CN112646232A - Synergistic heat stabilizer and application thereof in improving thermal stability of PVC (polyvinyl chloride) - Google Patents
Synergistic heat stabilizer and application thereof in improving thermal stability of PVC (polyvinyl chloride) Download PDFInfo
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Abstract
The invention discloses a synergistic heat stabilizer and application thereof in improving PVC thermal stability, wherein the synergistic heat stabilizer is enhanced after microwave radiation by taking organic tin, cerium metal soap and butyl titanate as active components and through the crosslinking action between a butyl titanate coupling agent and tin, cerium metal and PVC, and can be used for preparing a novel PVC composite film material with excellent thermal stability effect and potential microwave radiation resistance.
Description
Technical Field
The invention belongs to the field of polymer material processing aids, and particularly relates to a synergistic heat stabilizer and application thereof in improving PVC thermal stability.
Background
With the enhancement of environmental protection consciousness of people, the heat stabilizer of the polyvinyl chloride film or the product is developed towards non-toxicity, high efficiency, multiple functions, excellent cost performance and degradability. The usage amount of the organic tin heat stabilizer is continuously increased to gradually replace lead salt stabilizers, but the common organic tin stabilizer has high price, peculiar smell and unsatisfied heat stabilization effect. Therefore, the adoption of different components and different methods for improving the thermal stability of PVC, reducing the use amount of organic tin, reducing the application cost, searching for the synergistic effect and environmental degradability becomes urgent.
Microwaves are widely used in the fields of chemistry and chemical engineering and materials, and generally have three functions: 1) the microwave rapid heating is different from the traditional heating heat conduction; 2) the specificity of the microwave promotes the conversion rate and selectivity of the reaction; 3) performing microwave thermal degradation; while 1) and 3) are more common; 2) although having high selectivity and efficacy, it is closely related to the reactant composition. The microwave-assisted preparation of the cerium metal soap and butyl titanate composite stabilizer for PVC is not reported in documents.
Disclosure of Invention
The invention provides a synergistic heat stabilizer and application thereof in improving thermal stability of PVC (polyvinyl chloride) in order to solve the problems of high price and poor heat resistance of methyl tin mercaptide at present. The organic tin, cerium metal soap and butyl titanate are used as active components, and are enhanced after microwave radiation through the crosslinking action between the butyl titanate coupling agent and the tin, cerium metal and PVC, so that the organic tin-cerium metal soap can be used for preparing a novel PVC composite film material with excellent thermal stability effect and potential microwave radiation resistance.
Tetrabutyl titanate is a colorless to pale yellow oily liquid, relative density: 0.966, freezing point: -55 ℃, flash point: 76.7 ℃, boiling point: 310-314 ℃, is an organic titanium compound used as a catalyst for polycondensation and crosslinking reactions, is mainly used for esterification and transesterification reactions, such as the synthesis of polyester polyol, and can also be used as a tackifier of metal-plastic, a modifier of high-strength polyester paint, a crosslinking agent and the like.
The invention relates to a synergistic heat stabilizer, which takes organic tin as a main heat stabilizer and takes a tetrabutyl titanate modified cerium metal soap complex as an auxiliary stabilizer. The butyl titanate as the coupling agent has obvious synergistic stabilizing effect on organic tin and cerium metal soap, and can effectively improve the thermal stability of PVC.
The invention discloses a synergistic heat stabilizer, which comprises the following components in parts by weight:
1.0-5.0 parts of butyl titanate, 1.0-5.0 parts of cerium metal soap and 0.1-1.0 part of organic tin heat stabilizer.
More preferably: 1.0-5.0 parts of butyl titanate, 1.0-5.0 parts of cerium metal soap and 0.5 part of organic tin heat stabilizer.
The cerium metal soap is cerium stearate.
The organotin includes methyltin mercaptide, octyltin mercaptide, butyltin mercaptide, dioctyltin laurate, and the like.
The preparation method of the synergistic heat stabilizer comprises the following steps:
by adopting a microwave radiation technology, 50 parts by mass of DOTP, 1.0-5.0 parts by mass of butyl titanate, 1.0-5.0 parts by mass of cerium metal soap and 0.1-1.0 part by mass of organic tin heat stabilizer are mixed and dissolved, then the mixture is placed in a glass container, microwave (with power output of 17%) is started in a microwave oven to radiate and mix for 15min, and a uniform precursor is obtained, wherein the power of the microwave oven is 700 w.
DOTP added in the preparation process is dioctyl terephthalate which is a plasticizer of the PVC material, DOTP is added in advance to be used as a solvent in the preparation process of the synergistic heat stabilizer, unnecessary addition of other solvents is avoided, and the plasticizer is not required to be added in the subsequent preparation process of the PVC material.
The application of the synergistic heat stabilizer is to add the synergistic heat stabilizer into a PVC base material so as to improve the heat stability of the PVC material. Wherein the proportion of each component is as follows: 100 parts of PVC resin, 1.0-5.0 parts of butyl titanate, 1.0-5.0 parts of cerium metal soap and 0.1-1.0 part of organic tin heat stabilizer.
The preferable mixture ratio is as follows: 100 parts of PVC resin, 1.0-5.0 parts of butyl titanate, 1.0-5.0 parts of cerium metal soap and 0.5 part of organic tin heat stabilizer.
The application of the synergistic heat stabilizer is specifically that a synergistic heat stabilizer precursor is mixed with a PVC base material, the mixture is stirred at a high speed to obtain a premix, then the premix is placed in an internal mixer for internal mixing, the melt temperature is 170-175 ℃, the screw rotation speed is 40r/min, the internal mixing time is 2-3min, after the torque is rapidly increased and then decreased and is kept unchanged, the mixed material is taken out, and a flat vulcanizing machine is adopted for tabletting at 100 ℃ for 40 seconds, so that a PVC sheet with the thickness of 1mm is obtained for subsequent performance detection.
The synergistic heat stabilizer provided by the invention is used for improving the thermal stability of PVC, PVC is used as a base material, the butyl titanate modified cerium metal soap complex is used as an auxiliary stabilizer, organic tin is used as a heat stabilizer, and butyl titanate has a remarkable synergistic stabilizing effect on organic tin and cerium metal soap, so that the thermal stability of PVC can be effectively improved.
According to the invention, butyl titanate is used for surface modification, a microwave radiation process is adopted as a green and rapid preparation method, PVC composite films of butyl titanate modified cerium metal soap and organic tin with different addition amounts are prepared, and the hydrogen chloride release rates of different composite films are measured by adopting a 195 ℃ conductivity method. Butyl titanate produces strong synergistic effect with cerium metal soap and organic tin, and has obviously raised heat stability, no toxicity and high environment compatibility.
The method for evaluating the thermal stability of the PVC is conductivity or hydrogen chloride release rate, and the test device refers to ENIS 0182-3: 2000 standard; introducing high-purity nitrogen into PVC powder, heating to 195 ℃, keeping the temperature constant, and observing the change of the conductivity or the concentration of the hydrogen chloride absorbed and released by deionized water along with time. PVC can be rapidly decomposed at the temperature of 180-195 ℃ to release hydrogen chloride gas, and a platinum electrode in a conductivity meter can rapidly sense the conductivity change of hydrogen protons and chloride ions in deionized water. The composite stabilizer is added to inhibit the decomposition of the composite stabilizer, and the quality of the effect of the composite heat stabilizer can be judged by measuring the induction period and the stabilization time through a conductivity curve.
Compared with the prior art, the invention has the beneficial effects that:
1. the modifier adopted by the invention is butyl titanate, is environment-compatible and is easy to degrade; the modified cerium metal soap is used as a potential photodecomposition promoter, and can promote the photodegradation of polyvinyl chloride in the environment when the service life of the polyvinyl chloride is ended;
2. the tetrabutyl titanate can promote the generation of electrostatic attraction and chemical bond force between tin and cerium metal soaps and polyvinyl chloride molecules;
3. the butyl titanate has obvious synergistic stabilizing effect on the methyl tin mercaptide and the cerium metal soap, can reduce the using amount of the methyl tin mercaptide, has better effect than that of singly using the methyl tin mercaptide stabilizer, and effectively improves the heat resistance of the PVC;
4. the butyl titanate, the methyl tin mercaptide and the cerium metal soap belong to nontoxic or low-toxicity environment-friendly substances, completely meet the development requirements for environmental protection at home and abroad, and have wide application prospects.
Drawings
FIG. 1 is a graph of conductivity versus time for hydrogen chloride evolution from example 1, 2 different PVC films. In the figure, the abscissa represents the heating time/min, and the ordinate represents the electrical conductivity/. mu.Scm-1The dotted line is conventional heating, the solid line is microwave heating, and the components are 0.5 part of methyl tin mercaptide, 1 part of butyl titanate, 5 parts of cerium stearate, 50 parts of DOTP and 100 parts of PVC.
Detailed Description
The invention adopts butyl titanate as a coupling agent, and the usage amount of the butyl titanate is 1-5 parts per 100 parts of PVC.
Cerium stearate is used as a co-stabilizer, and the using amount of the cerium stearate is 1-10 parts per 100 parts of PVC, preferably 5 parts.
Cerium stearate and microwave heating
Taking PVC resin model S-65100 parts, DOTP50 parts, butyl titanate 1 part, methyl tin mercaptide 0.5 part and cerium stearate 5 parts.
Cerium (di) stearate + conventional heating
Taking PVC resin model S-65100 parts, DOTP50 parts, butyl titanate 1 part, methyl tin mercaptide 0.5 part and cerium stearate 5 parts.
Control + conventional heating
100 parts of PVC resin, 50 parts of DOTP, 1 part of butyl titanate, 0.5 part of methyl tin mercaptide and 5 parts of lanthanum stearate; 100 parts of PVC resin, 50 parts of DOTP, 1 part of butyl titanate, 0.5 part of methyl tin mercaptide and 5 parts of calcium stearate; 100 parts of PVC resin, 50 parts of DOTP, 1 part of butyl titanate, 0.5 part of methyl tin mercaptide and 5 parts of magnesium stearate; 100 parts of PVC resin, 50 parts of DOTP, 1 part of butyl titanate, 0.5 part of methyl tin mercaptide and 5 parts of zinc stearate; 100 parts of PVC resin, 50 parts of DOTP, 1 part of butyl titanate, 0.5 part of methyl tin mercaptide and 5 parts of calcium-zinc.
Control + microwave heating
100 parts of PVC resin, 50 parts of DOTP, 1 part of butyl titanate, 0.5 part of methyl tin mercaptide and 5 parts of lanthanum stearate; 100 parts of PVC resin, 50 parts of DOTP, 1 part of butyl titanate, 0.5 part of methyl tin mercaptide and 5 parts of calcium stearate; 100 parts of PVC resin, 50 parts of DOTP, 1 part of butyl titanate, 0.5 part of methyl tin mercaptide and 5 parts of magnesium stearate; 100 parts of PVC resin, 50 parts of DOTP, 1 part of butyl titanate, 0.5 part of methyl tin mercaptide and 5 parts of zinc stearate; 100 parts of PVC resin, 50 parts of DOTP, 1 part of butyl titanate, 0.5 part of methyl tin mercaptide and 5 parts of calcium-zinc.
Example 1: preparation of PVC/butyl titanate-cerium metal soap-organic tin composite film
Adopting a microwave radiation technology, mixing and dissolving 50 parts by mass of DOTP, 1 part by mass of butyl titanate, 5 parts by mass of cerium metal soap and 0.5 part by mass of organic tin stabilizer, and starting microwave (17% power output) in a microwave oven for mixed radiation for 15min to obtain a uniform precursor; and adding 100 parts by mass of PVC into the obtained precursor, stirring at a high speed to obtain a premix, placing the premix in a small internal mixer for internal mixing, wherein the melt temperature is 170-.
Example 2: preparation of PVC/butyl titanate-cerium metal soap-organic tin composite film
Adopting an ultrasonic radiation technology, mixing and dissolving 50 parts by mass of DOTP, 1 part by mass of butyl titanate, 5 parts by mass of cerium metal soap and 0.5 part by mass of organic tin stabilizer, and starting ultrasonic oscillation for 1 hour to obtain a uniform precursor; adding 100 parts by mass of PVC into the obtained precursor, stirring at a high speed to obtain a premix, placing the premix into a small internal mixer for internal mixing, wherein the melting temperature is 170-.
TABLE 1 conductivity of hydrogen chloride released by different PVC films under microwave irradiation
(Note: A-methyl tin mercaptide; B)1-cerium stearate; b is2-calcium stearate; b is3-magnesium stearate; b is4-zinc stearate; b is5-lanthanum stearate; b is6- (calcium-zinc) commercial products; c-butyl titanate; all samples contain 100 parts of PVC and 50 parts of DOTP; the power of the microwave oven is 700W; heating strength: 17% power output)
Comparative examples 1-5 use microwave irradiation techniques:
comparative example 1: preparation of PVC/butyl titanate-calcium metal soap-organic tin composite film
Adopting a microwave radiation technology, mixing and dissolving 50 parts by mass of DOTP, 1 part by mass of butyl titanate, 5 parts by mass of calcium metal soap and 0.5 part by mass of organic tin stabilizer, and starting microwave (17% power output) in a microwave oven for mixed radiation for 15min to obtain a uniform precursor; adding 100 parts by mass of PVC into the obtained precursor, stirring at a high speed to obtain a premix, placing the premix into a small internal mixer for internal mixing, wherein the melting temperature is 170-.
Comparative example 2: preparation of PVC/butyl titanate-magnesium metal soap-organic tin composite film
Adopting a microwave radiation technology, mixing and dissolving 50 parts by mass of DOTP, 1 part by mass of butyl titanate, 5 parts by mass of magnesium metal soap and 0.5 part by mass of organic tin stabilizer, and starting microwave (17% power output) in a microwave oven for mixed radiation for 15min to obtain a uniform precursor; adding 100 parts by mass of PVC into the obtained precursor, stirring at a high speed to obtain a premix, placing the premix into a small internal mixer for internal mixing, wherein the melting temperature is 170-.
Comparative example 3: preparation of PVC/butyl titanate-zinc metal soap-organic tin composite film
Adopting a microwave radiation technology, mixing and dissolving 50 parts by mass of DOTP, 1 part by mass of butyl titanate, 5 parts by mass of zinc metal soap and 0.5 part by mass of organic tin stabilizer, and starting microwave (17% power output) in a microwave oven for mixed radiation for 15min to obtain a uniform precursor; adding 100 parts by mass of PVC into the obtained precursor, stirring at a high speed to obtain a premix, placing the premix into a small internal mixer for internal mixing, wherein the melting temperature is 170-.
Comparative example 4: preparation of PVC/butyl titanate-lanthanum metal soap-organic tin composite film
Adopting a microwave radiation technology, mixing and dissolving 50 parts by mass of DOTP, 1 part by mass of butyl titanate, 5 parts by mass of lanthanum metal soap and 0.5 part by mass of organic tin stabilizer, and starting microwave (17% power output) in a microwave oven for mixed radiation for 15min to obtain a uniform precursor; adding 100 parts by mass of PVC into the obtained precursor, stirring at a high speed to obtain a premix, placing the premix into a small internal mixer for internal mixing, wherein the melting temperature is 170-.
Comparative example 5: PVC/butyl titanate- (calcium-zinc)*Preparation of organotin composite film
Adopting microwave radiation technology, taking 50 parts by mass of DOTP, 1 part by mass of butyl titanate and (calcium-zinc)*5 parts by mass and 0.5 part by mass of an organic tin stabilizer are mixed and dissolved, and the mixture is radiated for 15min by starting microwave (with 17% power output) in a microwave oven to obtain a uniform precursor; adding 100 parts by mass of PVC into the obtained precursor, stirring at a high speed to obtain a premix, placing the premix into a small internal mixer for internal mixing, wherein the melting temperature is 170-.
Comparative examples 6-10 use ultrasonic irradiation:
comparative example 6: preparation of PVC/butyl titanate-calcium metal soap-organic tin composite film
Adopting an ultrasonic radiation technology, mixing and dissolving 100 parts by mass of PVC, 50 parts by mass of DOTP, 1 part by mass of butyl titanate, 5 parts by mass of calcium metal soap and 0.5 part by mass of organic tin stabilizer, and performing ultrasonic stirring for 1 hour at 40 ℃ to obtain a uniform premix; and (3) placing the obtained premix into a small internal mixer for internal mixing, wherein the melting temperature is 170-.
Comparative example 7: preparation of PVC/butyl titanate-magnesium metal soap-organic tin composite film
Adopting an ultrasonic radiation technology, mixing and dissolving 100 parts by mass of PVC, 50 parts by mass of DOTP, 1 part by mass of butyl titanate, 5 parts by mass of magnesium metal soap and 0.5 part by mass of organic tin stabilizer, and performing ultrasonic stirring for 1 hour at 40 ℃ to obtain a uniform premix; and (3) placing the obtained premix into a small internal mixer for internal mixing, wherein the melting temperature is 170-.
Comparative example 8: preparation of PVC/butyl titanate-zinc metal soap-organic tin composite film
Adopting an ultrasonic radiation technology, mixing and dissolving 100 parts by mass of PVC, 50 parts by mass of DOTP, 1 part by mass of butyl titanate, 5 parts by mass of zinc metal soap and 0.5 part by mass of organic tin stabilizer, and performing ultrasonic stirring for 1 hour at 40 ℃ to obtain a uniform premix; and (3) placing the obtained premix into a small internal mixer for internal mixing, wherein the melting temperature is 170-.
Comparative example 9: preparation of PVC/butyl titanate-lanthanum metal soap-organic tin composite film
Adopting an ultrasonic radiation technology, mixing and dissolving 100 parts by mass of PVC, 50 parts by mass of DOTP, 1 part by mass of butyl titanate, 5 parts by mass of lanthanum metal soap and 0.5 part by mass of organic tin stabilizer, and performing ultrasonic stirring for 1 hour at 40 ℃ to obtain a uniform premix; and (3) placing the obtained premix into a small internal mixer for internal mixing, wherein the melting temperature is 170-.
Comparative example 10: preparation of PVC/butyl titanate- (calcium-zinc) organic tin composite film
Adopting ultrasonic radiation technology, taking 100 parts by mass of PVC, 50 parts by mass of DOTP, 1 part by mass of butyl titanate, (calcium-zinc)*5 parts by mass and 0.5 part by mass of an organic tin stabilizer are mixed and dissolved, and the mixture is ultrasonically stirred for 1 hour at the temperature of 40 ℃ to obtain a uniform premix; placing the obtained premix into a small internal mixer for internal mixing, wherein the melting temperature is 170-The PVC sheet with the thickness of 1mm is obtained after the machine is pressed for 40 seconds at the temperature of 100 ℃.
TABLE 2 conductivity of hydrogen chloride released by different PVC films under conventional heating
(Note: A-methyl tin mercaptide; B)1-cerium stearate; b is2-calcium stearate; b is3-magnesium stearate; b is4-zinc stearate; b is5-lanthanum stearate; b is6- (calcium-zinc)*A commercially available commercial product; c-butyl titanate; all samples contained PVC-100 parts, DOTP-50 parts)
The evaluation method of the PVC thermal stability comprises the following steps: the conductivity of the aqueous hydrogen chloride solution released was determined, with reference to ENIS 0182-3: 2000 standard; introducing high-purity nitrogen into a PVC powder heating test tube, using silicone oil as an oil bath, heating at 195 ℃, and observing the change curve of the conductivity of the deionized water absorbing and releasing hydrogen chloride along with time.
The PVC sample can be decomposed to release hydrogen chloride gas at the temperature of 180-195 ℃, and a platinum electrode in the conductivity meter can quickly sense the conductivity change of hydrogen protons and chloride ions in deionized water. The composite stabilizer is added to inhibit the decomposition of the heat stabilizer, and the quality of the effect of the heat stabilizer can be judged by measuring the induction period and the stabilization time through a conductivity curve.
As can be seen from Table 1, Table 2 and FIG. 1, when heated conventionally, the heat resistance of the alloy is improved by the metallic soaps of calcium, magnesium, zinc, lanthanum, cerium, (calcium-zinc)*The induction periods of hydrogen chloride released by the thermal degradation of PVC are respectively 60, 88, 45, 57, 60 and 36min in a nitrogen atmosphere at 195 ℃, and under the same condition, the induction periods of hydrogen chloride released by the thermal degradation of PVC are respectively 70, 75, 42, 45, 53 and 33min by adopting microwave (17% power output) radiation for 15min, so that the induction period of the thermal degradation of PVC only containing cerium metal soap is prolonged by 10min, and the rest of calcium, magnesium, zinc, lanthanum and (calcium-zinc)*Drop 13, 3, 12, 7 and 3min respectively. Thus, except for the cerium metal soaps of example 1 and example 2Besides, compared with conventional heating, the microwave heating only can enhance the thermal stability of the PVC film by using the cerium metal soap; for calcium, magnesium, zinc, lanthanum metal soaps and (calcium-zinc)*Compared with conventional heating, the microwave heating reduces the heat-resistant stability of the PVC film, namely the stability is in a descending trend. As shown in comparative examples 1-10.
TABLE 3 conductivity of hydrogen chloride released by PVC films at different irradiation times
(Note: A-methyl tin mercaptide; B)1-cerium stearate; c-butyl titanate; the samples contain 100 parts of PVC and 50 parts of DOTP; the power of the microwave oven is 700W; heating strength: 17% power output)
Table 3 shows the conductivity of the PVC film releasing hydrogen chloride at different irradiation times, and when the microwave irradiation is increased from 5min in example 3 to 15min in example 1, the induction period of the PVC film releasing hydrogen chloride is increased from 50min to 70min, thus it can be seen that the irradiation time is prolonged, which will improve the heat resistance of the PVC film.
Claims (9)
1. A synergistic heat stabilizer is characterized in that:
the synergistic heat stabilizer takes organic tin as a main heat stabilizer, takes a butyl titanate modified cerium metal soap complex as an auxiliary stabilizer, and takes butyl titanate as a coupling agent, so that the synergistic heat stabilizer has a remarkable synergistic stabilizing effect on the organic tin and the cerium metal soap, and can effectively improve the thermal stability of PVC.
2. The synergistic heat stabilizer according to claim 1, wherein:
the cerium metal soap is cerium stearate.
3. The synergistic heat stabilizer according to claim 1 or 2, characterized in that the components are composed of, in parts by mass:
1.0-5.0 parts of butyl titanate, 1.0-5.0 parts of cerium metal soap and 0.1-1.0 part of organic tin heat stabilizer.
4. The synergistic heat stabilizer according to claim 3, wherein the components comprise the following components in parts by mass:
1.0-5.0 parts of butyl titanate, 1.0-5.0 parts of cerium metal soap and 0.5 part of organic tin heat stabilizer.
5. The synergistic heat stabilizer according to claim 1, which is prepared by a process comprising the steps of:
by adopting a microwave radiation technology, 50 parts by mass of DOTP, 1.0-5.0 parts by mass of butyl titanate, 1.0-5.0 parts by mass of cerium metal soap and 0.1-1.0 part by mass of organic tin heat stabilizer are mixed and dissolved, then the mixture is placed in a glass container, and microwave radiation is started in a microwave oven for mixing for 15min to obtain a uniform synergistic heat stabilizer precursor.
6. The synergistic heat stabilizer of claim 5, wherein:
microwave oven power 700 w.
7. Use of a synergistic thermal stabilizer according to claim 1, 2 or 5, wherein:
adding the synergistic heat stabilizer to a PVC base material to improve the heat stability of the PVC material; wherein the proportion of each component is as follows: 100 parts of PVC resin, 1.0-5.0 parts of butyl titanate, 1.0-5.0 parts of cerium metal soap and 0.1-1.0 part of organic tin heat stabilizer.
8. Use according to claim 7, characterized in that:
mixing the synergistic heat stabilizer precursor with a PVC matrix material, stirring at a high speed to obtain a premix, then placing the premix in an internal mixer for internal mixing, taking out the mixed material after the torque is rapidly increased and then decreased and the internal mixing is finished after the torque is kept unchanged, and tabletting for 40 seconds at 100 ℃ by using a flat vulcanizing machine to obtain the PVC sheet with the thickness of 1 mm.
9. Use according to claim 8, characterized in that:
and controlling the melt temperature to be 170-175 ℃ during banburying, controlling the screw rotating speed to be 40r/min, and controlling the banburying time to be 2-3 min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114196135A (en) * | 2021-12-24 | 2022-03-18 | 安徽理工大学 | Preparation of ultrasonic-wave-radiated calcium and lanthanum-based polyvinyl chloride high-molecular heat stabilizer and application of ultrasonic-radiated calcium and lanthanum-based polyvinyl chloride high-molecular heat stabilizer in soft products |
| 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 |
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| US20160194478A1 (en) * | 2013-08-08 | 2016-07-07 | Galata Chemicals Llc | Heat stabilizer for halogen-containing polymers |
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| 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 |
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| CN107778720A (en) * | 2017-11-09 | 2018-03-09 | 新沂市星辰新材料科技有限公司 | A kind of environment-protecting and non-poisonous PVC zinc stearate compound stabilizers |
| 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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| CN109810290A (en) * | 2018-12-14 | 2019-05-28 | 安徽理工大学 | A kind of composite thermal stabilizer and its application containing organotin, cerium and titanium |
| CN110885514A (en) * | 2019-12-16 | 2020-03-17 | 安徽理工大学 | Microwave-assisted synthesized modified nano titanium dioxide and calcium-magnesium-zinc composite stabilizer for PVC and application thereof |
| 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 |
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| 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 |
| CN114196135A (en) * | 2021-12-24 | 2022-03-18 | 安徽理工大学 | Preparation of ultrasonic-wave-radiated calcium and lanthanum-based polyvinyl chloride high-molecular heat stabilizer and application of ultrasonic-radiated calcium and lanthanum-based polyvinyl chloride high-molecular heat stabilizer in soft products |
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