CN109810290A - A kind of composite thermal stabilizer and its application containing organotin, cerium and titanium - Google Patents
A kind of composite thermal stabilizer and its application containing organotin, cerium and titanium Download PDFInfo
- Publication number
- CN109810290A CN109810290A CN201811530345.2A CN201811530345A CN109810290A CN 109810290 A CN109810290 A CN 109810290A CN 201811530345 A CN201811530345 A CN 201811530345A CN 109810290 A CN109810290 A CN 109810290A
- Authority
- CN
- China
- Prior art keywords
- stabilizer
- composite thermal
- cerium
- thermal stabilizer
- tin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of composite thermal stabilizer containing organotin, cerium and titanium and its applications, and wherein composite thermal stabilizer is compounded by main stabilizer and auxiliary stabilizer；Wherein main stabilizer is thiol methyl tin, mercaptan tin octylate, thiol-butyl tin or dioctyltin laurate；Auxiliary stabilizer is cerium stearate, dipentaerythritol, butyl titanate and nano-titanium dioxide.The present invention obtains the composite thermal stabilizer with synergy, is applied in PVC, can be obviously improved the thermal stability of material, and have the degradable property of potential environment by optimal screening.
Description
Technical field
It is specifically a kind of containing the compound of organotin, cerium and titanium the present invention relates to a kind of processing of high molecular material auxiliary agent
Heat stabilizer and its application.
Background technique
Polyvinyl chloride and its product are the important high molecular materials that China's annual output is more than 18,000,000 tons, due to carbon chlorine key key
It can be that 243kJ/mol is smaller, it usually needs heat stabilizer such as lead salt, composite metal salt, organotin, rare earth and organic is added
Deng.Lead salts has been eliminated due to being more toxic, and stabilizer is mainly towards nontoxic, efficient, multi-functional, cost performance is excellent at present
Good, degradable direction is developed.Organic tin stabilizer polrvinyl chloride product processing in account for about the 1/4 of total amount, have efficiently,
Excellent heat resistance, the transparency and the shallow advantage of coloring, are better than other PVC heat stabilizers.Thiol methyl tin and its product by
Bundesgesundheitsamt (BGA), food and drug administration (FDA) and other world health supervisory organs regard as nothing
Poison, security article.But thiol methyl tin price, there is a peculiar smell, therefore reduce usage amount and use cost, find synergistic effect
The auxiliary agent for having both environmentally degradable becomes the task of top priority of auxiliary agent enterprise, therefore studies auxiliary stabilizer terres rares cerium stearate, idol
Join agent butyl titanate and nano-titanium dioxide auxiliary agent, explores possible synergistic effect and environmental-friendly, be of great significance.
Summary of the invention
The present invention is directed to the shortcoming in the presence of the prior art, it is desirable to provide a kind of answering containing organotin, cerium and titanium
Close heat stabilizer and its application.
Composite thermal stabilizer of the present invention containing organotin, cerium and titanium, is compounded by main stabilizer and auxiliary stabilizer；
Wherein main stabilizer (A) is thiol methyl tin, mercaptan tin octylate, thiol-butyl tin or dioctyltin laurate, preferably mercaptan
Methyl tin；Auxiliary stabilizer is cerium stearate (B), dipentaerythritol (C), butyl titanate (D) and nano-titanium dioxide (E).
Composite thermal stabilizer of the present invention containing organotin, cerium and titanium, each component are constituted as follows by mass fraction:
Each component is constituted preferably as follows by mass fraction:
Wherein dipentaerythritol can be substituted with the pentaerythrite of equivalent.
The application of composite thermal stabilizer of the present invention containing organotin, cerium and titanium is added to as thermostabilization auxiliary agent
In polyvinyl chloride, to improve its thermal stability.
Proportion is constituted as follows when composite thermal stabilizer of the present invention is added to PVC:
Evaluating composite thermal stabilizer of the present invention is using Congo Red test, i.e., at PVC to the effect of PVC thermal stability
Grain overhung Congored test paper, is heated to 195 DEG C of constant temperature, observes and records Congored test paper and initially becomes the blue time and become blue completely
Time.PVC can sharply decompose release hydrogen chloride gas at about 170~180 DEG C, and Congored test paper and hcl reaction become blue.
Heat stabilizer is added, it is suppressed that it is decomposed, and can determine whether composite thermal stabilizer effect by the initial and complete length for becoming the blue time
Superiority and inferiority.
The present invention is obtained the composite thermal stabilizer with synergy, is applied in PVC by optimal screening,
It can be obviously improved the thermal stability of material, and have the degradable property of potential environment.
Compared with prior art, the beneficial effects of the present invention are embodied in:
1, the present invention utilizes thiol methyl tin, cerium stearate, dipentaerythritol, butyl titanate and nano-titanium dioxide
Synergistic stability effect can reduce the usage amount of thiol methyl tin, and effect is better than thiol methyl tin stabilizer is used alone, effectively
The thermal stability of ground raising PVC；
2, cerium stearate (B) is used as potential photodegradation promotor, in environment when can promote polyvinyl chloride end-of-life
In light degradation；
3, butyl titanate (D) can promote the electrostatic attraction between tin, cerium and titanium oxide and polyvinyl chloride molecule
With the generation of chemical bond force, furthermore nano-titanium dioxide (E) can also be used as potential photodegradation rush when polyvinyl chloride end-of-life
Into agent, it is made to accelerate light degradation in the environment.
4, above-mentioned thiol methyl tin, cerium stearate, dipentaerythritol, butyl titanate and nano-titanium dioxide belong to nontoxic
Environmentally friendly substance complies fully with the demand for development both at home and abroad for environmental protection, has broad application prospects.
Specific embodiment
Polyvinyl chloride resin model S-65 used in the embodiment of the present invention.
Embodiment 1:
Weigh 100 parts of polyvinyl chloride resin, DOTP50 parts, 0.5 part of thiol methyl tin, 0.5 part of cerium stearate, dipentaerythritol 1.0
Part, 0.5 part of butyl titanate, thiol methyl tin liquid are uniformly mixed with DOTP liquid, then by cerium stearate, dipentaerythritol
And the solution mixed is added in butyl titanate, is stirred well to uniformly mixed.The stabiliser solution being completely dissolved is slowly added to
In polyvinyl chloride resin, high-speed stirred mixes it uniformly, and high speed mixer hopper is added in the feed powder mixed, and control smelting temperature is
It 170-180 DEG C, discharges after 2~3min of mixing, then uses vulcanizing press tabletting, that is, sample thin slice is made.
Embodiment 2:
Weigh 100 parts of polyvinyl chloride resin, DOTP50 parts, 0.5 part of thiol methyl tin, 0.5 part of cerium stearate, dipentaerythritol 1.0
Part, 1.0 parts of butyl titanate, thiol methyl tin liquid are uniformly mixed with DOTP liquid, then by cerium stearate, dipentaerythritol
And the solution mixed is added in butyl titanate, is stirred well to uniformly mixed.The stabiliser solution being completely dissolved is slowly added to
In polyvinyl chloride resin, stirring mixes it uniformly, and high speed mixer hopper is added in the feed powder mixed, and control smelting temperature is 170-
It 180 DEG C, discharges after 2~3min of mixing, then uses vulcanizing press tabletting, that is, sample thin slice is made.
Embodiment 3:
Weigh 100 parts of polyvinyl chloride resin, DOTP50 parts, 0.5 part of thiol methyl tin, 0.5 part of cerium stearate, dipentaerythritol 1.0
Part, thiol methyl tin liquid is uniformly mixed with DOTP liquid, is then mixed cerium stearate, dipentaerythritol addition molten
Liquid is stirred well to uniformly mixed.The stabiliser solution being completely dissolved is slowly added in polyvinyl chloride resin, stirring mixes it uniformly
It closing, high speed mixer hopper is added in the feed powder mixed, and control smelting temperature is 170~180 DEG C, it discharges after 2~3min of mixing,
Then vulcanizing press tabletting is used, that is, sample thin slice is made.
Embodiment 4:
100 parts of polyvinyl chloride resin, DOTP50 parts, 0.5 part of thiol methyl tin, 0.5 part of cerium stearate are weighed, by thiol methyl tin
Liquid is uniformly mixed with DOTP liquid, and then cerium stearate is added to the solution mixed, be stirred well to uniformly mixed.It will be complete
The stabiliser solution of fully dissolved is slowly added in polyvinyl chloride resin, and stirring mixes it uniformly, and high speed mixing is added in the feed powder mixed
Machine hopper, control smelting temperature are 170~180 DEG C, discharge after 2~3min of mixing, then use vulcanizing press tabletting, that is, be made
Sample thin slice.
Embodiment 5:
100 parts of polyvinyl chloride resin, DOTP50 parts, 1.0 parts of thiol methyl tin are weighed, by thiol methyl tin liquid and DOTP liquid
It is uniformly mixed, the stabiliser solution being completely dissolved is slowly added in polyvinyl chloride resin, stir, mix it uniformly, the material mixed
High speed mixer hopper is added in powder, and control smelting temperature is 170~180 DEG C, discharges after 2~3min of mixing, then uses plate sulphur
Change machine tabletting, that is, be made sample thin slice.
Embodiment 6:
100 parts of polyvinyl chloride resin, DOTP50 parts, 0.5 part of thiol methyl tin, 0.5 part of dipentaerythritol are weighed, by thiol methyl
Tin liquor body is uniformly mixed with DOTP liquid, and the solution that mixes then is added in dipentaerythritol, be stirred well to it is uniformly mixed,
The stabiliser solution being completely dissolved is slowly added in polyvinyl chloride resin, stirs, mixes it uniformly, the feed powder mixed is added high
Fast mixer hopper, control smelting temperature are 170~180 DEG C, discharge after 2~3min of mixing, then use vulcanizing press tabletting,
Sample thin slice is made.
Embodiment 7:
Weigh 100 parts of polyvinyl chloride resin, DOTP50 parts, 0.5 part of thiol methyl tin, 0.5 part of cerium stearate, dipentaerythritol 1.0
Part, 5.0 parts of nano-titanium dioxide, 1.0 parts of butyl titanate using nano-titanium dioxide and butyl titanate and are used as auxiliary stabilization
Agent and photocatalytic degradation agent；
(1) thiol methyl tin liquid is uniformly mixed with DOTP liquid, then cerium stearate, dipentaerythritol is added mixed
The solution got togather is thoroughly mixed uniformly to being completely dissolved, and (2) are by 1.0 parts of butyl titanate and nano-TiO25.0 parts of powder,
Butyl titanate coats nano-TiO2And heat mixing effect 30min.
Uniformly mixed stabilizer (1) and (2) are slowly added into polyvinyl chloride resin, stirring mixes them thoroughly, and then will
Compound powder is added in high speed mixer hopper, and control smelting temperature is 170~180 DEG C, is discharged after 2~3min of mixing, so
Vulcanizing press tabletting is used afterwards, that is, sample thin slice is made.
Embodiment 8:
100 parts of polyvinyl chloride resin, DOTP50 parts, 0.5 part of thiol methyl tin, 1.0 parts of dipentaerythritol are weighed, by thiol methyl
Tin liquor body is uniformly mixed with DOTP liquid, and the solution that mixes then is added in dipentaerythritol, be stirred well to it is uniformly mixed,
The stabiliser solution being completely dissolved is slowly added in polyvinyl chloride resin, stirs, mixes it uniformly, the feed powder mixed is added high
Fast mixer hopper, control smelting temperature are 170~180 DEG C, discharge after 2~3min of mixing, then use vulcanizing press tabletting,
Sample thin slice is made.
2.0 × 2.0 × 1.0mm size is made in sample, according to standard GB/T/T 2917.1-2002, is measured Congo red
Heat-stable time, test temperature are 195 DEG C, and Congored test paper lower end is shown in Table 1 apart from powder 2cm, sample heat-stable time.
1 Congo red test result of table
Note: A- thiol methyl tin；B- cerium stearate；C- dipentaerythritol；D- butyl titanate；E- nano-titanium dioxide；Oil
195 DEG C of bath temperature；Embodiment 7 is that butyl titanate coupling agent coats nano-titanium dioxide；TiIt is initial to become the blue time；TcBecome completely
The blue time；Blank sample be 100 parts of PVC, 50 parts of DOTP, the same embodiment of preparation method.
From table 1 it follows that the PVC of 100 parts of the use of embodiment 7,50 parts of DOTP, 0.5 part of thiol methyl tin,
0.5 part of cerium stearate, 1.0 parts of dipentaerythritol, 1.0 parts of butyl titanates coat 5.0 parts of nano-titanium dioxide, prepared
Polyvinyl chloride film initially become the blue time up to 49 minutes, become the blue time completely as 54 minutes, there is excellent heat resistance, it is stable
Property is best；
For comparison, blank sample becomes the blue time initially as 5 minutes, becomes blue into 7 minutes completely, thermo-labile；Embodiment 3 uses
Polyvinyl chloride film prepared by 0.5 part of thiol methyl tin, 0.5 part of cerium stearate and 1.0 parts of dipentaerythritol is initial
Become the blue time as 30 minutes, becomes thiol methyl tin heat stabilizer of the blue time into 45 minutes, with 1 part of the use of embodiment 5 completely
It is close.Remaining compound stabilizer superiority and inferiority compare in proper order are as follows: embodiment 2 > 8 > 4 > 6 > 1, it is initial to become the blue time and become blue completely
Time is from high to low, it is seen that uses cerium stearate and dipentaerythritol auxiliary agent, uses instead of 0.5 part of thiol methyl tin, part
The raising that can promote film heat resistance.And 7 butyl titanate coupling agent of embodiment coats nano-titanium dioxide, made polychlorostyrene second
Alkene film has optimal heat-resistant stability.
The above content is combining specific embodiment, to the further description done of the present invention, but it is of the invention
Embodiment is simultaneously not restricted to the described embodiments, and others are any to be done without departing from Spirit Essence or principle of the invention
Change, replacement modification combination and simplify in protection scope of the present invention.
Claims (7)
1. a kind of composite thermal stabilizer containing organotin, cerium and titanium, it is characterised in that:
The composite thermal stabilizer is compounded by main stabilizer and auxiliary stabilizer；Wherein main stabilizer is thiol methyl
Tin, mercaptan tin octylate, thiol-butyl tin or dioctyltin laurate；Auxiliary stabilizer is cerium stearate, dipentaerythritol, metatitanic acid
Butyl ester and nano-titanium dioxide.
2. composite thermal stabilizer according to claim 1, it is characterised in that:
The main stabilizer is thiol methyl tin.
3. composite thermal stabilizer according to claim 1 or 2, it is characterised in that each component is constituted as follows by mass fraction:
4. composite thermal stabilizer according to claim 3, it is characterised in that each component is constituted as follows by mass fraction:
5. a kind of application of composite thermal stabilizer of any of claims 1 or 2, it is characterised in that: helped as thermostabilization
Agent is added in polyvinyl chloride, to improve its thermal stability.
6. application according to claim 5, it is characterised in that:
Proportion is constituted as follows when the composite thermal stabilizer is added to PVC:
7. application according to claim 5, it is characterised in that:
Proportion is constituted as follows when the composite thermal stabilizer is added to PVC:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811530345.2A CN109810290B (en) | 2018-12-14 | 2018-12-14 | Composite heat stabilizer containing organic tin, cerium and titanium and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811530345.2A CN109810290B (en) | 2018-12-14 | 2018-12-14 | Composite heat stabilizer containing organic tin, cerium and titanium and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109810290A true CN109810290A (en) | 2019-05-28 |
| CN109810290B CN109810290B (en) | 2021-09-28 |
Family
ID=66601745
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811530345.2A Active CN109810290B (en) | 2018-12-14 | 2018-12-14 | Composite heat stabilizer containing organic tin, cerium and titanium and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109810290B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922640A (en) * | 2019-12-16 | 2020-03-27 | 安徽理工大学 | Modified titanium dioxide and rare earth composite stabilizer for ultrasonic-assisted synthesis of PVC (polyvinyl chloride) and application thereof |
| CN112646232A (en) * | 2020-12-25 | 2021-04-13 | 安徽理工大学 | Synergistic heat stabilizer and application thereof in improving thermal stability of PVC (polyvinyl chloride) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497727A (en) * | 2009-03-04 | 2009-08-05 | 南亚塑胶工业股份有限公司 | PVC resin composition and product thereof |
| JP2010209313A (en) * | 2009-02-13 | 2010-09-24 | Toray Ind Inc | Method for producing aliphatic polyester resin and composition |
| US20100292379A1 (en) * | 2009-05-12 | 2010-11-18 | Nan Ya Plastics Corporation | PVC resin composition and products made of the same |
| CN103849088A (en) * | 2014-03-11 | 2014-06-11 | 瑞科稀土冶金及功能材料国家工程研究中心有限公司 | Rare earth-kaolin PVC (Polyvinyl Chloride) thermal stabilizer and preparation method thereof |
| CN104212101A (en) * | 2014-09-22 | 2014-12-17 | 无为县华祥电缆材料有限公司 | Modified polyvinyl chloride power cable protection material |
| CN105936680A (en) * | 2016-07-01 | 2016-09-14 | 西安科技大学 | Rare earth complex, preparation method and applications thereof |
-
2018
- 2018-12-14 CN CN201811530345.2A patent/CN109810290B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010209313A (en) * | 2009-02-13 | 2010-09-24 | Toray Ind Inc | Method for producing aliphatic polyester resin and composition |
| CN101497727A (en) * | 2009-03-04 | 2009-08-05 | 南亚塑胶工业股份有限公司 | PVC resin composition and product thereof |
| US20100292379A1 (en) * | 2009-05-12 | 2010-11-18 | Nan Ya Plastics Corporation | PVC resin composition and products made of the same |
| CN103849088A (en) * | 2014-03-11 | 2014-06-11 | 瑞科稀土冶金及功能材料国家工程研究中心有限公司 | Rare earth-kaolin PVC (Polyvinyl Chloride) thermal stabilizer and preparation method thereof |
| CN104212101A (en) * | 2014-09-22 | 2014-12-17 | 无为县华祥电缆材料有限公司 | Modified polyvinyl chloride power cable protection material |
| CN105936680A (en) * | 2016-07-01 | 2016-09-14 | 西安科技大学 | Rare earth complex, preparation method and applications thereof |
Non-Patent Citations (2)
| Title |
|---|
| 周大纲 谢鸽成: "《塑料老化与防老化技术（第二版）》", 31 October 2017, 中国轻工业出版社 * |
| 王杏: "《纳米二氧化钛的生产与应用》", 31 July 2014, 贵州出版集团 贵州科技出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922640A (en) * | 2019-12-16 | 2020-03-27 | 安徽理工大学 | Modified titanium dioxide and rare earth composite stabilizer for ultrasonic-assisted synthesis of PVC (polyvinyl chloride) and application thereof |
| CN110922640B (en) * | 2019-12-16 | 2021-08-20 | 安徽理工大学 | Modified titanium dioxide and rare earth composite stabilizer for ultrasonic-assisted synthesis of PVC (polyvinyl chloride) and application thereof |
| CN112646232A (en) * | 2020-12-25 | 2021-04-13 | 安徽理工大学 | Synergistic heat stabilizer and application thereof in improving thermal stability of PVC (polyvinyl chloride) |
| WO2022135422A1 (en) * | 2020-12-25 | 2022-06-30 | 安徽理工大学 | Synergistic heat stabilizer and use thereof in improving heat stability of pvc |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109810290B (en) | 2021-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109851940A (en) | It is a kind of containing organotin, the composite thermal stabilizer of calcium zinc and titanium and its application | |
| EP1273629B1 (en) | Antistatic composition | |
| CN109810290A (en) | A kind of composite thermal stabilizer and its application containing organotin, cerium and titanium | |
| CN103194005A (en) | Method for preparing novel polyvinyl chloride (PVC) rare-earth heat stabilizer | |
| CN101891866B (en) | Polyvinyl chloride mixture with impact resistance and excellent processability | |
| CN101671497B (en) | Industrial preparing method for PVC dedicated filler nanometer calcium carbonate with thermostability function | |
| González-Ortiz et al. | Thermal stability of plasticized poly (vinyl chloride) compounds stabilized with pre-heated mixtures of calcium and/or zinc stearates | |
| CN110003522A (en) | A kind of PVC organic composite heat stabilizer and PVC product and preparation method thereof | |
| CN105482100B (en) | A kind of fast light heat-resistant polyamide and preparation method thereof | |
| CN103881142B (en) | Complex stabilizer and preparation method thereof | |
| CN101440173B (en) | Sulfur-containing zinc soap composition for chlorine-containing polymer thermostable systematic and preparation thereof | |
| CN101851161B (en) | Large molecular weight polyalcohol and polyprotic acid organic ester and synthesis method and application thereof | |
| CN109096578A (en) | A kind of Transparent environment-friendlycalcium calcium zinc stabilizer and preparation method thereof | |
| CN105131451B (en) | A kind of pentaerythrite phenyl-carbonic acid ester type PVC composite heat stabilizer and application | |
| CN105295246A (en) | Hydrotalcite-lanthanum cyanurate composite environmental protection stabilizer for PVC, and preparation method thereof | |
| CN107523284A (en) | Sour gas well micro-emulsion type high temperature resistant de-plugging agent and preparation method thereof | |
| CN109824943A (en) | A kind of composite thermal stabilizer and its application containing organotin, magnesium and titanium | |
| WO2020024308A1 (en) | Rare earth compound thermal stabilizer for pvc and preparation method therefor | |
| CN107090141B (en) | The preparation method of PVC heat stabilizer | |
| CN104710334B (en) | Metal thiolate compound for PVC stabilization and preparation method thereof | |
| CN102875931B (en) | Preparation process of environment-friendly calcium-zinc compound heat stabilizer for PVC (polyvinyl chloride) | |
| CN109776780A (en) | A kind of phosphor-containing flame-proof PTT and its preparation method and application | |
| CN115490918A (en) | Liquid antistatic agent containing inorganic salt ions for PVC | |
| CN109354796A (en) | A kind of elastomer and preparation method thereof of diisononyl adipate modified polyvinyl chloride | |
| CN105217955A (en) | A kind of transparent glass production technique |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |