CN103360695A - Durable polyvinyl chloride salt membrane composition and preparation method thereof - Google Patents
Durable polyvinyl chloride salt membrane composition and preparation method thereof Download PDFInfo
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- CN103360695A CN103360695A CN2012100903057A CN201210090305A CN103360695A CN 103360695 A CN103360695 A CN 103360695A CN 2012100903057 A CN2012100903057 A CN 2012100903057A CN 201210090305 A CN201210090305 A CN 201210090305A CN 103360695 A CN103360695 A CN 103360695A
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- polyvinyl chloride
- chloride salt
- salt film
- film composition
- permanent seal
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Abstract
The invention relates to a durable polyvinyl chloride salt membrane composition and a preparation method thereof and belongs to the technical field of high polymer materials. The durable polyvinyl chloride salt membrane is prepared from the following raw materials in parts by mass: 100 parts of polyvinyl chloride, 3-8 parts of stabilizer, 20-100 parts of plasticizer, 5-25 parts of low temperature modifier, 0.2-1.0 part of lubricating agent, 0.2-2.0 parts of antioxidant, 0.2-2.0 parts of light stabilizer, 1-5 parts of light screener and 0.2-2.0 parts of colouring agent. The preparation method comprises the processes of mixing raw materials, pelleting and calendaring or comprises the processes of mixing raw materials and calendaring. The durable polyvinyl chloride salt membrane adopts a migration-resistant plasticizer and the low temperature modifier, so that the salt membrane can have good durability and low temperature flexibility and can not be crisp after being used for a long time; and a production technology is simple, and the produced thin film has high cost performance.
Description
Technical field
The present invention relates to a kind of weather resistance polyvinyl chloride salt film composition and method of making the same, belong to technical field of polymer materials.
Background technology
Salt is indispensable in national economy and the daily life, mainly makes by evaporation seawater in shining the salt pond.Overcast and rainy when more, the salt of the own crystallization of rainwater solubilized reduces salt output.Adopt the salt film to cover crystallizing pond, can significantly improve salt output and quality.The salt film will stand summer high temperature, strong Exposure to Sunlight and winter low temperature in use, must have the performances such as high temperature resistant, low temperature resistant, ageing-resistant.
Now general salt film mainly is polyvinyl chloride, and the small molecules softening agent of its adding can be moved to the surface of film, so that the hardening of salt film becomes fragile, and cracky when folding and unfolding, thus affect work-ing life of salt film.
CN 201960781 U disclose a kind of polyvinyl chloride compound modified salt film that comprises that basement membrane, center powerful film and facial mask form, this uses novel salt film to adopt the three stacked forms that add, can improve intensity and resistance of aging, but manufacturing process is complicated, cost is higher.
CN 1865324 B have announced a kind of low temperature resistant, anti-aging polyvinyl chloride salt film, comprise following component: (A) 100 parts of weights of polyvinyl chloride (PVC) RESINS; (B) dioctyl phthalate (DOP) 10-40phr; (C) dioctyl terephthalate 10-40phr; (D) Octyl adipate 2-12phr; (E) thermo-stabilizer 2-5phr; (F) carbon black 1-4phr; (G) Octabenzone (or 2-hydroxy-4-methyl benzophenone) 0.1-0.8phr; (H) 4,4-isopropylidene bis-phenol 0.1-0.8phr.Salt film low temperature and the resistance of aging of this invention are better, but softening agent moves easily, and weather resistance is relatively poor.
CN 101544802 A have announced a kind of polyvinyl chloride salt film, mainly comprise with polyvinyl chloride and the following component take polyvinyl chloride as benchmark: paracril 0-20 quality %, phthalic ester 5-80 quality %, sebacic acid fat 1-15 quality %, phosphorous acid ester 1-10 quality %, rare earth metal salt 0.5-10 quality %, epoxy compounds 1-15 quality %, C
18-C
20Lipid acid 0.1-5 quality %, photostabilizer 0.1-2.0 quality %, oxidation inhibitor 0.1-2.0 quality %.The salt film of this invention uses simple plasticizer equally, and weather resistance is relatively poor.
Summary of the invention
Technical problem to be solved by this invention provides permanent seal cooling polyvinyl chloride salt film of a kind of high temperature resistant low temperature, low migration, ageing-resistant performance excellence and preparation method thereof.
Permanent seal cooling polyvinyl chloride salt film composition of the present invention is characterized in that being made by the raw material of following mass fraction:
Described polyvinyl chloride polymerization degree is 800～4000, preferred 1300～2500.
Described stablizer is organotin stabilizer or calcium-zinc composite stabilizing agent, the calcium-zinc composite stabilizing agent of preferred asepsis environment-protecting.
Described softening agent is two or more of trioctyl trimellitate (TOTM), tetraoctyl 1,2,4,5-benzenetetra-carboxylate (TOPM), polyester plasticizer or tributyl citrate (TBC), preferred 40～80 parts of consumption.
Described low temperature modification agent is ethylene-vinyl acetate copolymer (EVA) and/or chlorinatedpolyethylene (CPE).
Described lubricant is two or more in polyethylene wax, Microcrystalline Wax or the fatty acid ester.
Described antioxidant is that phenolic antioxidant or phosphorus are oxidation inhibitor, preferred phenolic antioxidant 1010, and consumption is 0.5～1.5 part.
Described photostabilizer is hindered amine light stabilizer or benzotriazole category ultraviolet absorbers, preferred benzotriazole category ultraviolet absorbers, and such as UV-419, consumption is 0.5～1.5 part.
Described photomask agent is titanium dioxide, preferred Rutile type Titanium Dioxide.
Described tinting material is carbon black, and consumption is 0.5～1.5 part.
The preparation method of described permanent seal cooling polyvinyl chloride salt film composition can be material compounding-granulation-calendering technology or material compounding-calendering technology, preferred feed compounding-granulation-calendering technology; When adopting material compounding-calendering technology, rolling temperature suitably improves 5～10 ℃.
Described material compounding-granulation-calendering technology comprises the steps:
(1) material compounding: polyvinyl chloride (PVC) RESINS, stablizer, softening agent, low temperature modification agent, lubricant, antioxidant, photostabilizer, photomask agent, tinting material are mixed in high low speed mixer group, when being 100～130 ℃ to mixing temperature, preferred 110 ℃～120 ℃, again material is put into low speed mixer, treats that temperature of charge is cooled to 35～45 ℃ of dischargings;
(2) granulation: the material that mixes is adopted twin screw granulation, 130～160 ℃ of prilling temperatures, preferred 140 ℃～150 ℃;
(3) calendering: with rolling press pellet is rolled into film, rolling temperature is 150～190 ℃.
Described compounding-calendering technology comprises the steps:
(1) material compounding: polyvinyl chloride (PVC) RESINS, stablizer, softening agent, low temperature modification agent, lubricant, antioxidant, photostabilizer, photomask agent, tinting material are mixed in high low speed mixer group, when being 100～130 ℃ to mixing temperature, preferred 110 ℃～120 ℃, again material is put into low speed mixer, treats that temperature of charge is cooled to 35～45 ℃ of dischargings;
(2) calendering: with rolling press pellet is rolled into film, rolling temperature is 160～200 ℃.
Beneficial effect of the present invention is as follows:
The present invention adopts the softening agent of anti-migration the and low temperature modification agent, guarantees that the salt film has good weather resistance and low-temperature pliability, and life-time service can not become fragile, and can use in the winter time; Production technique of the present invention is simple, and the film cost performance of production is high.
Embodiment
Below in conjunction with embodiment the present invention is described further.
The used product type of embodiment and manufacturer are as follows:
Calcium-zinc composite stabilizing agent 9700, German Baerlocher company; Organotin stabilizer TM-181-FS, U.S. Rhom and Hass; Softening agent TOTM, Zibo Plasticizing Agent Factory; Softening agent TOPM, Japan Chinese mugwort Dicon A/S; Polyester plasticizer c-880, Japan Chinese mugwort Dicon A/S; EVA 28-6, Mitsui company; Low temperature modification agent CPE 135A, Weifang AsiaSat chemistry company limited; Antioxidant 1010, the new Xiang in Zibo company limited; Stearate, Zibo Huaxing Additives Co., Ltd., PE wax, the excessive additives for plastics cooperative venture of Shanghai China; Titanium dioxide R-902, Taiwan E.I.Du Pont Company.
Embodiment 1～15
The prescription of embodiment 1～5 is as shown in table 1 below:
The formula table of table 1 embodiment 1～5
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| PVC(P＝2500) | 100 | 100 | 100 | 100 | 100 |
| Calcium-zinc composite stabilizing agent | 4 | 5 | 6 | 7 | 8 |
| TOTM | 10 | 10 | 10 | 20 | 20 |
| topM | 30 | 40 | 40 | 30 | 10 |
| Polyester plasticizer | 0 | 0 | 0 | 0 | 10 |
| EVA | 20 | 10 | 5 | 5 | 5 |
| CPE | 5 | 5 | 0 | 5 | 5 |
| Antioxidant 1010 | 1.0 | 1.5 | 1.5 | 1.0 | 0.5 |
| Stearate | 0.6 | 0.4 | 0.4 | 0.6 | 0.2 |
| PE wax | 0.4 | 0.2 | 0.4 | 0.2 | 0.2 |
| Titanium dioxide | 4 | 4 | 4 | 4 | 4 |
| Photostabilizer UV-419 | 1.0 | 1.0 | 1.0 | 1.5 | 1.5 |
| Carbon black | 0.5 | 0.8 | 1.0 | 1.0 | 1.5 |
The prescription of embodiment 6～10 is as shown in table 2 below:
The formula table of table 2 embodiment 6～10
| Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | |
| PVC(P＝2500) | 100 | 100 | 100 | 100 | 100 |
| Calcium-zinc composite stabilizing agent | 3 | 5 | 6 | 7 | 8 |
| TBC | 10 | 10 | 10 | 20 | 20 |
| topM | 20 | 30 | 30 | 30 | 20 |
| Polyester plasticizer | 10 | 10 | 0 | 10 | 10 |
| EVA | 20 | 10 | 5 | 5 | 5 |
| CPE | 5 | 5 | 0 | 5 | 5 |
| Antioxidant 1010 | 1.0 | 1.5 | 1.5 | 1.0 | 0.5 |
| Stearate | 0.6 | 0.4 | 0.4 | 0.6 | 0.2 |
| PE wax | 0.4 | 0.2 | 0.4 | 0.2 | 0.2 |
| Titanium dioxide | 2 | 2 | 2 | 2 | 2 |
| Photostabilizer UV-419 | 0.5 | 0.5 | 1.0 | 1.0 | 1.5 |
| Carbon black | 0.5 | 0.8 | 1.0 | 1.0 | 1.5 |
The prescription of embodiment 11～15 is as shown in table 3 below:
The formula table of table 3 embodiment 11～15
| Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | Embodiment 15 | |
| PVC(P＝1300) | 100 | 100 | 100 | 100 | 100 |
| Calcium-zinc composite stabilizing agent | 3 | 5 | 6 | 7 | 8 |
| topM | 40 | 40 | 40 | 30 | 25 |
| Polyester plasticizer | 0 | 10 | 10 | 20 | 30 |
| EVA | 20 | 10 | 5 | 5 | 5 |
| CPE | 5 | 5 | 0 | 5 | 5 |
| Antioxidant 1010 | 1.0 | 1.5 | 1.5 | 1.0 | 0.5 |
| Stearate | 0.6 | 0.4 | 0.4 | 0.6 | 0.2 |
| PE wax | 0.4 | 0.2 | 0.4 | 0.2 | 0.2 |
| Titanium dioxide | 2 | 2 | 2 | 2 | 2 |
| Photostabilizer UV-419 | 0.5 | 0.5 | 1.0 | 1.0 | 1.5 |
| Carbon black | 0.5 | 0.8 | 1.0 | 1.0 | 1.5 |
The preparation method of embodiment 1～10:
(1) raw material compounding: weigh up material by proportioning raw materials, then join high-speed mixer and mix, to 120 ℃ of mixing temperatures, material is put into low speed mixer, discharging when treating that temperature of charge is cooled to 40 ℃.
(2) granulation process: the material that mixes is adopted the twin screw granulation, and processing parameter arranges as follows:
Extruder temperature (℃): 1 district, 2 districts, 3 districts, 4 districts, 5 district's heads
110 120 130 140 150 150
(3) calendering technology: pellet is rolled into film with rolling press, and processing parameter arranges as follows:
The stack temperature (℃): 1 roller, 2 rollers, 3 rollers, 4 rollers, 5 rollers
190 185 175 170 150
The preparation method of embodiment 11～15:
(1) raw material compounding: weigh up material by proportioning raw materials, then join high-speed mixer and mix, to 120 ℃ of mixing temperatures, material is put into low speed mixer, discharging when treating that temperature of charge is cooled to 40 ℃.
(2) calendering technology: pellet is rolled into film with rolling press, and processing parameter arranges as follows:
The stack temperature (℃): 1 roller, 2 rollers, 3 rollers, 4 rollers, 5 rollers
200 195 185 180 160
Performance test methods: hack with two roller mills after the mixing of materials, at 180 ℃ of compactings of moulding press print, make test performance after the test samples.The result is as follows:
The performance test results of embodiment 1～5 is as shown in table 4 below:
Table 4 embodiment 1～5 the performance test results table
The performance test results of embodiment 6～10 is as shown in table 5 below:
Table 5 embodiment 6～10 the performance test results tables
The performance test results of embodiment 11～15 is as shown in table 6 below:
Table 6 embodiment 11～15 the performance test results tables
Comparative example 1～3
The prescription of comparative example 1～3 is as shown in table 7 below:
The formula table of table 7 comparative example 1～3
Comparative example performance test methods: hack with two roller mills after the mixing of materials, at 180 ℃ of compactings of moulding press print, test performance after the test samples of system.
The performance test results of comparative example 1～3 is as shown in table 8 below:
Table 8 comparative example 1～3 the performance test results table
| Test item | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Tensile strength (vertical/horizontal stroke) MPa | 21.6/20.2 | 22.5/21.7 | 21.4/19.9 |
| Elongation at break (vertical/horizontal stroke) % | 320.6/315.8 | 338.4/330.7 | 315.9/312.8 |
| Tear strength (vertical/horizontal stroke) kNm -1 | 50.3/49.8 | 49.7/47.6 | 48.7/48.2 |
| Low-temperature extension (vertical/horizontal stroke) % | 48.4/46.7 | 49.2/47.2 | 47.8/46.3 |
| 60 ℃ * 24h water extract % | 0.19 | 0.23 | 0.20 |
| 3000h ultraviolet light and aging back draft intensity (vertical/horizontal stroke) MPa | 22.3/20.9 | 22.9/22.0 | 21.9/20.5 |
| Mass loss rate % after 125 ℃ * 240h is aging | 8.4 | 8.6 | 9.1 |
Comparative example 1 and comparative example 2 adopt PVC with high and paracril to increase the intensity of material, comparative example 3 adopts 1000 lower type polyvinyl chloride resins of the polymerization degree, 3 used softening agent of comparative example all are universal small molecules softening agent, and relative embodiment is lower for its mechanical property.The index of reflection materials ' durability, aging such as 60 ℃ * 24h water extract and 125 ℃ * 240h after the index such as mass loss rate, comparative example will be higher than embodiment, sufficient proof the weather resistance of comparative example relatively poor.
Claims (11)
1. permanent seal cooling polyvinyl chloride salt film composition is characterized in that being made by the raw material of following mass fraction:
2. permanent seal cooling polyvinyl chloride salt film composition according to claim 1 is characterized in that described polyvinyl chloride polymerization degree is 800～4000.
3. permanent seal cooling polyvinyl chloride salt film composition according to claim 1 is characterized in that described stablizer is organotin stabilizer or calcium-zinc composite stabilizing agent.
4. permanent seal cooling polyvinyl chloride salt film composition according to claim 1 is characterized in that described softening agent is two or more in trioctyl trimellitate, tetraoctyl 1,2,4,5-benzenetetra-carboxylate, polyester plasticizer or the tributyl citrate, and consumption is 40～80 parts.
5. permanent seal cooling polyvinyl chloride salt film composition according to claim 1 is characterized in that described low temperature modification agent is ethylene-vinyl acetate copolymer and/or chlorinatedpolyethylene.
6. permanent seal cooling polyvinyl chloride salt film composition according to claim 1 is characterized in that described lubricant is two or more in polyethylene wax, Microcrystalline Wax or the fatty acid ester.
7. permanent seal cooling polyvinyl chloride salt film composition according to claim 1 is characterized in that described antioxidant is that phenolic antioxidant or phosphorus are oxidation inhibitor, and consumption is 0.5～1.5 part.
8. permanent seal cooling polyvinyl chloride salt film composition according to claim 1 is characterized in that described photostabilizer is hindered amine light stabilizer or benzotriazole category ultraviolet absorbers, and consumption is 0.5～1.5 part.
9. permanent seal cooling polyvinyl chloride salt film composition according to claim 1 is characterized in that described photomask agent is titanium dioxide.
10. permanent seal cooling polyvinyl chloride salt film composition according to claim 1 is characterized in that described tinting material is carbon black, and consumption is 0.5～1.5 part.
11. the preparation method of the arbitrary described permanent seal cooling polyvinyl chloride salt film composition of claim 1～10 is characterized in that raw material is made through compounding-calendering technology or compounding-granulation-calendering technology;
Described compounding-granulation-calendering technology comprises the steps:
(1) material compounding technique: polyvinyl chloride (PVC) RESINS, stablizer, softening agent, low temperature modification agent, lubricant, antioxidant, photostabilizer, photomask agent, tinting material are mixed in high low speed mixer group, when being 100～130 ℃ to mixing temperature, again material is put into low speed mixer, treats that temperature of charge is cooled to 35～45 ℃ of dischargings;
(2) granulation process: the material that mixes is adopted twin screw granulation, 130～160 ℃ of prilling temperatures;
(3) calendering technology: with rolling press pellet is rolled into film, rolling temperature is 150～190 ℃;
Described compounding-calendering technology comprises the steps:
(1) material compounding technique: polyvinyl chloride (PVC) RESINS, stablizer, softening agent, low temperature modification agent, lubricant, antioxidant, photostabilizer, photomask agent, tinting material are mixed in high low speed mixer group, when being 100～130 ℃ to mixing temperature, again material is put into low speed mixer, treats that temperature of charge is cooled to 35～45 ℃ of dischargings;
(2) calendering technology: with rolling press pellet is rolled into film, rolling temperature is 160～200 ℃.
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| CN105153566A (en) * | 2014-06-09 | 2015-12-16 | 南通慧源塑胶有限公司 | PVC film formula |
| CN105175941A (en) * | 2015-09-21 | 2015-12-23 | 广东联塑科技实业有限公司 | Environment-friendly high-weather-resistant PVC-M water supply pipe material and preparation method therepf |
| CN105255065A (en) * | 2015-11-17 | 2016-01-20 | 雅安市晶强板业有限公司 | Green environment-friendly composite paint-free decorative material and production technology thereof |
| CN106751113A (en) * | 2016-04-17 | 2017-05-31 | 佛山瑞箭体育器材有限公司 | A kind of polyvinyl chloride film composition |
| CN106751117A (en) * | 2016-04-23 | 2017-05-31 | 佛山瑞箭体育器材有限公司 | A kind of geomembrane hypotonicity polychloroethylene composition |
| CN108384147A (en) * | 2018-03-22 | 2018-08-10 | 台州久通塑胶有限公司 | PVC rolls laminated sheet |
| CN109071903A (en) * | 2016-03-29 | 2018-12-21 | 日本瑞翁株式会社 | Vinyl chloride resin composition, vinyl chloride resin formed body and laminated body |
| CN111471252A (en) * | 2020-05-25 | 2020-07-31 | 江苏大海塑料股份有限公司 | Environment-friendly migration-resistant PVC (polyvinyl chloride) film for packaging home textile products and production process thereof |
| WO2023019882A1 (en) * | 2021-08-17 | 2023-02-23 | 青岛理工大学 | Method for improving surface quality of alloy micro-region by salt film method and application |
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| CN106751117A (en) * | 2016-04-23 | 2017-05-31 | 佛山瑞箭体育器材有限公司 | A kind of geomembrane hypotonicity polychloroethylene composition |
| CN108384147A (en) * | 2018-03-22 | 2018-08-10 | 台州久通塑胶有限公司 | PVC rolls laminated sheet |
| CN111471252A (en) * | 2020-05-25 | 2020-07-31 | 江苏大海塑料股份有限公司 | Environment-friendly migration-resistant PVC (polyvinyl chloride) film for packaging home textile products and production process thereof |
| WO2023019882A1 (en) * | 2021-08-17 | 2023-02-23 | 青岛理工大学 | Method for improving surface quality of alloy micro-region by salt film method and application |
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Application publication date: 20131023 |