CN103497446A - Environmental-friendly polyvinyl chloride (PVC) extraction-resistant anti-seepage film and preparation method thereof - Google Patents
Environmental-friendly polyvinyl chloride (PVC) extraction-resistant anti-seepage film and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an environmental-friendly polyvinyl chloride (PVC) extraction-resistant anti-seepage film and a preparation method thereof, belonging to the technical field of salt film preparation. The environmental-friendly PVC extraction-resistant anti-seepage film contains the following ingredients in proportioning ratio: 100 parts by mass of PVC resin, 10-50PHR of primary plasticizer, 2-10PHR of secondary plasticizer, 2-5PHR of environmental-friendly heat stabilizer, 0.1-0.5PHR of antioxidant, 6-30PHR of filler and 0.1-0.3PHR of lubricant. The preparation method of the environmental-friendly PVC extraction-resistant anti-seepage film comprises the steps of (1) preparing a kneaded material: metering all the ingredients, mixing and cooling; (2) plasticizing: plasticizing by using a planetary extruder; (3) calendering: filtering the material in a filter, and feeding the material to a calender; (4) spreading: after the material passes through the calender, spreading to widen, and then, cooling for forming, thereby preparing the environmental-friendly PVC extraction-resistant anti-seepage film. According to the environmental-friendly PVC extraction-resistant anti-seepage film and the preparation method thereof, the preparation process is simple, and the controllability is good; the product has the advantages of good water and brine extraction resisting performance, high mechanical properties, little loss, high retention rate, and the like.
Description
Technical field
The invention belongs to salt membrane preparation technology field, particularly relate to a kind of environment-friendly polyvinyl chloride resistant to extraction barrier film and preparation method thereof.
Background technology
At present, salt pond crystallizing pond, refuse landfill, sewage and waste residue treatment plant, hypogee, defence engineering, tunnel and official reserves cave depot, roof waterproof engineering etc. are suitable for that the working conditions such as environmental protection is harsh, performance index require high engineering, use high-quality high density polyethylene(HDPE) antiseepage impregnating material always.And polyvinyl chloride film is larger with respect to the physical strength of polyethylene film, ageing resistance is better, and good springiness can restore after stretching; And can prevent that polyethylene film from not adding enough anti-aging materials when manufacturing film, the phenomenons such as check surface, embrittlement just easily occur prematurely under strong sunlight.
CN101544802A discloses a kind of modified polyvinyl chloride salt film and preparation method thereof.This salt film has mechanical property preferably, low-temperature performance and uvioresistant.CN101864129A discloses a kind of acrylonitrile butadiene rubber modified polyvinyl chloride geomembrane.The characteristics such as the method has the feel of rubber, and toughness is large, and intensity is high, and sealing property is superior.But product is when being gathered in the table bittern on earth's surface or lake bittern water and brackish water, especially be greater than 5 liquid mineral products for salt content, there is low temperature resistant be full of cracks in barrier film, ageing-resistant decomposition, soak the technical problems such as hardening is extracted in the post-plasticization agent out, mechanical property changes, and creep property is poor in water-fast, bittern.
Summary of the invention
The present invention provides a kind of environment-friendly polyvinyl chloride resistant to extraction barrier film and preparation method thereof for solving the technical problem existed in known technology.
The present invention utilizes the polyvinyl chloride of high-polymerization degree, add the environmental protection stablizers such as environmental protection Ca-Zn liquid composite stabilizing agent, environmental protection barium-zinc liquid compound stabilizer, barium stearate, Zinic stearas, a large amount of environment-friendly plasticizers such as trioctyl trimellitate, epoxy soybean oil, lipid acid di-isooctyl that use replace conventional plasticizers, by environment-friendly filler, modified additive etc., improve feel.Its effect is to utilize environmental protection stablizer and environment-friendly plasticizer, the International Environmental Protection standards such as compound EN71, ROSH.Add epoxy soybean oil and barium stearate, Zinic stearas compound use, play synergy and improve film weather resisteant, stability, increase the service life.Reasonably combined formation formula compound system by other modified additives and basic components system, make modified pvc film, and not only mechanical property increases, and the resistant to extraction performance all is improved.
One of purpose of the present invention is to provide a kind of have good water-fast, bittern extraction performance, and mechanical property is high, lose little, the environment-friendly polyvinyl chloride resistant to extraction barrier film of the characteristics such as conservation rate is large.
The technical scheme that environment-friendly polyvinyl chloride resistant to extraction barrier film of the present invention is taked is:
A kind of environment-friendly polyvinyl chloride resistant to extraction barrier film is characterized in: polyvinyl chloride resistant to extraction barrier film comprises that each component proportion is
Polyvinyl chloride (PVC) RESINS 100 mass parts;
Primary plasticizer 10-50PHR;
Extender plasticizer 2-10PHR;
Environment protection thermal stablizer 2-5PHR;
Antioxidant 0.1-0.5PHR;
Filler 6-30PHR;
Lubricant 0.1-0.3PHR;
Other 0.1-5PHR;
Wherein, the one or more combination that primary plasticizer is Phthalates, trimellitate class, citrate plasticizer; Preferably phthalic acid and trioctyl trimellitate class are mixed use, and more preferably DOP and TOTM mix, and improve the resistant to extraction performance;
The mixture of the one or more combination that extender plasticizer is aliphatic dibasic acid ester, polyol ester class, polyester plasticizer, epoxy plasticizer.Preferred fatty acid diester and epoxy plasticizer, more preferably Octyl adipate or dioctyl sebacate and epoxy soybean oil, improve weathering resistance and resistance to low temperature.
Environment-friendly polyvinyl chloride resistant to extraction barrier film of the present invention can also adopt following technical scheme:
Described environment-friendly polyvinyl chloride resistant to extraction barrier film is characterized in: polyvinyl chloride resistant to extraction barrier film proportioning component contains properties-correcting agent 0.1-5PHR.
Described environment-friendly polyvinyl chloride resistant to extraction barrier film is characterized in: the mixture of the one or more combination that properties-correcting agent is paracril, chlorinatedpolyethylene (CPE), ethylene vinyl acetate copolymer (EVA).Preferably paracril, improve toughness, improves angle tear strength.
Described environment-friendly polyvinyl chloride resistant to extraction barrier film is characterized in: polyvinyl chloride (PVC) RESINS is the mixture of one or more resins of polymerization degree 1000-3000.The SG-3 type polyvinyl chloride that preferred degree of polymerization is 1300 and the polymerization degree are 2500 mixing.
Described environment-friendly polyvinyl chloride resistant to extraction barrier film, be characterized in: the environment protection thermal stablizer is for without phenol environmental protection stablizer, for without the phenol calcium-zinc composite stabilizing agent, without phenol barium zinc composite stabilizer, without the mixture of the one or more combination of phenol environment protection metal soap class stablizer.Preferably without phenol environmental protection Ca-Zn liquid, powder stablizer with without phenol environmental protection barium-zinc liquid, powder stablizer powder, mix, without phenol environment protection metal soap class, with epoxy soybean oil, work in coordination with and play stabilization.
Described environment-friendly polyvinyl chloride resistant to extraction barrier film is characterized in: antioxidant is benzophenone class UV light absorber and the composite use of phosphite ester kind antioxidant.
Described environment-friendly polyvinyl chloride resistant to extraction barrier film is characterized in: antioxidant is Octabenzone and Doverphos DP-613.
Described environment-friendly polyvinyl chloride resistant to extraction barrier film is characterized in: lubricant is hydro carbons lubricant, aliphatics lubricant, aliphatic ester series lubricant agent or fatty amide series lubricant agent.Preferred aliphat ester lubricant, fatty amide series lubricant agent, more preferably fatty amide series lubricant agent.
Described environment-friendly polyvinyl chloride resistant to extraction barrier film, be characterized in: the mixture of the one or more combination that filler is calcium carbonate, talcum powder, magnesiumcarbonate, white carbon black, carbon black.Preferred activated Calcium carbonate, talcum powder and carbon black mix and match, more preferably the activated Calcium carbonate of coupling agent activation mixes with talcum powder, carbon black, improve dimensional stability, particularly after water, bittern, alkaline soak, guarantee dimensional stability, improve resistant to extraction performance and creep resistance, improve the feel smoothness, improve ageing resistance.
Two of the object of the invention is to provide a kind ofly has that technique is simple, controllability good, and products obtained therefrom has good water-fast, bittern extraction performance, and mechanical property is high, lose little, the environment-friendly polyvinyl chloride resistant to extraction barrier film preparation method of the characteristics such as conservation rate is large.
The technical scheme that environment-friendly polyvinyl chloride resistant to extraction barrier film preparation method of the present invention takes is:
A kind of preparation method of environment-friendly polyvinyl chloride resistant to extraction barrier film, be characterized in: the preparation method comprises the following steps:
(1) mediate the material preparation: by after polyvinyl chloride (PVC) RESINS, softening agent, thermo-stabilizer, filler, antioxidant, lubricant and properties-correcting agent automatic gauge, carry out high-speed mixing, high-speed mixing proceed to after evenly cold stir cooling;
(2) plasticizing: the compound of step (1) gained is dosed into to planetary extruder and is plastified;
(3) calendering: by the plasticizing of step (1) gained material completely, drop into that filter filters and feeding to rolling press;
(4) expanding: material is after rolling press, and expanding widens in proportion.
(5) cooling and shaping: will be tending towards the material of vitrifying state, cooling and shaping makes environment-friendly polyvinyl chloride resistant to extraction barrier film.
(6) batch: the environment-friendly polyvinyl chloride resistant to extraction barrier film by making, batch packing according to dimensional requirement.
The preparation method of environment-friendly polyvinyl chloride resistant to extraction barrier film of the present invention can also adopt following technical scheme:
The preparation method of described environment-friendly polyvinyl chloride resistant to extraction barrier film is characterized in: while mediating the material preparation, the high-speed mixing final temperature is 80-120 ℃, preferably 90-115 ℃; The cold final temperature that stirs is 20-60 ℃, preferably 35-45 ℃.
The preparation method of described environment-friendly polyvinyl chloride resistant to extraction barrier film is characterized in: during plasticizing, each district's temperature of planetary extruder is 140-200 ℃, preferred 150-180 ℃, and extruded velocity is 20-70 rev/min, preferably 40-60 rev/min;
During calendering: each district's temperature of filter is 120-160 ℃, preferably 140-150 ℃; Screw speed is 20-60 rev/min, preferably 35-50 rev/min; The rolling press temperature is 150-200 ℃, preferred 170-190 ℃, and calender speed is 5-40m/min, preferably 15-25m/min;
During expanding: expanding widens, and cross directional stretch is than being 1:1-1:4, and longitudinal stretching is than being 1:1-1:3.5, preferably 1:1-1:2.
The cooling and shaping temperature is 10-50 ℃, preferably 15-30 ℃.
Coiling speed is 30-70m/min, the preferred 45-55m/min of expanding rolling equipment.
Advantage and positively effect that the present invention has are:
Environment-friendly polyvinyl chloride resistant to extraction barrier film is owing to having adopted the brand-new technical scheme of the present invention, compared with prior art, the present invention utilizes the polyvinyl chloride of high-polymerization degree, and add therein appropriate softening agent and stablizer and other modified additives etc. make modified pvc film, not only mechanical property increases, and after soaking in water, bittern, mass loss is little, mechanical property changes little, and creep resistance is good, and the resistant to extraction performance all is improved.The present invention has that preparation technology is simple, controllability good; The impermeable film of environment-friendly polyvinyl chloride resistant to extraction meets domestic and international environmental requirement, good mechanical performance, and the liquid extraction performances such as anti-bittern are good, and conservation rate is large, the advantages such as long service life.
Embodiment
For further understanding summary of the invention of the present invention, Characteristic, hereby exemplify following examples, and be described in detail as follows:
Embodiment 1
A kind of environment-friendly polyvinyl chloride resistant to extraction barrier film, comprise that each component proportion is
Wherein, polyvinyl chloride (PVC) RESINS is that the weight ratios such as the polymerization degree SG-3 type polyvinyl chloride that is 1300 and the polymerization degree are 2500 are mixed; Primary plasticizer is that phthalic acid and trioctyl trimellitate class are mixed use, and more preferably the part by weight such as DOP and TOTM mixes; Extender plasticizer is lipid acid diester and epoxy plasticizer, and more preferably Octyl adipate or dioctyl sebacate and epoxy soybean wet goods weight ratio are mixed; Antioxidant is that the weight ratios such as Octabenzone and Doverphos DP-613 are composite; Filler is activated Calcium carbonate, talcum powder and carbon black mix and match, and more preferably the activated Calcium carbonate of coupling agent activation mixes with weight ratios such as talcum powder, carbon blacks.
Embodiment 2
A kind of environment-friendly polyvinyl chloride resistant to extraction barrier film, comprise that each component proportion is
Primary plasticizer is that phthalic acid and trioctyl trimellitate class are mixed use, and more preferably the part by weight such as DOP and TOTM mixes; Extender plasticizer is lipid acid diester and epoxy plasticizer, and more preferably Octyl adipate or dioctyl sebacate and epoxy soybean wet goods weight ratio are mixed; Antioxidant is that the weight ratios such as Octabenzone and Doverphos DP-613 are composite; Filler is that the weight ratios such as activated Calcium carbonate, talcum powder and carbon black are mixed.
Embodiment 3
A kind of preparation method of environment-friendly polyvinyl chloride resistant to extraction barrier film comprises the following steps:
(1) mediate the material preparation: by after polyvinyl chloride (PVC) RESINS, softening agent, thermo-stabilizer, filler, antioxidant, lubricant and properties-correcting agent automatic gauge, carry out high-speed mixing, high-speed mixing proceed to after evenly cold stir cooling; While mediating the material preparation, the high-speed mixing final temperature is 80-120 ℃, preferably 90-115 ℃; The cold final temperature that stirs is 20-60 ℃, preferably 35-45 ℃.
(2) plasticizing: the compound of step (1) gained is dosed into to planetary extruder and is plastified; During plasticizing, each district's temperature of planetary extruder is 140-200 ℃, preferred 150-180 ℃, and extruded velocity is 20-70 rev/min, preferably 40-60 rev/min;
(3) calendering: by the plasticizing of step (1) gained material completely, drop into that filter filters and feeding to rolling press; During calendering: each district's temperature of filter is 120-160 ℃, preferably 140-150 ℃; Screw speed is 20-60 rev/min, preferably 35-50 rev/min; The rolling press temperature is 150-200 ℃, preferred 170-190 ℃, and calender speed is 5-40m/min, preferably 15-25m/min
(4) expanding: material is after rolling press, and expanding widens, and cross directional stretch is than being 1:1-1:4, and longitudinal stretching is than being 1:1-1:3.5, preferably 1:1-1:2; After expanding widens, cooling and shaping makes environment-friendly polyvinyl chloride resistant to extraction barrier film.
(5) cooling and shaping: temperature is 10-50 ℃, preferably 15-30 ℃.
(6) batch: speed is 30-70m/min, the preferred 45-55m/min of expanding rolling equipment.
Example 4
A kind of preparation method of environment-friendly polyvinyl chloride resistant to extraction barrier film comprises the following steps:
(1) mediate the material preparation
The polyvinyl chloride (PVC) RESINS that is 1300 and 2500 by the polymerization degree, dimixo-octyl phthalate, fatty acid ester, epoxy soybean oil, the environmental protection Ca-Zn liquid composite stabilizing agent, Zinic stearas, barium stearate, activated Calcium carbonate, erucicamide, talcum powder, carbon black, 2-hydroxyl-4-n-octyl benzophenone, poly-4, 4, isopropylidene diphenol C12-15 alcohol phosphorous acid ester, the raw materials such as phthalocyanine blue are according to following proportioning mass fraction: 100 parts of resins, primary plasticizer 46, extender plasticizer 10, environmental protection calcium liquid composite thermal stabilizer 3, filler 10, pigment 0.003, 0.5 part of antioxidant, lubricant 0.12, properties-correcting agent 1.Drop into the high-speed kneading machine after the automatic metering system metering, mediated automatic discharge and lowered the temperature to the cold pot that stirs, drop into paracril simultaneously.After mixing, be cooled to 40 ℃ of automatic discharges to storage vat.
(2) plasticizing masking
Set the planetary extruder rate of feeding according to the condition of production, be generally 20 rev/mins; 40 rev/mins of extruded velocities, each section temperature, 150-180 ℃, full-automatic assembly line filter, rolling press, the calendering cooling forming makes film, and carries out performance test, the results are shown in Table 2.The film performance test method is in Table 1.
Table 1 film performance test method
Example 5
Method according to example 4 prepares the polyvinyl chloride calendered film, and different is by primary plasticizer kind difference, and filler carries out, and makes the performance test results of film in Table 2.
Example 6
Method according to example 4 prepares the polyvinyl chloride calendered film, and primary plasticizer is mixed use that different is, make the performance test results of film in Table 2.
Example 7
Method according to example 4 prepares the polyvinyl chloride calendered film, and different is that main and auxiliary softening agent is mixed, and, by the filler use that is mixed, makes the performance test results of film in Table 2.
Example 8
Method according to example 4 prepares the polyvinyl chloride calendered film, the use that is mixed of different main and auxiliary softening agent, and and properties-correcting agent be mixed compound.Make the performance test results of film in Table 2.
Table 2
Above-described embodiment has that preparation technology of the present invention is simple, controllability good; Product has good water-fast, bittern extraction performance, and mechanical property is high, lose little, the positive effect of the large grade of conservation rate.This product is suitable for that the working conditions such as environmental protection is harsh, performance index require high engineering, as the engineerings such as saltern crystallizing pond, refuse landfill, sewage and waste residue treatment plant, hypogee, tunnel and official reserves cave depot, roof waterproof are used.
Claims (10)
1. an environment-friendly polyvinyl chloride resistant to extraction barrier film, it is characterized in that: polyvinyl chloride resistant to extraction barrier film comprises that each component proportion is
Polyvinyl chloride (PVC) RESINS 100 mass parts;
Primary plasticizer 20-50PHR;
Extender plasticizer 2-10PHR;
Environment protection thermal stablizer 2-5PHR;
Antioxidant 0.1-0.5PHR;
Filler 6-30PHR;
Lubricant 0.1-0.3PHR;
Wherein, the one or more combination that primary plasticizer is Phthalates, trimellitate class, citrate plasticizer; The mixture of the one or more combination that extender plasticizer is aliphatic dibasic acid ester, polyol ester class, polyester plasticizer, epoxy plasticizer.
2. environment-friendly polyvinyl chloride resistant to extraction barrier film according to claim 1, it is characterized in that: polyvinyl chloride resistant to extraction barrier film proportioning component contains properties-correcting agent 0.1-5PHR.
3. environment-friendly polyvinyl chloride resistant to extraction barrier film according to claim 2, is characterized in that: the mixture of the one or more combination that properties-correcting agent is paracril, CPE, EVA.
4. according to claim 1,2 or 3 described environment-friendly polyvinyl chloride resistant to extraction barrier films, it is characterized in that: polyvinyl chloride (PVC) RESINS is the mixture of one or more resins of polymerization degree 1000-3000.
5. environment-friendly polyvinyl chloride resistant to extraction barrier film according to claim 1, it is characterized in that: the environment protection thermal stablizer is for without phenol environmental protection stablizer, for without the phenol calcium-zinc composite stabilizing agent, without phenol barium zinc composite stabilizer, without the mixture of the one or more combination of phenol environment protection metal soap class stablizer.
6. according to claim 1,2 or 3 described environment-friendly polyvinyl chloride resistant to extraction barrier films, it is characterized in that: antioxidant is benzophenone class UV light absorber and the composite use of phosphite ester kind antioxidant; Preferred anti-oxidant is Octabenzone and Doverphos DP-613.
7. according to claim 1,2 or 3 described environment-friendly polyvinyl chloride resistant to extraction barrier films, it is characterized in that: lubricant is hydro carbons lubricant, aliphatics lubricant, aliphatic ester series lubricant agent or fatty amide series lubricant agent; The mixture of the one or more combination that filler is calcium carbonate, talcum powder, magnesiumcarbonate, white carbon black, carbon black.
8. the preparation method of environment-friendly polyvinyl chloride resistant to extraction barrier film according to claim 1, it is characterized in that: the preparation method comprises the following steps:
(1) mediate the material preparation: by after polyvinyl chloride (PVC) RESINS, softening agent, thermo-stabilizer, filler, antioxidant, lubricant and properties-correcting agent automatic gauge, carry out high-speed mixing, high-speed mixing proceed to after evenly cold stir cooling;
(2) plasticizing: the compound of step (1) gained is dosed into to planetary extruder and is plastified;
(3) calendering: by the plasticizing of step (1) gained material completely, drop into that filter filters and feeding to rolling press;
(4) expanding: material is after rolling press, and expanding widens in proportion;
(5) cooling and shaping: will be tending towards the material of vitrifying state, cooling and shaping makes environment-friendly polyvinyl chloride resistant to extraction barrier film;
(6) batch: the environment-friendly polyvinyl chloride resistant to extraction barrier film by making, batch packing according to dimensional requirement.
9. the preparation method of environment-friendly polyvinyl chloride resistant to extraction barrier film according to claim 8 is characterized in that: while mediating the material preparation, the high-speed mixing final temperature is 80-120 ℃, preferably 90-115 ℃; The cold final temperature that stirs is 20-60 ℃, preferably 35-45 ℃.
10. the preparation method of environment-friendly polyvinyl chloride resistant to extraction barrier film according to claim 8 or claim 9, it is characterized in that: during plasticizing, each district's temperature of planetary extruder is 140-200 ℃, preferably 150-180 ℃, extruded velocity is 20-70 rev/min, preferably 40-60 rev/min;
During calendering: each district's temperature of filter is 120-160 ℃, preferably 140-150 ℃; Screw speed is 20-60 rev/min, preferably 35-50 rev/min; The rolling press temperature is 150-200 ℃, preferred 170-190 ℃, and calender speed is 5-40m/min, preferably 15-25m/min;
During expanding: expanding widens, and cross directional stretch is than being 1:1-1:4, and longitudinal stretching is than being 1:1-1:3.5, preferably 1:1-1:2;
The cooling and shaping temperature is 10-50 ℃, preferably 15-30 ℃;
Coiling speed is 30-70m/min, the preferred 45-55m/min of expanding rolling equipment.
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