tolerance and processing characteristics.
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 1:0.5-1.5 rubber particles and zeolite granular of described slipproofing agent.
The present invention is by adopting rubber particles and zeolite granular as the composite use of slipproofing agent, and to control its weight ratio be 1:0.5-1.5, can improve the non-skid property 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 carpet environment-friendly 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 carpet environment-friendly 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 carpet environment-friendly 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 carpet environment-friendly 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 carpet environment-friendly PVC of the present invention is all beyond national standard, wear resisting property and non-skid property better, 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.Carpet environment-friendly 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 of furniture such as carpet.
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 carpet environment-friendly PVC is material modified, the material modified raw material comprising following weight part of described carpet environment-friendly PVC:
Polyvinyl chloride resin 80 parts
40 parts, softening agent
Weighting agent 20 parts
Copolymer resins 8 parts
Abrasion resistance modifier 3 parts
Thermo-stabilizer 2 parts
Slipproofing agent 0.8 part
Lubricant 0.4 part.
Described polyvinyl chloride resin be the polymerization degree 1600 ethylene process polyvinyl chloride resin.
Described softening agent is the mixture be made up of with weight ratio 10:1 hexanaphthene 1,2-dioctyl phthalate diisononyl esters and epoxy soybean oil.
Described weighting agent is the nm-class active calcium carbonate of particle diameter at 10nm.
The mixture that described copolymer resins is made up of with weight ratio 0.8:1 acrylic resin copolymer and copolymerized panlite.
The mixture that described abrasion resistance modifier is made up of with weight ratio 1.8:1 styrene-butadiene rubber(SBR) and natural rubber.
The mixture that described thermo-stabilizer is made up of with weight ratio 0.8:1 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 slipproofing agent is made up of with weight ratio 1:0.5 rubber particles and zeolite granular; 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 carpet environment-friendly 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 carpet environment-friendly 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 carpet environment-friendly 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 carpet environment-friendly 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 carpet environment-friendly PVC is material modified, the material modified raw material comprising following weight part of described carpet environment-friendly PVC:
Polyvinyl chloride resin 90 parts
44 parts, softening agent
Weighting agent 22 parts
Copolymer resins 9 parts
Abrasion resistance modifier 4 parts
Thermo-stabilizer 2 parts
Slipproofing agent 1.0 parts
Lubricant 0.5 part.
Described polyvinyl chloride resin be the polymerization degree 1700 ethylene process polyvinyl chloride resin.
Described softening agent is the mixture be made up of with weight ratio 10.5:1 hexanaphthene 1,2-dioctyl phthalate diisononyl esters and epoxy soybean oil.
Described weighting agent is the nm-class active calcium carbonate of particle diameter at 30nm.
The mixture that described copolymer resins is made up of with weight ratio 0.9:1 acrylic resin copolymer and copolymerized panlite.
The mixture that described abrasion resistance modifier is made up of with weight ratio 2.0:1 styrene-butadiene rubber(SBR) and natural rubber.
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 slipproofing agent is made up of with weight ratio 1:0.8 rubber particles and zeolite granular; The mixture that described lubricant is made up of with weight ratio 1.8:0.9:1 oxidized polyethlene wax, pentaerythritol stearate and ethylene bis stearic acid amide.
Described carpet environment-friendly 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 carpet environment-friendly 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 carpet environment-friendly 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 carpet environment-friendly 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 carpet environment-friendly PVC is material modified, the material modified raw material comprising following weight part of described carpet environment-friendly PVC:
Polyvinyl chloride resin 100 parts
48 parts, softening agent
Weighting agent 25 parts
Copolymer resins 10 parts
Abrasion resistance modifier 5 parts
Thermo-stabilizer 4 parts
Slipproofing agent 1.2 parts
Lubricant 0.6 part.
Described polyvinyl chloride resin be the polymerization degree 1800 ethylene process polyvinyl chloride resin.
Described softening agent is the mixture be made up of with weight ratio 11:1 hexanaphthene 1,2-dioctyl phthalate diisononyl esters and epoxy soybean oil.
Described weighting agent is the nm-class active calcium carbonate of particle diameter at 50nm.
The mixture that described copolymer resins is made up of with weight ratio 1:1 acrylic resin copolymer and copolymerized panlite.
The mixture that described abrasion resistance modifier is made up of with weight ratio 2.2:1 styrene-butadiene rubber(SBR) and natural rubber.
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 slipproofing agent is made up of with weight ratio 1:1 rubber particles and zeolite granular; 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 carpet environment-friendly 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 carpet environment-friendly 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 carpet environment-friendly 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 carpet environment-friendly 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 carpet environment-friendly PVC is material modified, the material modified raw material comprising following weight part of described carpet environment-friendly PVC:
Polyvinyl chloride resin 110 parts
52 parts, softening agent
Weighting agent 28 parts
Copolymer resins 11 parts
Abrasion resistance modifier 6 parts
Thermo-stabilizer 5 parts
Slipproofing agent 1.4 parts
Lubricant 0.7 part.
Described polyvinyl chloride resin be the polymerization degree 1900 ethylene process polyvinyl chloride resin.
Described softening agent is the mixture be made up of with weight ratio 11.5:1 hexanaphthene 1,2-dioctyl phthalate diisononyl esters and epoxy soybean oil.
Described weighting agent is the nm-class active calcium carbonate of particle diameter at 80nm.
The mixture that described copolymer resins is made up of with weight ratio 1.1:1 acrylic resin copolymer and copolymerized panlite.
The mixture that described abrasion resistance modifier is made up of with weight ratio 2.4:1 styrene-butadiene rubber(SBR) and natural rubber.
The mixture that described thermo-stabilizer is made up of with weight ratio 1.1:1 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 1.2:1:1.2:1.1 calcium stearate, ricinolic acid calcium, Zinic stearas and zinc ricinate.
The mixture that described slipproofing agent is made up of with weight ratio 1:1.2 rubber particles and zeolite granular; 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 carpet environment-friendly 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 carpet environment-friendly 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 carpet environment-friendly 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 carpet environment-friendly 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 carpet environment-friendly PVC is material modified, the material modified raw material comprising following weight part of described carpet environment-friendly PVC:
Polyvinyl chloride resin 120 parts
56 parts, softening agent
Weighting agent 30 parts
Copolymer resins 12 parts
Abrasion resistance modifier 7 parts
Thermo-stabilizer 6 parts
Slipproofing agent 1.6 parts
Lubricant 0.8 part.
Described polyvinyl chloride resin be the polymerization degree 2000 ethylene process polyvinyl chloride resin.
Described softening agent is the mixture be made up of with weight ratio 12:1 hexanaphthene 1,2-dioctyl phthalate diisononyl esters and epoxy soybean oil.
Described weighting agent is the nm-class active calcium carbonate of particle diameter at 100nm.
The mixture that described copolymer resins is made up of with weight ratio 1.2:1 acrylic resin copolymer and copolymerized panlite.
The mixture that described abrasion resistance modifier is made up of with weight ratio 2.6:1 styrene-butadiene rubber(SBR) and natural rubber.
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 slipproofing agent is made up of with weight ratio 1:1.5 rubber particles and zeolite granular; 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 carpet environment-friendly 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 carpet environment-friendly 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 carpet environment-friendly 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 carpet environment-friendly 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 carpet environment-friendly 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 | 26.8 | 28.2 | 28.7 | 27.7 | 26.2 |
| Flexural strength (MPa) | ≥15.0 | 51.9 | 54.5 | 53.7 | 52.6 | 50.4 |
| Elongation at break (%) | ≥150 | 273 | 284 | 288 | 276 | 271 |
| Heat-drawn wire (DEG C) | ≥50.0 | 131 | 133 | 135 | 132 | 130 |
| Impact embrittlement temperature (DEG C) | ≤-20 | -25 | -25 | -30 | -30 | -25 |
| Heat-stable time (min) when 200 DEG C | ≥60 | 90 | 110 | 120 | 120 | 100 |
| Hardness/Shore D | ≥50 | 81 | 84 | 86 | 87 | 82 |
| Fire-retardant | V0 | V0 | V0 | V0 | V0 | V0 |
| Abrasion resistance (secondary) | ≥4500 | 5100 | 5300 | 5600 | 5800 | 5200 |
| Non-skid property | Generally | Better | Better | Better | Better | Better |
As can be seen from Table 1, the material modified properties of the carpet environment-friendly PVC that the present invention obtains is all beyond national standard, wear resisting property and non-skid property better, 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 carpet environment-friendly PVC is material modified, it is characterized in that: the material modified raw material comprising following weight part of described carpet environment-friendly PVC:
Polyvinyl chloride resin 80-120 part
Softening agent 40-56 part
Weighting agent 20-30 part
Copolymer resins 8-12 part
Abrasion resistance modifier 3-7 part
Thermo-stabilizer 2-6 part
Slipproofing agent 0.8-1.6 part
Lubricant 0.4-0.8 part.
2. a kind of carpet environment-friendly PVC according to claim 1 is material modified, it is characterized in that: described polyvinyl chloride resin is the ethylene process polyvinyl chloride resin of the polymerization degree at 1600-2000.
3. a kind of carpet environment-friendly 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 10-12:1 hexanaphthene 1,2-dioctyl phthalate diisononyl esters and epoxy soybean oil.
4. a kind of carpet environment-friendly PVC according to claim 1 is material modified, it is characterized in that: described weighting agent is the nm-class active calcium carbonate of particle diameter at 10-100nm.
5. a kind of carpet environment-friendly PVC according to claim 1 is material modified, it is characterized in that: the mixture that described copolymer resins is made up of with weight ratio 0.8-1.2:1 acrylic resin copolymer and copolymerized panlite.
6. a kind of carpet environment-friendly PVC according to claim 1 is material modified, it is characterized in that: the mixture that described abrasion resistance modifier is made up of with weight ratio 1.8-2.6:1 styrene-butadiene rubber(SBR) and natural rubber.
7. a kind of carpet environment-friendly 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.
8. a kind of carpet environment-friendly PVC according to claim 1 is material modified, it is characterized in that: the mixture that described slipproofing agent is made up of with weight ratio 1:0.5-1.5 rubber particles and zeolite granular; 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 carpet environment-friendly 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 carpet environment-friendly PVC is material modified.
10. the preparation method that a kind of carpet environment-friendly 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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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106046627A (en) * | 2016-08-15 | 2016-10-26 | 东莞市悠悠美居家居制造有限公司 | Polyvinyl chloride massage pad and preparation method thereof |
| CN106479197A (en) * | 2016-11-22 | 2017-03-08 | 苏州肯福特纺织品有限公司 | A kind of environment protection modification thermoplastic elastic material and its application |
| 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 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504446A (en) * | 2011-12-02 | 2012-06-20 | 潍坊易捷新材料有限公司 | Environment-friendly carpet |
| EP2283073B1 (en) * | 2008-04-30 | 2012-09-12 | E. I. du Pont de Nemours and Company | Plastic surfaces having improved surface characteristics |
| CN103059470A (en) * | 2012-12-25 | 2013-04-24 | 东莞市祺龙电业有限公司 | High-abrasion-resistant and environment-friendly polyvinyl chloride (PVC) modified materials and preparation method thereof |
-
2015
- 2015-12-31 CN CN201511015848.2A patent/CN105419167A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2283073B1 (en) * | 2008-04-30 | 2012-09-12 | E. I. du Pont de Nemours and Company | Plastic surfaces having improved surface characteristics |
| CN102504446A (en) * | 2011-12-02 | 2012-06-20 | 潍坊易捷新材料有限公司 | Environment-friendly carpet |
| CN103059470A (en) * | 2012-12-25 | 2013-04-24 | 东莞市祺龙电业有限公司 | High-abrasion-resistant and environment-friendly polyvinyl chloride (PVC) modified materials and preparation method thereof |
Cited By (7)
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|---|---|---|---|---|
| CN106046627A (en) * | 2016-08-15 | 2016-10-26 | 东莞市悠悠美居家居制造有限公司 | Polyvinyl chloride massage pad and preparation method thereof |
| CN106479197A (en) * | 2016-11-22 | 2017-03-08 | 苏州肯福特纺织品有限公司 | A kind of environment protection modification thermoplastic elastic material and its application |
| 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 |
| CN106928595A (en) * | 2017-04-18 | 2017-07-07 | 东莞市祺龙电业有限公司 | A kind of wheel for land skate is material modified and preparation method thereof with PVC |
| CN106977846A (en) * | 2017-04-18 | 2017-07-25 | 东莞市祺龙电业有限公司 | A kind of waterproof oil resistant carpet is material modified and preparation method thereof with PVC |
| CN107189278A (en) * | 2017-07-18 | 2017-09-22 | 合肥峰腾节能科技有限公司 | A kind of sound-absorbing damping flame-proof environmental protection carpet backing material and preparation method thereof |
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