CN102585394B - 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 PDF

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CN102585394B
CN102585394B CN201110399084.7A CN201110399084A CN102585394B CN 102585394 B CN102585394 B CN 102585394B CN 201110399084 A CN201110399084 A CN 201110399084A CN 102585394 B CN102585394 B CN 102585394B
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molecular sieve
calcium
zinc
composite stabilizer
chloroethylene
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CN102585394A (en
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李德刚
唐守余
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Huike High Tech Co.,Ltd.
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SHANDONG HUIKE ADDITIVES CO Ltd
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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

Calcium-zinc molecular sieve composite stabilizer for chloroethylene and preparation method thereof
Technical field
The present invention relates to a kind of calcium-zinc molecular sieve composite stabilizer for chloroethylene and preparation method thereof, belong to chemical field.
Background technology
Polyvinyl chloride (PVC) is one of the most frequently used plastics, its advantage is that intensity is high, insulativity and the transparency good etc.Its disadvantage is under processing temperature conditioned disjunction is heated for a long time, easily decomposes, and terms of settlement is to add thermo-stabilizer in the PVC course of processing, stops or delays this process.In addition, when polyvinyl chloride is heated or is subject to ultraviolet radiation, also can cause degraded and the de-HCl of polymkeric substance.Stablizer is a kind of chemical assistant, and it can suppress degraded and the variable color that PVC causes due to heat, light action in machine-shaping and use procedure.Stablizer can be divided into base lead salt stablizer, metal soap, organo-tin compound, organic stabilizer and the large class of one package stabilizer five by its chemical structure.
As everyone knows, calcium zinc meets in stablizer, and zinc soap has the effect that improves 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 prematurely that zinc burns, and the adding of calcium soap can delay zinc and burn, but the initial stage form and aspect of warrier between making it worsens.Balance this contradiction between the two, becomes the research emphasis of category.
In recent years, not short perfect along with the enhancing of environmental consciousness and various laws, the application that lead salts meets stablizer is restricted, and strong interest has been expressed in the exploitation that enterprise meets stablizer to calcium zinc class.Our company is an interior unique composite assistant production company with academician's workstation of the same trade at home, has advanced technology production strength, and this project is also had to profound research.
Calcium-zinc composite stabilizing agent great advantage is nontoxic, and its main deficiency is that stability at later stage is undesirable, need be composite with various auxiliary stabilizers.The auxiliary agents such as the oxidation inhibitor here mainly adding, sequestrant.
Summary of the invention
According to the deficiencies in the prior art, the technical problem to be solved in the present invention is: a kind of calcium-zinc molecular sieve composite stabilizer for chloroethylene and preparation method thereof is provided, 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 comprised 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;
Stearic acid 10-12 part;
Ester modified molecular sieve 20-25 part.
Described ester modified molecular sieve is prepared in accordance with the following methods:
4A type molecular sieve is placed in to retort furnace dries except water treatment, temperature arranges 250~260 ℃, keep 2h, after taking-up, it being placed in to high-speed mixer with phosphorous acid ester with the mixture of pentaerythritol resin mixes, mixing time 10min, be cooled to room temperature, fully grind, obtain ester modified molecular sieve.
The mass ratio of described phosphorous acid ester and pentaerythritol resin is 1: 1.
The mass ratio of the 4A type molecular sieve after described 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 as follows:
In high-speed mixer, add stearic acid, be warmed up to 60~65 ℃, add Zinic stearas and calcium stearate, after stirring, add beta-diketon, bis-phenol-a and Sai Ke, after fully stirring, continue again to add insulation at 110 ℃, ester modified molecular sieve, after material stirring is even, material is emitted, obtain product.
The invention has the beneficial effects as follows: stablizer is that to take calcium stearate and Zinic stearas be main stabilizer, all the other add auxiliary stabilizer and modified molecular screen, it has good synergisticing stable effect and has certain oilness, needn't add other stablizer or lubricant in use, easy to use, can reduce batching program, save labor force and reduce Aggregate Feeding 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 undesirable drawback of calcium-zinc composite stabilizing agent later stage stabilising effect, reduced again the content of various auxiliary agents, and reduced cost and to environment without harm.
By GB GB2113-82 " plastics whiteness experimental technique ", calcium Zn molecular sieve stablizer prepared by the present invention is compared with traditional calcium zinc stabilizer, has outstanding thermostability.By dynamic thermal stability simultaneous test, also can be found, the calcium Zn molecular sieve stablizer that uses the present invention to prepare can make the plasticizing capacity of PVC plastics strengthen, and the dynamic thermal stability time obviously extends.
Embodiment
Below in conjunction with embodiment, the present invention is described further.
Embodiment 1~3
The preparation of ester modified molecular sieve
Phosphorous acid ester and pentaerythritol resin are carried out to 1: 1 combination treatment, take 30g stand-by.Take 120g4A type molecular sieve, be placed in retort furnace and carry out high temperature dehydration processing, keep after two hours, the molecular sieve that taking-up is handled well, taking 100g mixes in homogenizer with ester mixture 30g, keep 5 minutes, after taking-up, fully grind, sieve and obtain the ester modified molecular sieve of white powder.
The preparation of calcium Zn molecular sieve stablizer
In high-speed mixer, add stearic acid, be warmed up to 60~65 ℃, add Zinic stearas and calcium stearate, after stirring, add beta-diketon, bis-phenol-a and Sai Ke, after fully stirring, continue again to add insulation at 110 ℃, ester modified molecular sieve, until material stirring evenly after, material is emitted, obtain product.
The formula of embodiment 1~3 is in Table 1.
Table 1
Figure BDA0000116140040000031
Formula contrast that concrete production section bar that polyvinyl-chloride use calcium Zn molecular sieve one package stabilizer that one-tenth produces produces uses that table 2 is practical the present embodiment 1~3.
Table 2
Figure BDA0000116140040000032
Carrying out heat-resisting whiteness experiment by three kinds of PVC plastics of table 2 preparation, table 2 is that test piece is placed on to the relative whiteness value of testing in the whiteness instrument of checking with the standard white body that whiteness is 85%.From table 2, can find, prepared polyvinyl-chloride use calcium Zn molecular sieve one package stabilizer is compared with comparative example tradition calcium zinc stabilizer, has outstanding thermostability.
By dynamic thermal stability simultaneous test, also can be found, use polyvinyl-chloride use calcium Zn molecular sieve one package stabilizer can make the dynamic thermal stability time of PVC plastics obviously extend (in Table 3).
Table 3
Figure BDA0000116140040000041
The plasticizing process that has each stage in flow curve analysis formula, refers to table 4.
Table 4
Figure BDA0000116140040000042

Claims (5)

1. a polyvinyl-chloride use calcium Zn molecular sieve one package stabilizer, is characterized in that being comprised 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;
Stearic acid 10-12 part;
Ester modified molecular sieve 20-25 part.
2. calcium-zinc molecular sieve composite stabilizer for chloroethylene according to claim 1, is characterized in that described ester modified molecular sieve prepared in accordance with the following methods:
4A type molecular sieve is placed in to retort furnace dries except water treatment, temperature arranges 250~260 ℃, keep 2h, after taking-up, it being placed in to high-speed mixer with phosphorous acid ester with the mixture of pentaerythritol resin mixes, mixing time 10min, be cooled to room temperature, fully grind, obtain ester modified molecular sieve.
3. calcium-zinc molecular sieve composite stabilizer for chloroethylene according to claim 2, the mass ratio that it is characterized in that described phosphorous acid ester and pentaerythritol resin is 1: 1.
4. calcium-zinc molecular sieve composite stabilizer for chloroethylene according to claim 2, is characterized in that 4A type molecular sieve after described oven dry and the mass ratio of phosphorous acid ester and tetramethylolmethane lipoprotein mixture are 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 as follows:
In high-speed mixer, add stearic acid, be warmed up to 60~65 ℃, add Zinic stearas and calcium stearate, after stirring, add beta-diketon, bis-phenol-a and Sai Ke, after fully stirring, continue again to add insulation at 110 ℃, ester modified molecular sieve, after material stirring is even, material is emitted, obtain product.
CN201110399084.7A 2011-12-05 2011-12-05 Calcium-zinc molecular sieve composite stabilizer for chloroethylene and preparation method thereof Active CN102585394B (en)

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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
CN105419130B (en) * 2015-12-31 2017-10-24 山东慧科助剂股份有限公司 Impact-resistant modified toughener of polyvinyl-chloride use molecular sieve and preparation 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
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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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

Patent Citations (5)

* Cited by examiner, † Cited by third party
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

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