CN101544802A - Modified polyvinyl chloride salt film and preparation method thereof - Google Patents
Modified polyvinyl chloride salt film and preparation method thereof Download PDFInfo
- Publication number
- CN101544802A CN101544802A CN200810102829A CN200810102829A CN101544802A CN 101544802 A CN101544802 A CN 101544802A CN 200810102829 A CN200810102829 A CN 200810102829A CN 200810102829 A CN200810102829 A CN 200810102829A CN 101544802 A CN101544802 A CN 101544802A
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- quality
- polyvinyl chloride
- salt film
- sebate
- phthalic ester
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Classifications
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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
-
- 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
-
- 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
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Abstract
The invention relates to a modified polyvinyl chloride salt film which comprises polyvinyl chloride and the following components by weight: 0-20 percent of nitrile rubber, 5-80 percent of phthalic acid ester, 1-15 percent of decanedioic acid ester, 1-10 percent of phosphorous acid ester, 0.5-10 percent of rare earth metal salt, 1-15 percent of epoxy compound, 0.1-5 percent of C18-C20 fatty acid, 0.1-2.0 percent of light stabilizer and 0.1-2.0 percent of oxidation inhibitor which are calculated by taking the polyvinyl chloride as a standard. The salt film has better mechanical property, low-temperature property and uvioresistant property.
Description
Technical field
The present invention is a kind of modified pvc film and preparation method, specifically, is a kind of salt film of covering in the salt pond and preparation method thereof that is used to.
Background technology
Salt plays a part very important in national economy and daily life as the basic material and the necessity of people life of chemical industry.The production of salt is divided into three phases: the fs is an evaporation stage, and subordinate phase is the conciliation stage, and when the bittern salt concentration reached 25 degree Beaume, entering crystallizing pond, to change the phase III over to be crystallisation stage.If weather is better during the crystallization, in every year five, June, general crystallization was dialled salt once in 10～20 days, but as run into rainy weather, crystalline salt is dissolved for part, and crystallization time is prolonged, its result descends salt output and quality significantly, has a strong impact on the economic benefit in saltern.In order to address this problem, saltern employing film covers the crystallizing pond novel process and improves salt output and quality, this method less investment, and instant effect, effect of increasing production is very obvious.The salt film will stand summer high temperature, Exposure to Sunlight and drench with rain in actual application, also to stand severe cold and the etch of bittern throughout the year below-20 ℃ simultaneously, characteristics such as ageing-resistant, anti-bittern extracts out so the salt film must possess, cold-resistant, big, the anti-puncture of intensity.The quality quality of salt film will directly have influence on economic benefit.
At present, general salt film is mainly made by polyvinyl chloride (PVC) RESINS, softening agent, stablizer and other processing aid, and its low temperature flexibility is subjected to certain restriction, and mechanical performance index neither be too high, so exist the salt film damaged easily, causes the salt production cost to improve.
CN1056460A discloses a kind of non-porous polyvinyl chloride film for saltworks, is applicable to the saltern film special, is made through compound side cut by the two-layer pvc film.The additive that its used polyvinyl chloride film contains has barium stearate cadmium, dibasic lead phosphite and carbon black.These two layers of laminated films have overcome the pin hole problem that the individual layer polyvinyl chloride salt film exists, and the edge is smooth, can reach to prevent that bittern runs off and dashed what is said or talked about bittern because of drenching with rain, and have improved the output and the quality of salt, and can alleviate working strength of workers.
CN1865324A discloses a kind of low temperature resistant polyvinyl chloride, salt film for anti-aging, comprises 100 parts of weights of following component formulated (A) polyvinyl chloride (PVC) RESINS; (B) dioctyl phthalate (DOP) 10-40 part; (C) dioctyl terephthalate 10-40 part; (D) Octyl adipate 2-12 part; (E) thermo-stabilizer 2-5 part; (F) carbon black 1-4 part; (G) Octabenzone (or 2-hydroxy-4-methyl benzophenone) 0.1-0.6 part; (H) 4,4-isopropylidene bis-phenol 0.1-0.8 part.The thermo-stabilizer that this salt film uses is selected from barium stearate or lead stearate as the mixture of liquid stabilisers and metallic soap class stablizer, described soap class stablizer.The polyvinyl chloride film that makes is fully improved in the performance aspect low temperature resistant, anti-aging, solved salt film out of use situation under the lesser temps state, and the work-ing life of having improved the salt film effectively, but mechanical property does not further improve.
Summary of the invention
The purpose of this invention is to provide a kind of modified polyvinyl chloride salt film, the mechanical property of this salt film can further improve the life cycle of salt film far above present general salt film, reduces production costs.
Modified polyvinyl chloride salt film provided by the invention comprises polyvinyl chloride and is the following component of content that benchmark calculates with the polyvinyl chloride:
Paracril 0～20 quality %,
Phthalic ester 5～80 quality %,
Sebate 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 0.1～3.0 quality %,
Oxidation inhibitor 0.1～3.0 quality %.
The present invention mixes suitable softening agent in polyvinyl chloride and thermo-stabilizer carries out modification, the modified polyvinyl chloride that makes, and not only mechanical property increases, and low-temperature performance and anti-ultraviolet property also are improved.
Embodiment
The present invention makes modified polyvinyl chloride by add suitable softening agent, thermo-stabilizer and lubricant in polyvinyl chloride, the film made from this modified polyvinyl chloride, be that the salt film has higher draw tensile strength and elongation at break, anti-ultraviolet property and low temperature performance excellent add paracril and can further improve material modified elasticity and resistance to low temperature in above-mentioned modified polyvinyl chloride simultaneously.
The preferred salt mould material of the present invention comprises polyvinyl chloride and is the following component of content that benchmark calculates with the polyvinyl chloride:
Paracril 1～10 quality %,
Phthalic ester 20～60 quality %,
Sebate 1～10 quality %,
Phosphorous acid ester 1～5 quality %,
Rare earth metal salt 0.5～5 quality %,
Epoxy compounds 1～10 quality %,
C
18～C
20Lipid acid 0.1～1.0 quality %,
Photostabilizer 0.1～1.0 quality %,
Oxidation inhibitor 0.1～1.0 quality %.
For reducing salt film cost, wherein preferably include the inorganic fillers of 5～30 quality %.The preferred lime carbonate of described inorganic fillers, more preferably density is 2～3 gram per centimeters
3Light calcium carbonate.
The polymerization degree of polyvinyl chloride of the present invention is 800～3000, preferred 1000～3000.
The content of vinyl cyanide is 25～60 quality % in the described paracril, preferred 25～45 quality %.
The present invention selects three kinds of ester plasticizers for use, wherein said phthalic ester pref-erable dioctyl phthalate, and the preferred dioctyl sebacate of described sebate, the preferred trialkyl phenyl phosphites of described phosphorous acid ester, wherein said alkyl is C
9～C
18Alkyl, preferred C
3～C
10The phenyl that alkyl replaces.
The thermo-stabilizer that the present invention selects for use is rare earth metal salt and epoxy compounds.The carboxylate salt of the preferred lanthanide series metal of described rare earth metal salt, the more preferably acetate of lanthanide series metal.The preferred epoxy soybean oil of described epoxy compounds.
The lubricant that the present invention selects for use is C
18～C
20Lipid acid, preferred stearic acid.
For the modified polyvinyl chloride that the present invention is made has light stability and antioxygen property, need to add photostabilizer and oxidation inhibitor.Photostabilizer and oxidation inhibitor all can use conventional photostabilizer and oxidation inhibitor.
The preferred hindered amine as light stabilizer of described photostabilizer is as poly-{ [6-[(1,1,3, the 3-tetramethyl butyl) amino]]-1,3,5-triazines-2,4-two [(2,2,6,6 ,-tetramethyl-4-piperidyl) imino-]-1, oneself two supports [(2 of 6-, 2,6,6-tetramethyl--4-piperidyl) imino-] (photostabilizer 944), two (1,2,2,6,6-pentamethyl--4-piperidines) sebate and 1-methyl-8-(1,2,2,6,6-pentamethyl--4-piperidines) mixture of sebate, poly-[1-(2`-hydroxyethyl)-2,2,6,6-tetramethyl--4-hydroxy piperidine Succinic Acid fat], sebacic acid two 2,2,6,6-tetramethyl piperidine alcohol ester, more preferably photostabilizer 944.
The preferred phenolic antioxidant of described oxidation inhibitor is as four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010).
The preparation method of salt film provided by the invention comprises the steps:
(1) polyvinyl chloride and other component except that phthalic ester and sebate are put into agitator and mix, add phthalic ester and sebate again and continue to be stirred to even, make the modified polyvinyl chloride base-material,
(2) above-mentioned base-material is put into the forcing machine extruding pelletization, it is 150～200 ℃ that the control forcing machine is respectively distinguished temperature,
(3) pellet is used press mold machine press mold.
The inventive method (1) step is a preparation modified polyvinyl chloride base-material, and described polyvinyl chloride and other component can together add in the agitator, also each component can be added agitator respectively.Preferably phthalic ester and sebate after mixing, other component are added several times again, preferred branch adds for three times, add behind phthalic ester and the sebate whipping temp improved and continue to stir, till all adding phthalic ester and sebate in the compound.
The whipping temp that described method (1) adds in the step before phthalic ester and the sebate is 30～50 ℃, and adding phthalic ester and sebate whipping temp afterwards is 60～90 ℃.Mix when stirring, the control stir speed (S.S.) is 100～200 rev/mins, preferred 120～150 rev/mins.Churning time 5～20 minutes, preferred 10～15 minutes.
Described method (2) step is that the modified polyvinyl chloride base-material is carried out extruding pelletization, and extruding pelletization can carry out in single screw extrusion machine, also can carry out in twin screw extruder, preferably uses the twin screw extruder extruding pelletization.Forcing machine is respectively distinguished temperature and is controlled to be 150～200 ℃, preferred 150～180 ℃.Screw speed is 20～50 rev/mins when extruding, preferred 20～30 rev/mins.
Further describe the present invention below by example, but the present invention is not limited to this.
The performance test methods of institute's salt manufacturing film is as follows in the example:
Example 1
(1) preparation modified polyvinyl chloride base-material
With the polymerization degree is that (Shandong branch office of China Petrochemical Industry produces for 2500 polyvinyl chloride, trade mark QL2500), paracril (acrylonitrile content 33 quality %, France Yi Liou company produces), three nonyl phenyl phosphites (the luxuriant imperial chemical industry of Maoming City company limited produces), lanthanum acetate (production of Shanghai Long John metallic substance company limited), epoxy soybean oil (production of Changshu, Jiangsu first plastic molding and processing plant), stearic acid (production of Jiangsu span chemical company), lime carbonate, photostabilizer 944 and antioxidant 1010 are put into high speed agitator by feed ratio, at 40 ℃, stir speed (S.S.) is to stir under 120～150 rev/mins the condition to make compound in 12 minutes, then dioctyl phthalate (DOP) (DOP) and dioctyl sebacate (DOS) branch are added for three times in the compound, each dosage is 1/3 of its total amount.Proceed to stir behind each DOP of adding and the DOS, stir speed (S.S.) still is 120～150 rev/mins, and whipping temp is 70 ℃, churning time 15 minutes.Obtain the modified polyvinyl chloride base-material at last.The mass fraction that feeds intake of used each component of preparation base-material sees Table 1.
(2) extruding pelletization and press mold
With above-mentioned base-material extruding pelletization on twin screw extruder, it is 150～180 ℃ that the control forcing machine is respectively distinguished temperature, and the extruder screw rotating speed is 20～50 rev/mins, obtains the modified polyvinyl chloride pellet.
With modified polyvinyl chloride pellet press mold mechanism salify membrane sample, and test its performance, the results are shown in Table 2.
Example 2
Method according to example 1 prepares modified polyvinyl chloride pellet and press mold, and the polymerization degree of different is used polyvinyl chloride is 1300, and the The performance test results that makes the salt film sees Table 2.
Example 3
Method according to example 1 prepares modified polyvinyl chloride pellet and press mold, and the consumption of different is paracril is 10 mass parts, and the The performance test results that makes the salt film sees Table 2.
Example 4
Method according to example 1 prepares modified polyvinyl chloride pellet and press mold, and the consumption of different is paracril is 15 mass parts, and the The performance test results that makes the salt film sees Table 2.
Example 5
Method according to example 1 prepares modified polyvinyl chloride pellet and press mold, and the acrylonitrile content of different is used paracril is 40 quality %, and the The performance test results that makes the salt film sees Table 2.
Table 1
Table 2
| Instance number | Tensile strength (vertical/horizontal stroke), MPa | Elongation at break (vertical/horizontal stroke), % | Angle tear strength (vertical/horizontal stroke)/KNm -1 | Low-temperature extension (vertical/horizontal stroke), % | The yellow index (500 hours ultraviolet ray ageings) of salt film |
| 1 | 20.6/20.4 | 470.3/440.7 | 50.1/45.7 | 45.9/40.3 | 42.41 |
| 2 | 18.1/17.7 | 450.1/410.6 | 48.8/44.3 | 41.6/38.5 | 45.64 |
| 3 | 19.2/19.1 | 476.2/454.5 | 48.5/44.1 | 47.2/41.6 | 43.56 |
| 4 | 17.9/17.3 | 480.1/466.6 | 47.3/42.5 | 49.6/43.5 | 42.38 |
| 5 | 19.7/18.6 | 462.6/431.3 | 48.1/40.5 | 42.3/36.7 | 45.39 |
| General salt film standard | 8.6/16.5 | 220.0/220.0 | 40.0/40.0 | 20.0/20.0 | 55.00 |
Claims (13)
1, a kind of modified polyvinyl chloride salt film comprises polyvinyl chloride and is the following component of content that benchmark calculates with the polyvinyl chloride:
Paracril 0～20 quality %,
Phthalic ester 5～80 quality %,
Sebate 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 0.1～3.0 quality %,
Oxidation inhibitor 0.1～3.0 quality %.
2,, it is characterized in that described salt film comprises polyvinyl chloride and be the following component of content that benchmark calculates with the polyvinyl chloride according to the described salt film of claim 1:
Paracril 1～10 quality %,
Phthalic ester 20～60 quality %,
Sebate 1～10 quality %,
Phosphorous acid ester 1～5 quality %,
Rare earth metal salt 0.5～5 quality %,
Epoxy compounds 1～10 quality %,
C
18～C
20Lipid acid 0.1～1.0 quality %,
Photostabilizer 0.1～1.0 quality %,
Oxidation inhibitor 0.1～1.0 quality %.
3,, it is characterized in that described salt film also comprises the inorganic fillers of 5～30 quality % according to the described salt film of claim 1.
4,, it is characterized in that described inorganic fillers is a lime carbonate according to the described salt film of claim 3.
5, according to the described salt film of one of claim 1～3, the polymerization degree that it is characterized in that described polyvinyl chloride is 800～3000.
6, according to the described salt film of one of claim 1～3, the content that it is characterized in that vinyl cyanide in the described paracril is 25～60 quality %.
7, according to the described salt film of one of claim 1～3, it is characterized in that described phthalic ester is a dioctyl phthalate (DOP), described sebate is a dioctyl sebacate, described phosphorous acid ester is the trialkyl phenyl phosphites.
8, according to the described salt film of one of claim 1～3, it is characterized in that described rare earth metal salt is the carboxylate salt of lanthanide series metal, described epoxy compounds is an epoxy soybean oil.
9, according to the described salt film of one of claim 1～3, it is characterized in that described C
18～C
20Lipid acid be stearic acid.
10, according to the described salt film of one of claim 1～3, it is characterized in that described photostabilizer is a hindered amine as light stabilizer, oxidation inhibitor is phenolic antioxidant.
11, the preparation method of the described salt film of a kind of claim 1 comprises the steps:
(1) polyvinyl chloride and other component except that phthalic ester and sebate are put into agitator and mix, add phthalic ester and sebate again and continue to be stirred to even, make the modified polyvinyl chloride base-material,
(2) above-mentioned base-material is put into the forcing machine extruding pelletization, it is 150～200 ℃ that the control forcing machine is respectively distinguished temperature,
(3) pellet is used press mold machine press mold.
12, in accordance with the method for claim 11, the whipping temp that it is characterized in that adding in (1) step before phthalic ester and the sebate is 30～50 ℃, and the whipping temp that adds after phthalic ester and the sebate is 60～90 ℃.
13, in accordance with the method for claim 11, it is characterized in that described phthalic ester of (1) step and sebate add in the compound several times.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101028297A CN101544802B (en) | 2008-03-27 | 2008-03-27 | Modified polyvinyl chloride salt film and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101028297A CN101544802B (en) | 2008-03-27 | 2008-03-27 | Modified polyvinyl chloride salt film and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN101544802A true CN101544802A (en) | 2009-09-30 |
| CN101544802B CN101544802B (en) | 2012-01-25 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864129A (en) * | 2010-07-21 | 2010-10-20 | 天津市天塑科技集团有限公司第四塑料制品厂 | Polyvinyl chloride geomembrane modified by nitrile-butadiene rubber |
| CN103360695A (en) * | 2012-03-30 | 2013-10-23 | 中国石油化工股份有限公司 | Durable polyvinyl chloride salt membrane composition and preparation method thereof |
| CN103497446A (en) * | 2013-09-25 | 2014-01-08 | 天津市天塑科技集团有限公司第四塑料制品厂 | Environmental-friendly polyvinyl chloride (PVC) extraction-resistant anti-seepage film and preparation method thereof |
| CN104403231A (en) * | 2014-11-24 | 2015-03-11 | 苏州市贝克生物科技有限公司 | Medical packaging calendering film and preparation method thereof |
| CN112358695A (en) * | 2020-10-31 | 2021-02-12 | 苏州特聚新材料科技有限公司 | Salt film with rust resistance function |
-
2008
- 2008-03-27 CN CN2008101028297A patent/CN101544802B/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864129A (en) * | 2010-07-21 | 2010-10-20 | 天津市天塑科技集团有限公司第四塑料制品厂 | Polyvinyl chloride geomembrane modified by nitrile-butadiene rubber |
| CN103360695A (en) * | 2012-03-30 | 2013-10-23 | 中国石油化工股份有限公司 | Durable polyvinyl chloride salt membrane composition and preparation method thereof |
| CN103497446A (en) * | 2013-09-25 | 2014-01-08 | 天津市天塑科技集团有限公司第四塑料制品厂 | Environmental-friendly polyvinyl chloride (PVC) extraction-resistant anti-seepage film and preparation method thereof |
| CN104403231A (en) * | 2014-11-24 | 2015-03-11 | 苏州市贝克生物科技有限公司 | Medical packaging calendering film and preparation method thereof |
| CN112358695A (en) * | 2020-10-31 | 2021-02-12 | 苏州特聚新材料科技有限公司 | Salt film with rust resistance function |
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| Publication number | Publication date |
|---|---|
| CN101544802B (en) | 2012-01-25 |
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