CN102585394A - Calcium-zinc molecular sieve composite stabilizer for chloroethylene and preparation method thereof - Google Patents
Calcium-zinc molecular sieve composite stabilizer for chloroethylene and preparation method thereof Download PDFInfo
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- CN102585394A CN102585394A CN2011103990847A CN201110399084A CN102585394A CN 102585394 A CN102585394 A CN 102585394A CN 2011103990847 A CN2011103990847 A CN 2011103990847A CN 201110399084 A CN201110399084 A CN 201110399084A CN 102585394 A CN102585394 A CN 102585394A
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Abstract
The invention relates to a calcium-zinc molecular sieve composite stabilizer for chloroethylene and a preparation method of the calcium-zinc molecular sieve composite stabilizer for chloroethylene, belonging to the field of chemical engineering. The calcium-zinc molecular sieve composite stabilizer for chloroethylene is characterized by comprising the following raw materials in parts by weight: 30-35 parts of zinc stearate, 12-12.5 parts of calcium stearate, 4-4.5 parts of beta-diketone, 13-15 parts of Sencor, 1.5-2 parts of bisphenol-a, 10-12 parts of stearic acid and 20-25 parts of ester modified molecular sieve. According to the calcium-zinc molecular sieve composite stabilizer for chloroethylene, the calcium stearate and the zinc stearate are taken as main stabilizers, and auxiliary stabilizers and the modified molecular sieve are added for the rest, so that a good synergistic stabilizing effect and a certain lubricating property are gained; other stabilizers or lubricants do not need to be added when the composite stabilizer is used, so that the composite stabilizer can be conveniently used; and the preparation steps can be reduced to save labor and reduce preparation error, so that the aim of high-efficiency operation is fulfilled.
Description
Technical field
The present invention relates to a kind of vinylchlorid with calcium Zn molecular sieve one package stabilizer and preparation method thereof, belong to chemical field.
Background technology
SE (PVC) is one of the most frequently used plastics, and its advantage is that intensity is high, insulativity and the transparency are good etc.Its disadvantage is to be heated for a long time down at the processing temperature conditioned disjunction, and easy the decomposition, terms of settlement is in the PVC course of processing, to add thermo-stabilizer, stops or delays this process.In addition, SE is heated or when receiving ultraviolet radiation, also can causes the degraded of polymkeric substance and take off HCl.Stablizer is a kind of chemical assistant, and it can suppress degraded and the variable color that PVC causes owing to heat, light action in machine-shaping and use.Stablizer can be divided into base lead salt stablizer, metallic soap class, organo-tin compound, organic stabilizer and one package stabilizer five big classes by its chemical structure.
As everyone knows, calcium zinc meets in the stablizer, and zinc soap has the effect that improves the goods initial coloration, and calcium soap has the effect that improves permanent stability.The shortcoming of zinc soap is to make goods in the course of processing, occur zinc prematurely to burn, and the adding of calcium soap can delay zinc and burn, but the initial stage form and aspect of warrier between making it worsen.Balance this contradiction between the two becomes the research emphasis of category.
In recent years, short perfect along with the enhancing of environmental consciousness and various laws, the application that lead salts meets stablizer is restricted, and enterprise has expressed intensive interest to the exploitation that calcium zinc class meets stablizer.Our company at home in the same industry a unique family have the composite assistant production company of academician's workstation, have advanced technological production strength, this project is also had profound research.
The calcium-zinc composite stabilizing agent great advantage is nontoxic, and its main deficiency is that later stage stability is undesirable, needs composite with various auxiliary stabilizers.Auxiliary agents such as the main here oxidation inhibitor that adds, sequestrant.
Summary of the invention
Deficiency according to prior art; The technical problem that the present invention will solve is: provide a kind of vinylchlorid with calcium Zn molecular sieve one package stabilizer and preparation method thereof; Add ester modified molecular sieve, reduce the consumption of calcium zinc stabilizer, improve the stability in calcium-zinc composite stabilizing agent later stage.
The technical solution adopted for the present invention to solve the technical problems is: a kind of polyvinyl-chloride use calcium Zn molecular sieve one package stabilizer is provided, it is characterized in that being made up of the raw material of following weight part:
Zinic stearas 30-35 part;
Calcium stearate 12-12.5 part;
Beta-diketon 4-4.5 part;
Match gram 13-15 part;
Bis-phenol-a 1.5-2 part;
Triple Pressed Stearic Acid 10-12 part;
Ester modified molecular sieve 20-25 part.
Said ester modified molecular sieve prepares according to following method:
Place retort furnace to dry in 4A type molecular sieve except that water treatment; Temperature is provided with 250～260 ℃, keeps 2h, places high-speed mixer to mix with phosphorous acid ester with the mixture of pentaerythritol resin it after the taking-up; Mixing time 10min; Be cooled to room temperature, fully grind, obtain ester modified molecular sieve.
The mass ratio of said phosphorous acid ester and pentaerythritol resin is 1: 1.
The mass ratio of 4A type molecular sieve after the said oven dry and phosphorous acid ester and tetramethylolmethane lipoprotein mixture is 10: 3.
The preparation method of described polyvinyl-chloride use calcium Zn molecular sieve one package stabilizer is following:
In high-speed mixer, add Triple Pressed Stearic Acid, be warmed up to 60～65 ℃; Add Zinic stearas and calcium stearate, the back that stirs adds beta-diketon, bis-phenol-a and Sai Ke, continues to add 110 ℃ of insulations down of ester modified molecular sieve after fully stirring again; After material stirs, emit material, get product.
The invention has the beneficial effects as follows: stablizer is to be main stabilizer with calcium stearate and Zinic stearas; All the other add auxiliary stabilizer and modified molecular screen, and it has good synergisticing stable effect and has certain oilness, needn't add other stablizer or lubricant in use; Easy to use; Can reduce the batching program, save the labor force and reduce the batching error, reach efficient operation.
Calcium Zn molecular sieve stablizer of the present invention is by calcium zinc stabilizer and ester modified molecular sieve is composite forms; Both solved the unfavorable drawback of calcium-zinc composite stabilizing agent later stage stabilising effect; Reduced the content of various auxiliary agents again, and reduced cost and environment is not had harm.
By GB GB2113-82 " plastics whiteness experimental technique ", the calcium Zn molecular sieve stablizer of the present invention's preparation is compared with traditional calcium zinc stabilizer, has outstanding thermostability.Can find also that by the dynamic thermal stability simultaneous test use the calcium Zn molecular sieve stablizer of the present invention's preparation that the plasticizing capacity of PVC plastics is strengthened, the dynamic thermal stability time obviously prolongs.
Embodiment
Below in conjunction with embodiment the present invention is done and to further describe.
Embodiment 1～3
The preparation of ester modified molecular sieve
Phosphorous acid ester and pentaerythritol resin are carried out 1: 1 combination treatment, and it is for use to take by weighing 30g.Take by weighing 120g4A type molecular sieve; Place retort furnace to carry out high temperature dehydration and handle, keep after two hours, take out the molecular sieve of handling well; Taking by weighing 100g mixes in impeller with ester mixture 30g; Kept 5 minutes, and fully ground after the taking-up, sieving obtains the ester modified molecular sieve of white powder.
The preparation of calcium Zn molecular sieve stablizer
In high-speed mixer, add Triple Pressed Stearic Acid, be warmed up to 60～65 ℃; Add Zinic stearas and calcium stearate; The back that stirs adds beta-diketon, bis-phenol-a and Sai Ke, continues to add 110 ℃ of insulations down of ester modified molecular sieve after fully stirring again, treat that material stirs after; Emit material, get product.
The prescription of embodiment 1～3 is seen table 1.
Table 1
Table 2 by practical present embodiment 1～3 the employed prescription contrast of concrete production section bar of being produced of the polyvinyl-chloride use calcium Zn molecular sieve one package stabilizer that produces of one-tenth.
Table 2
Carry out heat-resisting whiteness experiment to three kinds of PVC plastics by table 2 preparation, table 2 is test piece to be placed on to use whiteness be the relative whiteness value of testing in the whiteness appearance checked of 85% standard white body.Can find that from table 2 prepared polyvinyl-chloride use calcium Zn molecular sieve one package stabilizer is compared with Comparative Examples tradition calcium zinc stabilizer, has outstanding thermostability.
Also can find by the dynamic thermal stability simultaneous test, use polyvinyl-chloride use calcium Zn molecular sieve one package stabilizer can make the dynamic thermal stability time of PVC plastics obviously prolong (seeing table 3).
Table 3
The plasticizing process in each stage in the flow curve analysis prescription is arranged, see table 4 for details.
Table 4
Claims (5)
1. polyvinyl-chloride use calcium Zn molecular sieve one package stabilizer is characterized in that being made up of the raw material of following weight part:
Zinic stearas 30-35 part;
Calcium stearate 12-12.5 part;
Beta-diketon 4-4.5 part;
Match gram 13-15 part;
Bis-phenol-a 1.5-2 part;
Triple Pressed Stearic Acid 10-12 part;
Ester modified molecular sieve 20-25 part.
2. vinylchlorid according to claim 1 is characterized in that with calcium Zn molecular sieve one package stabilizer said ester modified molecular sieve prepares according to following method:
Place retort furnace to dry in 4A type molecular sieve except that water treatment; Temperature is provided with 250～260 ℃, keeps 2h, places high-speed mixer to mix with phosphorous acid ester with the mixture of pentaerythritol resin it after the taking-up; Mixing time 10min; Be cooled to room temperature, fully grind, obtain ester modified molecular sieve.
3. vinylchlorid according to claim 2 is with calcium Zn molecular sieve one package stabilizer, and the mass ratio that it is characterized in that said phosphorous acid ester and pentaerythritol resin is 1: 1.
4. vinylchlorid according to claim 2 is with calcium Zn molecular sieve one package stabilizer, it is characterized in that 4A type molecular sieve and the mass ratio of phosphorous acid ester and tetramethylolmethane lipoprotein mixture after the said oven dry is 10: 3.
5. polyvinyl-chloride use calcium Zn molecular sieve one package stabilizer according to claim 1 is characterized in that the preparation method of described polyvinyl-chloride use calcium Zn molecular sieve one package stabilizer is following:
In high-speed mixer, add Triple Pressed Stearic Acid, be warmed up to 60～65 ℃; Add Zinic stearas and calcium stearate, the back that stirs adds beta-diketon, bis-phenol-a and Sai Ke, continues to add 110 ℃ of insulations down of ester modified molecular sieve after fully stirring again; After material stirs, emit material, get product.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110399084.7A CN102585394B (en) | 2011-12-05 | 2011-12-05 | Calcium-zinc molecular sieve composite stabilizer for chloroethylene and preparation method thereof |
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| CN201110399084.7A CN102585394B (en) | 2011-12-05 | 2011-12-05 | Calcium-zinc molecular sieve composite stabilizer for chloroethylene and preparation method thereof |
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| CN102585394B CN102585394B (en) | 2014-02-26 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419130A (en) * | 2015-12-31 | 2016-03-23 | 山东慧科助剂股份有限公司 | Molecular sieve impact modification flexibilizer for polyvinyl chloride and preparing method thereof |
| CN105482166A (en) * | 2015-12-31 | 2016-04-13 | 山东慧科助剂股份有限公司 | Non-toxic environment-friendly stabilizer auxiliary agent and preparation method thereof |
| CN105713316A (en) * | 2016-02-23 | 2016-06-29 | 东莞市尚诺新材料有限公司 | Transparent phenol-free pasty heat stabilizer and preparing method thereof |
| CN106519304A (en) * | 2016-10-14 | 2017-03-22 | 九江天盛塑料助剂有限公司 | Molecular sieve supported polyvinyl chloride thermal stabilizer and preparation method thereof |
| CN107936300A (en) * | 2017-12-20 | 2018-04-20 | 山东慧科助剂股份有限公司 | Perchlorate modified molecular screen stabilizer and preparation method thereof |
| CN110483579A (en) * | 2019-07-24 | 2019-11-22 | 胡宝建 | A kind of match gram phosphorous acid alcohol ester and preparation method thereof and application |
| CN111171584A (en) * | 2019-12-30 | 2020-05-19 | 安徽华文塑胶科技有限公司 | Stabilizer for PCB and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1098115A (en) * | 1992-09-25 | 1995-02-01 | 希巴-盖吉股份公司 | The stabilising method and the stabilizer blend thereof of the plastic hybrid that reclaims |
| CN1154381A (en) * | 1995-10-13 | 1997-07-16 | 希巴特殊化学控股公司 | Stabiliser combinations for chlorine-containing polymers |
| CN1232836A (en) * | 1998-04-20 | 1999-10-27 | 邵万春 | Modified hard polyvinyl chloride film |
| CN1296033A (en) * | 1999-11-12 | 2001-05-23 | 中国石油化工集团公司北京化工研究院 | Process for preparation of polyvinyl-chloride foaming material |
| CN1341681A (en) * | 2000-09-07 | 2002-03-27 | 苏州德威实业有限公司 | Flexible polyvinyl chloride plastics for making wire and cable |
-
2011
- 2011-12-05 CN CN201110399084.7A patent/CN102585394B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1098115A (en) * | 1992-09-25 | 1995-02-01 | 希巴-盖吉股份公司 | The stabilising method and the stabilizer blend thereof of the plastic hybrid that reclaims |
| CN1154381A (en) * | 1995-10-13 | 1997-07-16 | 希巴特殊化学控股公司 | Stabiliser combinations for chlorine-containing polymers |
| CN1232836A (en) * | 1998-04-20 | 1999-10-27 | 邵万春 | Modified hard polyvinyl chloride film |
| CN1296033A (en) * | 1999-11-12 | 2001-05-23 | 中国石油化工集团公司北京化工研究院 | Process for preparation of polyvinyl-chloride foaming material |
| CN1341681A (en) * | 2000-09-07 | 2002-03-27 | 苏州德威实业有限公司 | Flexible polyvinyl chloride plastics for making wire and cable |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419130A (en) * | 2015-12-31 | 2016-03-23 | 山东慧科助剂股份有限公司 | Molecular sieve impact modification flexibilizer for polyvinyl chloride and preparing method thereof |
| CN105482166A (en) * | 2015-12-31 | 2016-04-13 | 山东慧科助剂股份有限公司 | Non-toxic environment-friendly stabilizer auxiliary agent and preparation method thereof |
| CN105482166B (en) * | 2015-12-31 | 2018-05-25 | 山东慧科助剂股份有限公司 | Asepsis environment-protecting stablizes agent aid and preparation method thereof |
| CN105713316A (en) * | 2016-02-23 | 2016-06-29 | 东莞市尚诺新材料有限公司 | Transparent phenol-free pasty heat stabilizer and preparing method thereof |
| CN105713316B (en) * | 2016-02-23 | 2017-11-10 | 东莞市尚诺新材料有限公司 | A kind of transparent no phenol paste shape heat stabilizer and preparation method thereof |
| CN106519304A (en) * | 2016-10-14 | 2017-03-22 | 九江天盛塑料助剂有限公司 | Molecular sieve supported polyvinyl chloride thermal stabilizer and preparation method thereof |
| CN106519304B (en) * | 2016-10-14 | 2018-11-09 | 九江天盛塑料助剂有限公司 | A kind of molecular sieve carried type polychloroethylene heat stabilizer and preparation method thereof |
| CN107936300A (en) * | 2017-12-20 | 2018-04-20 | 山东慧科助剂股份有限公司 | Perchlorate modified molecular screen stabilizer and preparation method thereof |
| CN110483579A (en) * | 2019-07-24 | 2019-11-22 | 胡宝建 | A kind of match gram phosphorous acid alcohol ester and preparation method thereof and application |
| CN111171584A (en) * | 2019-12-30 | 2020-05-19 | 安徽华文塑胶科技有限公司 | Stabilizer for PCB and preparation method thereof |
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| CN102585394B (en) | 2014-02-26 |
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Denomination of invention: Calcium-zinc molecular sieve composite stabilizer for chloroethylene and preparation method thereof Effective date of registration: 20200519 Granted publication date: 20140226 Pledgee: China postal savings bank, Yiyuan County branch, Limited by Share Ltd Pledgor: SHANDONG HUIKE ADDITIVES Co.,Ltd. Registration number: Y2020980002322 |
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Date of cancellation: 20220211 Granted publication date: 20140226 Pledgee: China postal savings bank, Yiyuan County branch, Limited by Share Ltd. Pledgor: SHANDONG HUIKE ADDITIVES Co.,Ltd. Registration number: Y2020980002322 |
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Address after: 256100 Yiyuan Economic Development Zone, Zibo City, Shandong Province Patentee after: Huike High Tech Co.,Ltd. Address before: 256100 Yiyuan Economic Development Zone, Zibo City, Shandong Province Patentee before: SHANDONG HUIKE ADDITIVES Co.,Ltd. |
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