CN109810290B - Composite heat stabilizer containing organic tin, cerium and titanium and application thereof - Google Patents
Composite heat stabilizer containing organic tin, cerium and titanium and application thereof Download PDFInfo
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- CN109810290B CN109810290B CN201811530345.2A CN201811530345A CN109810290B CN 109810290 B CN109810290 B CN 109810290B CN 201811530345 A CN201811530345 A CN 201811530345A CN 109810290 B CN109810290 B CN 109810290B
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Abstract
The invention discloses a composite heat stabilizer containing organic tin, cerium and titanium and application thereof, wherein the composite heat stabilizer is prepared by compounding a main stabilizer and an auxiliary stabilizer; wherein the main stabilizer is methyl tin mercaptide, octyl tin mercaptide, butyl tin mercaptide or dioctyl tin laurate; the auxiliary stabilizer is cerium stearate, dipentaerythritol, butyl titanate and nano titanium dioxide. According to the invention, through optimization screening, the composite heat stabilizer with a synergistic effect is obtained, and when the composite heat stabilizer is applied to PVC, the thermal stability of the material can be obviously improved, and the composite heat stabilizer has potential environmental photodegradability.
Description
Technical Field
The invention relates to a polymer material processing aid, in particular to a composite heat stabilizer containing organic tin, cerium and titanium and application thereof.
Background
The polyvinyl chloride and the products thereof are important high polymer materials with annual output of more than 1800 ten thousand tons in China, and because the carbon-chlorine bond energy is 243kJ/mol, heat stabilizers such as lead salt, composite metal salt, organic tin, rare earth, organic and the like are generally required to be added. Lead salts are eliminated due to high toxicity, and the current stabilizer mainly develops towards the direction of no toxicity, high efficiency, multiple functions, excellent cost performance and degradability. The organic tin stabilizer accounts for about 1/4 in the total amount in the processing of polyvinyl chloride products, has the advantages of high efficiency, excellent heat resistance, transparency and light coloring, and is superior to other PVC heat stabilizers. Methyltin mercaptide and its products have been identified as non-toxic, safe products by the german federal health administration (BGA), the U.S. Food and Drug Administration (FDA), and other world health regulatory agencies. However, the methyl tin mercaptide is expensive and has peculiar smell, so that the use amount and the use cost are reduced, the synergistic effect and the environment-degradable additive are searched, and the assistant enterprise becomes a preoccupation of assistant enterprises, so that the research on the assistant stabilizer rare earth cerium stearate, the coupling agent butyl titanate and the nano titanium dioxide additive has important significance in exploring possible synergistic effect and environment friendliness.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a composite heat stabilizer containing organic tin, cerium and titanium and application thereof.
The composite heat stabilizer containing organic tin, cerium and titanium is prepared by compounding a main stabilizer and an auxiliary stabilizer; wherein the primary stabilizer (A) is methyl tin mercaptide, octyl tin mercaptide, butyl tin mercaptide or dioctyl tin laurate, and methyl tin mercaptide is preferred; the auxiliary stabilizer is cerium stearate (B), dipentaerythritol (C), butyl titanate (D) and nano titanium dioxide (E).
The composite heat stabilizer containing organic tin, cerium and titanium comprises the following components in parts by weight:
the components are preferably as follows according to the mass portion:
wherein dipentaerythritol may be replaced by equal amounts of pentaerythritol.
The composite heat stabilizer containing organic tin, cerium and titanium is applied by adding the composite heat stabilizer serving as a heat stabilizing auxiliary agent into polyvinyl chloride so as to improve the heat stability of the polyvinyl chloride.
When the composite heat stabilizer is added into PVC, the composite heat stabilizer is prepared by the following components in proportion:
the effect of the composite heat stabilizer on PVC heat stability is evaluated by adopting a Congo red experiment, namely, Congo red test paper is hung above PVC particles, the temperature is kept constant at 195 ℃, and the initial blue changing time and the complete blue changing time of the Congo red test paper are observed and recorded. PVC is decomposed rapidly at about 170-180 ℃ to release hydrogen chloride gas, and Congo red test paper reacts with hydrogen chloride to turn blue. The thermal stabilizer is added to inhibit the decomposition of the composite thermal stabilizer, and the quality of the effect of the composite thermal stabilizer can be judged according to the initial and complete blue changing time.
According to the invention, through optimization screening, the composite heat stabilizer with a synergistic effect is obtained, and when the composite heat stabilizer is applied to PVC, the thermal stability of the material can be obviously improved, and the composite heat stabilizer has potential environmental photodegradability.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention utilizes the synergistic stabilization effect of methyl tin mercaptide, cerium stearate, dipentaerythritol, butyl titanate and nano titanium dioxide, can reduce the usage amount of the methyl tin mercaptide, has better effect than the single use of the methyl tin mercaptide stabilizer, and effectively improves the thermal stability of PVC;
2. the cerium (B) stearate is used as a potential photodecomposition promoter and can promote the photodegradation of the polyvinyl chloride in the environment when the service life of the polyvinyl chloride is ended;
3. the butyl titanate (D) can promote the generation of electrostatic attraction and chemical bond force between tin, cerium and titanium metal oxides and polyvinyl chloride molecules, and the nano titanium dioxide (E) can also be used as a potential photodecomposition promoter when the service life of the polyvinyl chloride is terminated, so that the nano titanium dioxide (E) can accelerate photodegradation in the environment.
4. The methyl tin mercaptide, the cerium stearate, the dipentaerythritol, the butyl titanate and the nano titanium dioxide all belong to nontoxic environment-friendly substances, completely meet the development requirements for environmental protection at home and abroad, and have wide application prospects.
Detailed Description
The PVC resin used in the embodiment of the invention is S-65.
Example 1:
100 parts of PVC resin, 50 parts of DOTP, 0.5 part of methyl tin mercaptide, 0.5 part of cerium stearate, 1.0 part of dipentaerythritol and 0.5 part of butyl titanate are weighed, methyl tin mercaptide liquid and DOTP liquid are uniformly mixed, then cerium stearate, dipentaerythritol and butyl titanate are added into the well-mixed solution, and the mixture is fully stirred until the mixture is uniformly mixed. And slowly adding the completely dissolved stabilizer solution into the PVC resin, stirring at a high speed to uniformly mix the stabilizer solution, adding the mixed material powder into a hopper of a high-speed internal mixer, controlling the internal mixing temperature to be 170-180 ℃, carrying out internal mixing for 2-3 min, then discharging, and tabletting by using a flat vulcanizing machine to obtain the sample slice.
Example 2:
100 parts of PVC resin, 50 parts of DOTP, 0.5 part of methyl tin mercaptide, 0.5 part of cerium stearate, 1.0 part of dipentaerythritol and 1.0 part of butyl titanate are weighed, methyl tin mercaptide liquid and DOTP liquid are uniformly mixed, then cerium stearate, dipentaerythritol and butyl titanate are added into the well-mixed solution, and the mixture is fully stirred until the mixture is uniformly mixed. And slowly adding the completely dissolved stabilizer solution into the PVC resin, stirring to uniformly mix the stabilizer solution, adding the mixed material powder into a hopper of a high-speed internal mixer, controlling the internal mixing temperature to be 170-180 ℃, carrying out internal mixing for 2-3 min, then discharging, and tabletting by using a flat vulcanizing machine to obtain the sample sheet.
Example 3:
100 parts of PVC resin, 50 parts of DOTP, 0.5 part of methyl tin mercaptide, 0.5 part of cerium stearate and 1.0 part of dipentaerythritol are weighed, the methyl tin mercaptide liquid and the DOTP liquid are uniformly mixed, then the cerium stearate and the dipentaerythritol are added into the well-mixed solution, and the mixture is fully stirred until the mixture is uniformly mixed. And slowly adding the completely dissolved stabilizer solution into the PVC resin, stirring to uniformly mix the stabilizer solution and the PVC resin, adding the mixed material powder into a hopper of a high-speed internal mixer, controlling the internal mixing temperature to be 170-180 ℃, discharging after internal mixing for 2-3 min, and then tabletting by using a flat vulcanizing machine to prepare the sample sheet.
Example 4:
100 parts of PVC resin, 50 parts of DOTP, 0.5 part of methyl tin mercaptide and 0.5 part of cerium stearate are weighed, the methyl tin mercaptide liquid and the DOTP liquid are uniformly mixed, then the cerium stearate is added into the well mixed solution, and the mixture is fully stirred until the mixture is uniformly mixed. And slowly adding the completely dissolved stabilizer solution into the PVC resin, stirring to uniformly mix the stabilizer solution and the PVC resin, adding the mixed material powder into a hopper of a high-speed internal mixer, controlling the internal mixing temperature to be 170-180 ℃, discharging after internal mixing for 2-3 min, and then tabletting by using a flat vulcanizing machine to prepare the sample sheet.
Example 5:
weighing 100 parts of PVC resin, 50 parts of DOTP and 1.0 part of methyl tin mercaptide, uniformly mixing the methyl tin mercaptide liquid and the DOTP liquid, slowly adding the completely dissolved stabilizer solution into the PVC resin, stirring to uniformly mix the mixture, adding the mixed powder into a hopper of a high-speed internal mixer, controlling the internal mixing temperature to be 170-180 ℃, discharging after internal mixing for 2-3 min, and then tabletting by using a flat vulcanizing machine to prepare a sample sheet.
Example 6:
weighing 100 parts of PVC resin, 50 parts of DOTP, 0.5 part of methyl tin mercaptide and 0.5 part of dipentaerythritol, uniformly mixing methyl tin mercaptide liquid and DOTP liquid, adding dipentaerythritol into the mixed solution, fully stirring until the mixture is uniform, slowly adding the completely dissolved stabilizer solution into the PVC resin, stirring to uniformly mix the mixture, adding the mixed powder into a hopper of a high-speed internal mixer, controlling the internal mixing temperature to be 170-180 ℃, discharging after internal mixing for 2-3 min, and tabletting by using a flat plate vulcanizing machine to prepare a sample sheet.
Example 7:
weighing 100 parts of PVC resin, 50 parts of DOTP, 0.5 part of methyl tin mercaptide, 0.5 part of cerium stearate, 1.0 part of dipentaerythritol, 5.0 parts of nano titanium dioxide and 1.0 part of butyl titanate, and taking nano titanium dioxide and butyl titanate as an auxiliary stabilizer and a photocatalytic degradation agent;
(1) uniformly mixing methyl tin mercaptide liquid and DOTP liquid, then adding cerium stearate and dipentaerythritol into the well-mixed solution, fully stirring and uniformly mixing until the cerium stearate and the dipentaerythritol are completely dissolved, (2) mixing 1.0 part of butyl titanate and nano TiO25.0 parts of powder, and butyl titanate coated nano TiO2And heating, mixing and stirring for 30 min.
Slowly adding the uniformly mixed stabilizers (1) and (2) into PVC resin, stirring to fully mix the PVC resin, adding the mixed powder into a hopper of a high-speed internal mixer, controlling the internal mixing temperature to be 170-180 ℃, discharging after internal mixing for 2-3 min, and tabletting by a flat vulcanizing machine to obtain the sample sheet.
Example 8:
weighing 100 parts of PVC resin, 50 parts of DOTP, 0.5 part of methyl tin mercaptide and 1.0 part of dipentaerythritol, uniformly mixing methyl tin mercaptide liquid and DOTP liquid, adding dipentaerythritol into the mixed solution, fully stirring until the mixture is uniform, slowly adding the completely dissolved stabilizer solution into the PVC resin, stirring to uniformly mix the mixture, adding the mixed powder into a hopper of a high-speed internal mixer, controlling the internal mixing temperature to be 170-180 ℃, discharging after internal mixing for 2-3 min, and tabletting by using a flat plate vulcanizing machine to prepare a sample sheet.
The sample is made into the size of 2.0 multiplied by 1.0mm, the thermal stability time of the Congo red is determined according to the national standard GB/T2917.1-2002, the test temperature is 195 ℃, the distance between the lower end of the Congo red test paper and the powder is 2cm, and the thermal stability time of the sample is shown in the table 1.
TABLE 1 Congo Red test results
Note: a-methyl tin mercaptide; b-cerium stearate; c-dipentaerythritol; d-butyl titanate; e-nano titanium dioxide; the oil bath temperature is 195 ℃; example 7 is nano titanium dioxide coated with a butyl titanate coupling agent; t isi-an initial bluing time; t isc-a full blue time; the blank is 100 parts of PVC and 50 parts of DOTP, and the preparation method is the same as the example.
As can be seen from Table 1, in example 7, 100 parts of PVC, 50 parts of DOTP, 0.5 part of methyl tin mercaptide, 0.5 part of cerium stearate, 1.0 part of dipentaerythritol and 1.0 part of butyl titanate are used for coating 5.0 parts of nano titanium dioxide, so that the initial blue turning time of the prepared polyvinyl chloride film reaches 49 minutes, the complete blue turning time is 54 minutes, the polyvinyl chloride film has excellent heat resistance and optimal stability;
in contrast, the blank sample is not heat-resistant, the initial blue-changing time is 5 minutes, and the complete blue-changing time is 7 minutes; example 3 a polyvinyl chloride film prepared using 0.5 parts of methyltin mercaptide, 0.5 parts of cerium stearate and 1.0 part of dipentaerythritol had an initial blue change time of 30 minutes and a complete blue change time of 45 minutes, similar to that of example 5 using 1 part of methyltin mercaptide as a heat stabilizer. Compared with other composite stabilizers, the advantages and disadvantages of the composite stabilizers are as follows: example 2>8>4>6>1, the initial blue-turning time and the complete blue-turning time of which are from high to low, it can be seen that the use of cerium stearate and dipentaerythritol as an adjuvant, instead of 0.5 parts of methyl tin mercaptide, can partially promote the improvement of the heat resistance of the film. And in example 7, the butyl titanate coupling agent coats the nano titanium dioxide, and the prepared polyvinyl chloride film has the best heat-resistant stability.
The present invention is described in further detail with reference to the specific embodiments, but the embodiments of the present invention are not limited by the above examples, and any other modifications, alternative combinations, and simplifications without departing from the spirit or principle of the present invention are within the scope of the present invention.
Claims (2)
1. The application of the composite heat stabilizer is characterized in that: the composite heat stabilizer is added into the polyvinyl chloride to improve the heat stability of the polyvinyl chloride;
the composite heat stabilizer is prepared by compounding a main stabilizer and an auxiliary stabilizer; wherein the main stabilizer is methyl tin mercaptide, octyl tin mercaptide, butyl tin mercaptide or dioctyl tin laurate; the auxiliary stabilizer is cerium stearate, dipentaerythritol, butyl titanate and nano titanium dioxide;
when the composite heat stabilizer is added into PVC, the composite heat stabilizer is prepared by the following components in proportion:
2. use according to claim 1, characterized in that:
the main stabilizer is methyl tin mercaptide.
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| 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 |
| CN112646232B (en) * | 2020-12-25 | 2022-10-21 | 安徽理工大学 | Synergistic heat stabilizer and application thereof in improving thermal stability of PVC (polyvinyl chloride) |
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| 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 |
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| 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 |
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