CN101575422A - Method for preparing environmental-friendly calcium-zinc composite liquid stabilizing agent - Google Patents
Method for preparing environmental-friendly calcium-zinc composite liquid stabilizing agent Download PDFInfo
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- CN101575422A CN101575422A CNA2009100997283A CN200910099728A CN101575422A CN 101575422 A CN101575422 A CN 101575422A CN A2009100997283 A CNA2009100997283 A CN A2009100997283A CN 200910099728 A CN200910099728 A CN 200910099728A CN 101575422 A CN101575422 A CN 101575422A
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Abstract
The invention relates to a method for preparing environment-friendly calcium-zinc composite stabilizing agent, in particular to a method for preparing the environmental-friendly calcium-zinc composite stabilizing agent by adopting efficient chelating technology. The four ingredients of binary or multivariate saturated acid calcium, binary or multivariate saturated acid zinc, antioxidant and co-stabilizer are mixed in a reaction kettle according to certain mass ratios, the mixture is heated in the reaction kettle, and chelating agent with the mass ratio of 5 to 10 percent is added, when the reaction temperature is controlled to be higher than the melting point of lubricant, about 10 to 20 percent of the lubricant is added to the reaction kettle, the mixture is fully mixed, and then the mixture is cooled to a normal-temperature state and stirred at a low speed, thus obtaining the product. The method has the advantages that the coating of the calcium-zinc composite stabilizing agent is modified at a temperature higher than the melting point of the lubricant, thus greatly reducing the hydroscopic property and further increasing the electric resistivity of PVC products. Simultaneously, the stabilizer of static coating modification is more beneficial to PVC dispersion, thus improving the stabilizing effect.
Description
Technical field
The present invention relates to a kind of preparation method of chemical stabilizer, specifically be meant a kind of preparation method of environmental-friendly calcium-zinc composite liquid stabilizing agent.
Technical background
Polyvinyl chloride (PVC) is one of synthetic resins of large usage quantity in the world, has light weight, intensity height, fire-retardant, corrosion-resistant, insulation, characteristics such as transparent.PVC begins obvious decomposition under 100-150 ℃, UV-light mechanical force, oxygen, ozone, hydrogenchloride and active metallic ion etc. all can quicken the decomposition of PVC greatly.The thermo-oxidative ageing of PVC is complicated, toward firmly having carried out several chemical reaction processes simultaneously.Existing decomposition dehydrochlorination has oxidative cleavage and crosslinked again, also has the fracture of a small amount of aromizing and macromolecular chain to generate the reaction process of hydrocarbon in addition, and wherein decomposing dehydrochlorination is to cause PVC aged major cause.The thermostability that improves PVC mainly adopts the method for adding stablizer.The situation that thermo-stabilizer uses separately in the industry PVC production of articles is few, mainly is to carry out composite use according to the property of each product.Composite thermal stabilizer mainly can divide following 5 classes: (1) co-precipitation metallic soap one package stabilizer; (2) liquefaction metallic soap one package stabilizer; (3) ultralow lead salt one package stabilizer; (4) rare earth composite stabilizer; (5) organotin one package stabilizer.
The use of thermo-stabilizer and industrial polyvinyl chloride resin and PVC is soft, the proportion of production of boardy product has substantial connection.Although world's stablizer various countries situation difference, the structure difference of PVC goods, the consumption of its thermo-stabilizer and structure have bigger difference, and unleaded, low plumbous, low dust, nontoxic, composite highly effective are consumption of PVC thermo-stabilizer and developing direction.The not leaded oxious component that waits of calcium-zinc composite liquid stabilizing agent, cost is cheap relatively, is important new stabilizer product.
Present domestic liquid calcium zinc stabilizer generally is to do raw material with lipid acid, adopt metal oxide such as alkaline-earth metal such as saponification-metathesis process or direct oxidation technology and barium, calcium, magnesium or zinc, magnesium, aluminium and reactant salt thereof and obtain the fatty acid metal soap, auxiliaryly again add multiple auxiliary agent and form.The quality product that saponification-metathesis process obtains is more stable, but reaction time is long, the flow process complexity, and produce sewage, the direct oxidation technological reaction time shortens, but needs pyroreaction, and reaction is thorough inadequately.
Summary of the invention
Deficiency at above-mentioned present synthetic fluid calcium zinc stabilizer, the innovation provides a kind of can significantly shorten reaction process, fast reaction speed, and the monomeric synthetic method of eco-friendly fatty acid metal salt is used again and calcium zinc metallic soap has good synergistic a kind of special auxiliary to be deployed into the liquid calcium zinc complex stabilizer with good thermal stability.
The present invention is achieved by following technical proposals:
A kind of preparation method of environmental-friendly calcium-zinc composite liquid stabilizing agent is characterized in that comprising the steps:
(1) one or more organic acids in adding identical olefin(e) acid, naphthenic acid or the isocaprylic acid in reaction vessel, add calcium hydroxide or calcium oxide, zinc oxide while stirring, control reaction temperature is at 80-100 ℃, the control reaction pressure is at 0.05-0.1MPa, reacted 2-3 hour, and obtained the fatty acid metal soap;
Corresponding reaction formula is expressed as follows:
2RCOOH+Ca(OH)
2＝Ca(RCOO)
2+2H
2O
2RCOOH+Zn(OH)
2＝Zn(RCOO)
2+2H
2O
(2) fatty acid metal soap solution and oxidation inhibitor, lubricant, co-stabilizer, solvent, promotor is composite;
Wherein, oxidation inhibitor is polynary hindered phenol type antioxidant;
Lubricant is one or more the composite mixtures in butyl stearate, glyceryl monostearate, ester type waxes or the saponified wax;
Co-stabilizer is phosphorous acid ester or diphenylpropane-1,3-dione(DPPO);
Solvent is one or more the mixture in mineral oil, solvent oil, the softening agent;
Promotor is beta-diketone compounds;
The temperature of above-mentioned composite reaction is controlled at 100-150 ℃, evenly stirs cool to room temperature 10-50 minute;
(3) reactant is made with extra care, press filtration obtains finished product.
As preferably, add inert solvent benzene or chloroform in the step among the above-mentioned preparation method (1) in the reaction vessel, can protect the reaction in reaction vessel to carry out better.
As preferably, organic acid is one or more in olefin(e) acid, naphthenic acid or the isocaprylic acid of 12-18 carbon in the step among the above-mentioned preparation method (1).
As preferably, add several organic acids in olefin(e) acid, naphthenic acid or the isocaprylic acid of same concentrations in the step among the above-mentioned preparation method (1).
As preferably, in the step among the above-mentioned preparation method (2)
Oxidation inhibitor is 2, three grades of butyl of 6--4-methylphenol, two (3, three grades of butyl of 5--4-hydroxy phenyl) thioether, four (β-(3, three grades of butyl of 5--4-hydroxy phenyl) one or more mixtures in pentaerythritol ester, (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, tricresyl phosphite monooctyl ester, tridecyl phosphite propionic acid);
Lubricant is butyl stearate or glyceryl monostearate;
Co-stabilizer is the phosphorous acid alkyl aryl ester, and adds a kind of in epoxy soybean oil (ESO), epoxyoleic acid, epoxy ricinolic acid or the epoxy aliphatic acid methyl ester;
Solvent is mineral oil, whiteruss;
Above-mentioned each component is as follows by the proportioning of quality:
Fatty acid metal soap consumption: 20-40%
Solvent load: 10-40%
Oxidation inhibitor: consumption: 1-10%
Lubricant: consumption: 1-10%
Co-stabilizer: consumption: 10-50%
Promotor: consumption: 1-5%
The temperature of above-mentioned composite reaction is controlled at 100-120 ℃, evenly stirred 10-20 minute, and cool to room temperature, stirring at low speed 10-20 minute again, the control mixing speed was at 400-600 commentaries on classics/min.
Be reflected under certain pressure during fatty acid metal soap monomer in the present technique synthetic fluid calcium-zinc composite stabilizing agent and carry out, the pressure of system maintains 0.05-0.15MPa, temperature is about 80-100 ℃, and it is complete to react 2-3 hour primitive reaction, and productive rate can reach more than 99%.The compounding technology that adopts can effectively suppress zinc and burn optionally in conjunction with the metallic zinc in the stronger Lewis acid zinc chloride on the one hand, and the oxidation that can suppress polyene structure on the other hand is with crosslinked, thus the raising thermal stability.
Compare with other technology:
1, the patent disclosure of publication number: CN101200557A a kind of liquid rare earth calcium zinc stabilizer and preparation method thereof.Reaction is adopted and is used rare earth oxide in the material, increased production cost, need to use 3-10 part catalyst oxidizing reaction in the reaction process, increased the burden of aftertreatment, the calcium that obtains, zinc, lucium just can enter subsequent reactions after needing to handle through vacuum hydro-extraction earlier, about 5 hours reaction times, the reaction times is long.
2, the patent disclosure of publication number: CN1740225A a kind of preparation method of epoxy composite zinc soap thermo-stabilizer of polyvinyl chloride plastic material formula.The main epoxy composite zinc soap stablizer that uses mixes with the optimum quantity of other organic compound co-stabilizers, wherein used white dyes, in the addition 10%, fluorescent agent is absorbed by the body afterwards and the protein in the human body combines, increased the weight of the burden of liver, according to the clinical medicine experiment confirm, fluorescent substance can make cell produce variability, be listed in one of potential carcinogenic factor, run counter to environmental protection and the health idea advocated at present.
Beneficial effect: the method for employing of the present invention has higher, the more environmental protection, energy-conservation of efficient, and advantage such as quality product is more stable.
Embodiment
Below enforcement of the present invention is specified
The fatty acid metal soap is a basic material of making stablizer, is that grease and calcium zinc oxide, oxyhydroxide chemical combination form, and is the basic material of using always in the industry.
Embodiment 1
According to following recipe configuration environmental protection calcium zinc stabilizer (by weight proportion):
25 parts of calcium zinc metallic soaps
20 parts of epoxy soybean oils
Oxidation inhibitor 2, the mixture of three grades of butyl of 6--4-methylphenol and two (3, three grades of butyl of 5--4-hydroxy phenyl) thioethers.2 parts
Lubricant stearic acid butyl ester and glyceryl monostearate mixture: 2 parts
40 parts of phosphorous acid esters
2 parts of promotor beta-diketone compounds
In the experiment of the enterprising action attitude of two rod mills thermostability, temperature 175-180 ℃, got sample one time every 5 minutes, it is as follows to fill a prescription:
PVC(SG-5) 100
Calcium zinc stabilizer 3
ESO 3
The result shows adding self-control liquid calcium zinc heat stabilizer, and the PVC sheet began variable color after 22 minutes.
Embodiment 2
30 parts of calcium zinc metallic soaps
18 parts in solvent oil, epoxy aliphatic acid methyl ester mixture
4 parts in oxidation inhibitor
1.5 parts in lubricant glyceryl monostearate and ester type waxes mixture
45 parts of the inferior acid esters of co-stabilizer
1.5 parts of promotor beta-diketone compounds
In the experiment of the enterprising action attitude of two rod mills thermostability, temperature 175-180 ℃, got sample one time every 5 minutes, it is as follows to fill a prescription:
PVC(SG-5) 100
Calcium zinc stabilizer 3
ESO 3
The result shows adding self-control liquid calcium zinc heat stabilizer, and the PVC sheet began variable color after 30 minutes.
Embodiment 3
35 parts of calcium zinc metallic soaps
15 parts of solvent mineral oil, epoxy soybean oil mixts
3 parts in oxidation inhibitor
1 part of lubricant stearic acid glyceryl ester
45 parts of co-stabilizer diphenylpropane-1,3-dione(DPPO), bi-ester of phosphite
1 part of promotor beta-diketone compounds
In the experiment of the enterprising action attitude of two rod mills thermostability, temperature 175-180 ℃, got sample one time every 5 minutes, it is as follows to fill a prescription:
100 parts of PVC (SG-5)
40 parts of dioctyl phthalate (DOP)s (DOP)
3 parts of calcium zinc stabilizers
3 parts of ESO
The result shows adding self-control liquid calcium zinc heat stabilizer, and the PVC sheet began variable color after 25 minutes.
According to identical prescription more commercially available liquid calcium zinc heat stabilizer in two rod mills, the PVC sheet just begins variable color after 12 minutes as a result simultaneously, and this shows that homemade liquid calcium zinc heat stabilizer has good stability.
Claims (5)
1, a kind of preparation method of environmental-friendly calcium-zinc composite liquid stabilizing agent is characterized in that comprising the steps:
(1) one or more organic acids in adding identical olefin(e) acid, naphthenic acid or the isocaprylic acid in reaction vessel, add calcium hydroxide or calcium oxide, zinc oxide while stirring, control reaction temperature is at 80-100 ℃, the control reaction pressure is at 0.05-0.1MPa, reacted 2-3 hour, and obtained the fatty acid metal soap;
(2) fatty acid metal soap solution and oxidation inhibitor, lubricant, co-stabilizer, solvent, promotor is composite;
Wherein, oxidation inhibitor is polynary hindered phenol type antioxidant;
Lubricant is one or more the composite mixtures in butyl stearate, glyceryl monostearate, ester type waxes or the saponified wax;
Co-stabilizer is inferior acid esters or diphenylpropane-1,3-dione(DPPO);
Solvent is one or more the mixture in mineral oil, solvent oil, the softening agent;
Promotor is beta-diketone compounds;
The temperature of above-mentioned composite reaction is controlled at 100-150 ℃, evenly stirs cool to room temperature 10-50 minute;
(3) reactant is made with extra care, press filtration obtains finished product.
2, a kind of preparation method according to claim 1 is characterized in that adding in the reaction vessel in the described step (1) solvent benzol or chloroform.
3, a kind of preparation method according to claim 1 is characterized in that organic acid in the described step (1) is one or more in olefin(e) acid, naphthenic acid or the isocaprylic acid of 12-18 carbon.
4, a kind of preparation method according to claim 1 is characterized in that adding in the described step (1) several organic acids in olefin(e) acid, naphthenic acid or the isocaprylic acid of same concentrations.
5, a kind of preparation method according to claim 1 is characterized in that in the described step (2)
Oxidation inhibitor is 2, three grades of butyl of 6--4-methylphenol, two (3, three grades of butyl of 5--4-hydroxy phenyl) thioether, four (β-(3, three grades of butyl of 5--4-hydroxy phenyl) one or more mixtures in pentaerythritol ester, (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, tricresyl phosphite monooctyl ester, tridecyl phosphite propionic acid);
Lubricant is butyl stearate or glyceryl monostearate;
Co-stabilizer is the phosphorous acid alkyl aryl ester, and adds a kind of in epoxy soybean oil, epoxyoleic acid, epoxy ricinolic acid or the epoxy aliphatic acid methyl ester;
Solvent is mineral oil, whiteruss;
Above-mentioned each component is as follows by the proportioning of quality:
Fatty acid metal soap consumption: 20-40%
Solvent load: 10-40%
Oxidation inhibitor: consumption: 1-10%
Lubricant: consumption: 1-10%
Co-stabilizer: consumption: 10-50%
Promotor: consumption: 1-5%
The temperature of above-mentioned composite reaction is controlled at 100-120 ℃, evenly stirred 10-20 minute, and cool to room temperature, stirring at low speed 10-20 minute again, the control mixing speed was at 400-600 commentaries on classics/min.
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| CNA2009100997283A CN101575422A (en) | 2009-06-18 | 2009-06-18 | Method for preparing environmental-friendly calcium-zinc composite liquid stabilizing agent |
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|---|---|---|---|
| CNA2009100997283A CN101575422A (en) | 2009-06-18 | 2009-06-18 | Method for preparing environmental-friendly calcium-zinc composite liquid stabilizing agent |
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Family
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|---|---|---|---|
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Cited By (21)
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|---|---|---|---|---|
| CN101967252A (en) * | 2010-10-25 | 2011-02-09 | 常州嘉仁禾化学有限公司 | Calcium magnesium zinc composite thermal stabilizer, preparation method and application thereof |
| CN101747529B (en) * | 2009-12-16 | 2011-09-21 | 杭州三叶新材料股份有限公司 | Ca-Zn liquid composite stabilizing agent and application thereof |
| CN102516597A (en) * | 2011-12-13 | 2012-06-27 | 江南大学 | Special metal salt monomer for vegetable oil based liquid heat stabilizer and preparation method thereof |
| CN102516684A (en) * | 2011-11-22 | 2012-06-27 | 山东瑞丰高分子材料股份有限公司 | Novel liquid calcium and zinc stabilizing agent and preparation method thereof |
| CN102604271A (en) * | 2012-04-09 | 2012-07-25 | 浙江嘉澳环保科技股份有限公司 | Magnesium-zinc composite thermal stabilizer for polyvinyl chloride products and preparation method thereof |
| CN102838819A (en) * | 2012-09-21 | 2012-12-26 | 中国林业科学研究院林产化学工业研究所 | Preparation method of oil/rosin base liquid calcium-zinc composite stabilizing agent used for PVC (Polyvinyl Chloride) |
| CN102875923A (en) * | 2012-10-12 | 2013-01-16 | 中塑联新材料科技湖北有限公司 | Special stability function regulator for polyvinyl chloride (PVC) injection moulding |
| CN102977407A (en) * | 2012-11-27 | 2013-03-20 | 广州嘉德乐生化科技有限公司 | Composition containing glycerin monostearate and rare earth fatty acid soap and preparation method thereof |
| CN105111620A (en) * | 2015-09-10 | 2015-12-02 | 广州盈塑新材料科技有限公司 | Liquid calcium/zinc heat stabilizer, preparing method thereof and device for implementing method |
| CN105218973A (en) * | 2015-10-13 | 2016-01-06 | 云南锡业股份有限公司 | A kind of high efficiency composition polychloroethylene heat stabilizer and preparation method thereof |
| US20160032078A1 (en) * | 2013-03-15 | 2016-02-04 | Baerlocher Gmbh | Stabilized polymer compositions and methods of making same |
| CN106189282A (en) * | 2016-08-19 | 2016-12-07 | 深圳市志海实业股份有限公司 | A kind of calcium-zinc composite stabilizing agent based on sulfonated polyimide and preparation method thereof |
| CN106280106A (en) * | 2016-08-23 | 2017-01-04 | 深圳市志海实业股份有限公司 | Electric wire high temperature resistant environment-protective nontoxic calcium zinc stabilizer and production method thereof |
| CN106893138A (en) * | 2017-03-07 | 2017-06-27 | 中国林业科学研究院林产化学工业研究所 | PVC laurene source composite thermal stabilizers and its preparation method and application |
| CN107189258A (en) * | 2017-06-15 | 2017-09-22 | 苏州莱特复合材料有限公司 | A kind of preparation method of metal-based compound polychloroethylene heat stabilizer |
| CN107501604A (en) * | 2017-07-31 | 2017-12-22 | 湖州裕宇塑料有限公司 | A kind of Ca-Zn liquid stabilizer and preparation method thereof |
| CN108384052A (en) * | 2018-02-28 | 2018-08-10 | 华南理工大学 | A kind of calcium zinc heat stabilizer of vinyl chloride-vinyl acetate resin and preparation method thereof for pigment carrier |
| CN108774402A (en) * | 2018-06-27 | 2018-11-09 | 杭州三叶新材料股份有限公司 | A kind of PVC calendered sheets special environment protection zinc-base SY-310 stabilizer synthetic methods |
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2009
- 2009-06-18 CN CNA2009100997283A patent/CN101575422A/en active Pending
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| CN101747529B (en) * | 2009-12-16 | 2011-09-21 | 杭州三叶新材料股份有限公司 | Ca-Zn liquid composite stabilizing agent and application thereof |
| CN101967252A (en) * | 2010-10-25 | 2011-02-09 | 常州嘉仁禾化学有限公司 | Calcium magnesium zinc composite thermal stabilizer, preparation method and application thereof |
| CN102516684A (en) * | 2011-11-22 | 2012-06-27 | 山东瑞丰高分子材料股份有限公司 | Novel liquid calcium and zinc stabilizing agent and preparation method thereof |
| CN102516597B (en) * | 2011-12-13 | 2013-04-17 | 江南大学 | Special metal salt monomer for vegetable oil based liquid heat stabilizer and preparation method thereof |
| CN102516597A (en) * | 2011-12-13 | 2012-06-27 | 江南大学 | Special metal salt monomer for vegetable oil based liquid heat stabilizer and preparation method thereof |
| CN102604271A (en) * | 2012-04-09 | 2012-07-25 | 浙江嘉澳环保科技股份有限公司 | Magnesium-zinc composite thermal stabilizer for polyvinyl chloride products and preparation method thereof |
| WO2014044160A1 (en) * | 2012-09-21 | 2014-03-27 | 中国林业科学研究院林产化学工业研究所 | Method for preparing grease/turpentine base liquid calcium-zinc composite thermal stabilizer for pvc use |
| CN102838819B (en) * | 2012-09-21 | 2014-08-20 | 中国林业科学研究院林产化学工业研究所 | Preparation method of oil/rosin base liquid calcium-zinc composite stabilizing agent used for PVC (Polyvinyl Chloride) |
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| CN102875923A (en) * | 2012-10-12 | 2013-01-16 | 中塑联新材料科技湖北有限公司 | Special stability function regulator for polyvinyl chloride (PVC) injection moulding |
| CN102977407A (en) * | 2012-11-27 | 2013-03-20 | 广州嘉德乐生化科技有限公司 | Composition containing glycerin monostearate and rare earth fatty acid soap and preparation method thereof |
| US10119010B2 (en) * | 2013-03-15 | 2018-11-06 | Baerlocher Gmbh | Stabilized polymer compositions and methods of making same |
| US20160032078A1 (en) * | 2013-03-15 | 2016-02-04 | Baerlocher Gmbh | Stabilized polymer compositions and methods of making same |
| CN105111620A (en) * | 2015-09-10 | 2015-12-02 | 广州盈塑新材料科技有限公司 | Liquid calcium/zinc heat stabilizer, preparing method thereof and device for implementing method |
| CN105218973A (en) * | 2015-10-13 | 2016-01-06 | 云南锡业股份有限公司 | A kind of high efficiency composition polychloroethylene heat stabilizer and preparation method thereof |
| CN106189282A (en) * | 2016-08-19 | 2016-12-07 | 深圳市志海实业股份有限公司 | A kind of calcium-zinc composite stabilizing agent based on sulfonated polyimide and preparation method thereof |
| CN106189282B (en) * | 2016-08-19 | 2020-05-26 | 深圳市志海实业股份有限公司 | Calcium-zinc composite stabilizer based on sulfonated polyimide and preparation method thereof |
| CN106280106A (en) * | 2016-08-23 | 2017-01-04 | 深圳市志海实业股份有限公司 | Electric wire high temperature resistant environment-protective nontoxic calcium zinc stabilizer and production method thereof |
| CN106893138A (en) * | 2017-03-07 | 2017-06-27 | 中国林业科学研究院林产化学工业研究所 | PVC laurene source composite thermal stabilizers and its preparation method and application |
| CN106893138B (en) * | 2017-03-07 | 2019-03-29 | 中国林业科学研究院林产化学工业研究所 | PVC laurene source composite thermal stabilizer and its preparation method and application |
| CN107189258A (en) * | 2017-06-15 | 2017-09-22 | 苏州莱特复合材料有限公司 | A kind of preparation method of metal-based compound polychloroethylene heat stabilizer |
| CN107501604A (en) * | 2017-07-31 | 2017-12-22 | 湖州裕宇塑料有限公司 | A kind of Ca-Zn liquid stabilizer and preparation method thereof |
| CN108384052A (en) * | 2018-02-28 | 2018-08-10 | 华南理工大学 | A kind of calcium zinc heat stabilizer of vinyl chloride-vinyl acetate resin and preparation method thereof for pigment carrier |
| CN108774402A (en) * | 2018-06-27 | 2018-11-09 | 杭州三叶新材料股份有限公司 | A kind of PVC calendered sheets special environment protection zinc-base SY-310 stabilizer synthetic methods |
| CN109233984A (en) * | 2018-10-30 | 2019-01-18 | 长沙博大机械零部件有限公司 | A kind of environment-friendly and energy-efficient phosphatization saponification formula and preparation method thereof and saponification process |
| CN110692632A (en) * | 2019-09-04 | 2020-01-17 | 深圳诺普信农化股份有限公司 | Stabilizing agent for sulfonylurea herbicide and preparation method and application thereof |
| CN110698867A (en) * | 2019-09-28 | 2020-01-17 | 浙江杰上杰新材料有限公司 | Preparation method of calcium-zinc stabilizer for shoe material |
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