CN105295245A - Hydrotalcite-zinc glutarate composite environmental protection stabilizer for PVC, and preparation method thereof - Google Patents
Hydrotalcite-zinc glutarate composite environmental protection stabilizer for PVC, and preparation method thereof Download PDFInfo
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- CN105295245A CN105295245A CN201510793097.0A CN201510793097A CN105295245A CN 105295245 A CN105295245 A CN 105295245A CN 201510793097 A CN201510793097 A CN 201510793097A CN 105295245 A CN105295245 A CN 105295245A
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Abstract
The present invention provides a hydrotalcite-zinc glutarate composite environmental protection stabilizer for PVC, wherein the hydrotalcite-zinc glutarate composite environmental protection stabilizer is prepared from the following raw materials by weight: 20-30 parts of modified magnesium aluminum hydrotalcite, 10-12 parts of monobutyltin oxide, 6-9 parts of lanthanum laurate, 4-6 parts of cerium stearate, 1-3 parts of cyclic phosphoric ester, 3-6 parts of zinc glutarate, 2-4 parts of epoxidized soybean oil, 12-14 parts of phthalic acid polyester, 1-2 parts of polyethylene wax, 5-6 parts of carbitol, 2-3 parts of tris(1,2,2,6,6-pentamethylpiperidyl)phosphite, 4-6 parts of zinc stearate, and 4-5 parts of calcined pot clay. According to the present invention, the PVC stabilizer has characteristics of good thermal stability, good processing performance, environmental protection, no toxicity, low cost, good plasticity and balance torque reducing during the PVC processing process, and low cost.
Description
Technical field
The present invention relates to PVC auxiliary agent field, be specifically related to a kind of PVC hydrotalcite pentanedioic acid zinc composite environmental-friendly stablizer agent and preparation method thereof.
Background technology
PVC is generally applied in the fields such as chemical industry, material, machinery, agricultural, daily necessities with its superior physicals and cheap cost, is especially widely used at plastic applications, is called as one of five large general-purpose plastics.But PVC has a very important defect, be exactly when hot-work, easily decompose and produce HCl gas, the degraded that autocatalysis causes PVC violent, and affect the various performances of PVC product, as made the variable color of PVC product or reducing its mechanical property etc.In order to overcome this defect of PVC, mainly in the hot procedure of PVC, add appropriate stablizer at present.
The thermo-stabilizer of present widespread commercialization only has lead salts, organic tin and metal soap.And lead salt stabilizer exists toxicity and cause series of environmental problems, therefore lead salt composite thermal stabilizer is complied with trend and is born, although the usage quantity of lead salt decreases, but still exists and poisons, and eliminating of the plumbous thermo-stabilizer of cadmium has been the certainty of history.And although organotin thermostability is high, pollution hazard is little, expensive, and cost is high, and has peculiar smell, does not meet the production national conditions of China's present stage, makes it develop and be in constrained state.Metal soap thermal stabilizers effect limited capacity.
Along with the enhancing of people to environmental consciousness and the requirement to environment more and more higher, the Non-toxic of PVC stablizer is the certainty of following stablizer development.Rare earth thermal stabilizer has good thermal stability, but early stage thermostability is not high, initial coloring is poor, main stabilizer can not be done separately, it is made to apply and popularization is subject to a definite limitation, the application of single rare earth thermo-stabilizer is often difficult to the requirement meeting PVC processing and application performance, and Composite, multifunctional type rare earth thermal stabilizer have been the trend of development.Rare earth thermal stabilizer and other auxiliary agents with the use of time, can produce synergistic effect, effectively can improve thermostable effect, the over-all properties of its double matching type heat stabilizer is often better than traditional lead salt and metal soap stablizer, in some applications, rare earth composite stabilizer partly or entirely can replace organotin.China's rare earth resources enriches, and accounts for 23% of world saving.Therefore the rare earth resources making full use of China develops the distinctive performance efficiency of a kind of China, nontoxic, the low price rare earth complex heat stabilizer that meets the current production national conditions of China, realize the efficiency utilization of China's rare earth resources, have very important significance, developing PVC is efficient, nontoxic composite heat stabilizer has become must.
Summary of the invention
The invention discloses a kind of PVC hydrotalcite pentanedioic acid zinc composite environmental-friendly stablizer and preparation method thereof.PVC stabilizer of the present invention has good thermostability and processing characteristics, and environment-protecting asepsis, with low cost, and in the course of processing of PVC, soffening is good and can reduce balancing torque, and light transmission is good, and cost is low.
The technical solution used in the present invention is as follows for achieving the above object:
A kind of PVC hydrotalcite pentanedioic acid zinc composite environmental-friendly stablizer, it is characterized in that: it is prepared by the component raw material of following weight part and obtains: modification magnesium aluminum-hydrotalcite 20-30, Mono-n-butyltin 10-12, lauric acid lanthanum 6-9, cerium stearate 4-6, annular phosphate 1-3, pentanedioic acid zinc 3-6, epoxy soybean oil 2-4, phthalic acid polyester 12-14, polyethylene wax 1-2, Trivalin SF 5-6, three (1,2,2,6,6-Pempiten base) phosphorous acid ester 2-3, Zinic stearas 4-6, calcinated argil 4-5.
The preparation method of described PVC hydrotalcite pentanedioic acid zinc composite environmental-friendly stablizer, is characterized in that, comprise the following steps:
(1) preparation of modified hydrotalcite:
A, get a certain amount of Mg (NO3) 26H2O and Al (NO3) 39H2O and be added to the water and be made into the salts solution that total mol concentration is 0.6mol/L, get a certain amount of NaOH and Na2CO3 and add in deionized water that to be made into total mol concentration be 0.6mol/L alkaline solution, by alkaline solution with 1-2 drip/s speed drops in salts solution, N
2the lower violent stirring of protection, constant temperature 38-42 DEG C, pH value remains between 9.5 ~ 10, at stirring 1-1.5h after dropwising, after 75 DEG C of crystallization 8h suction filtrations, washing is to neutral, will precipitate 45-50 DEG C of oven dry, obtain Mg/Al hydrotalcite, wherein the mol ratio of Mg (NO3) 26H2O and Al (NO3) 39H2O is the mol ratio 2:1 of 2:3, NaOH and Na2CO3, the volume ratio 1-1.2:1 of alkaline solution and salts solution during dropping;
B, toxilic acid and citric acid take according to the ratio that mol ratio is 1:1-2 and are a certain amount ofly dissolved in analytical pure ethylene glycol, after abundant mixing, add the Mg/Al hydrotalcite that step (1) is obtained, under 85-88 DEG C of constant temperature, stir 9-10h, by product suction filtration, washing, 75 DEG C of freeze-day with constant temperature 20-22h, i.e. obtained modification magnesium aluminum-hydrotalcite, the quality of described toxilic acid and the quality both citric acid and the volume ratio 0.01-0.02g/mL with ethylene glycol, Mg/Al hydrotalcite and toxilic acid and citric acid and ratio be 1:1-1.5;
(2) by formula rate, modification magnesium aluminum-hydrotalcite obtained for step (1), Mono-n-butyltin, lauric acid lanthanum, cerium stearate, annular phosphate, pentanedioic acid zinc, epoxy soybean oil are placed in high energy vibration equipment with the abundant vibration 40-50 minute of the rotating speed of 600-800 rev/min, vibration temperature 50-60 DEG C, obtains mixture A;
(3) add in stirring tank by phthalic acid polyester, be slowly warming up to 65-68 DEG C, add all the other components in the obtained mixture A of step (2) and formula, keep homo(io)thermism, fully stir 1.5-2.0 hour, cooling obtains one package stabilizer.
beneficial effect
One package stabilizer of the present invention is by modified hydrotalcite LDH, Mono-n-butyltin, lauric acid lanthanum, the one package stabilizer that cerium stearate and other additive compound obtain, there is between raw material fine synergistic stability effect, modified hydrotalcite obviously can improve the long-term thermal stability of PVC, rare earth element has stronger ligand complex ability, with the unstable chlorine effect in PVC, thus heat stabilization is played to PVC, adding of rare-earth stabilizer can suppress Zinic stearas to PVC, " zinc burning " occur and produce metachromatism, the fusion time of PVC can be shortened simultaneously, reduce the energy consumption adding man-hour.Modified hydrotalcite, rare earth thermal stabilizer and other auxiliary agent with the use of time, synergistic effect can be produced, effectively can improve thermostable effect, the over-all properties of its double matching type heat stabilizer is better than traditional lead salt and metal soap stablizer and organotin, organotin can be replaced, reduce goods cost, this one package stabilizer is novel, compound, High-efficient Water talcum rare earth composite environmental-friendly thermo-stabilizer.
Embodiment
A kind of PVC hydrotalcite pentanedioic acid zinc composite environmental-friendly stablizer, it is prepared by the component raw material of following weight (kg) and obtains: modification magnesium aluminum-hydrotalcite 24, Mono-n-butyltin 11, lauric acid lanthanum 7, cerium stearate 5, annular phosphate 2, pentanedioic acid zinc 5, epoxy soybean oil 3, phthalic acid polyester 13, polyethylene wax 1, Trivalin SF 5, three (1,2,2,6,6-Pempiten base) phosphorous acid ester 3, Zinic stearas 5, calcinated argil 5
Preparation method is as follows:
(1) preparation of modified hydrotalcite:
A, get a certain amount of Mg (NO3) 26H2O and Al (NO3) 39H2O and be added to the water and be made into the salts solution that total mol concentration is 0.6mol/L, get a certain amount of NaOH and Na2CO3 and add in deionized water that to be made into total mol concentration be 0.6mol/L alkaline solution, by alkaline solution with 1-2 drip/s speed drops in salts solution, N
2the lower violent stirring of protection, constant temperature 38-42 DEG C, pH value remains between 9.5 ~ 10, at stirring 1-1.5h after dropwising, after 75 DEG C of crystallization 8h suction filtrations, washing is to neutral, will precipitate 45-50 DEG C of oven dry, obtain Mg/Al hydrotalcite, wherein the mol ratio of Mg (NO3) 26H2O and Al (NO3) 39H2O is the mol ratio 2:1 of 2:3, NaOH and Na2CO3, the volume ratio 1-1.2:1 of alkaline solution and salts solution during dropping;
B, toxilic acid and citric acid take according to the ratio that mol ratio is 1:1-2 and are a certain amount ofly dissolved in analytical pure ethylene glycol, after abundant mixing, add the Mg/Al hydrotalcite that step (1) is obtained, under 85-88 DEG C of constant temperature, stir 9-10h, by product suction filtration, washing, 75 DEG C of freeze-day with constant temperature 20-22h, i.e. obtained modification magnesium aluminum-hydrotalcite, the quality of described toxilic acid and the quality both citric acid and the volume ratio 0.01-0.02g/mL with ethylene glycol, Mg/Al hydrotalcite and toxilic acid and citric acid and ratio be 1:1-1.5;
(2) by formula rate, modification magnesium aluminum-hydrotalcite obtained for step (1), Mono-n-butyltin, lauric acid lanthanum, cerium stearate, annular phosphate, pentanedioic acid zinc, epoxy soybean oil are placed in high energy vibration equipment with the abundant vibration 40-50 minute of the rotating speed of 600-800 rev/min, vibration temperature 50-60 DEG C, obtains mixture A;
(3) add in stirring tank by phthalic acid polyester, be slowly warming up to 65-68 DEG C, add all the other components in the obtained mixture A of step (2) and formula, keep homo(io)thermism, fully stir 1.5-2.0 hour, cooling obtains one package stabilizer.
Carried out a series of test by congo red method to the thermal stability of thermo-stabilizer, concrete grammar is joined
According to GB/T2917.1-2002 " releasing the mensuration congo red method of hydrogenchloride and any other acid product based on the blend of vinyl chloride homo and multipolymer and goods when high temperature ".The compound rare-earth thermo-stabilizer of the interpolation modified hydrotalcite obtained by the present embodiment and the rare earth thermal stabilizer not adding modified hydrotalcite contrast, draw through test, modified hydrotalcite and auxiliary stabilizer is added in rare earth compound, its performance as PVC heat stabilizer can be improved, PVC thermostability can be brought up to more than 50 minutes, and common rare earth thermal stabilizer is generally at about 30 minutes.
Claims (2)
1. a PVC hydrotalcite pentanedioic acid zinc composite environmental-friendly stablizer, it is characterized in that: it is prepared by the component raw material of following weight part and obtains: modification magnesium aluminum-hydrotalcite 20-30, Mono-n-butyltin 10-12, lauric acid lanthanum 6-9, cerium stearate 4-6, annular phosphate 1-3, pentanedioic acid zinc 3-6, epoxy soybean oil 2-4, phthalic acid polyester 12-14, polyethylene wax 1-2, Trivalin SF 5-6, three (1,2,2,6,6-Pempiten base) phosphorous acid ester 2-3, Zinic stearas 4-6, calcinated argil 4-5.
2. the preparation method of PVC hydrotalcite pentanedioic acid zinc composite environmental-friendly stablizer according to claim 1, is characterized in that, comprise the following steps:
(1) preparation of modified hydrotalcite:
A, get a certain amount of Mg (NO3) 26H2O and Al (NO3) 39H2O and be added to the water and be made into the salts solution that total mol concentration is 0.6mol/L, get a certain amount of NaOH and Na2CO3 and add in deionized water that to be made into total mol concentration be 0.6mol/L alkaline solution, by alkaline solution with 1-2 drip/s speed drops in salts solution, N
2the lower violent stirring of protection, constant temperature 38-42 DEG C, pH value remains between 9.5 ~ 10, at stirring 1-1.5h after dropwising, after 75 DEG C of crystallization 8h suction filtrations, washing is to neutral, will precipitate 45-50 DEG C of oven dry, obtain Mg/Al hydrotalcite, wherein the mol ratio of Mg (NO3) 26H2O and Al (NO3) 39H2O is the mol ratio 2:1 of 2:3, NaOH and Na2CO3, the volume ratio 1-1.2:1 of alkaline solution and salts solution during dropping;
B, toxilic acid and citric acid take according to the ratio that mol ratio is 1:1-2 and are a certain amount ofly dissolved in analytical pure ethylene glycol, after abundant mixing, add the Mg/Al hydrotalcite that step (1) is obtained, under 85-88 DEG C of constant temperature, stir 9-10h, by product suction filtration, washing, 75 DEG C of freeze-day with constant temperature 20-22h, i.e. obtained modification magnesium aluminum-hydrotalcite, the quality of described toxilic acid and the quality both citric acid and the volume ratio 0.01-0.02g/mL with ethylene glycol, Mg/Al hydrotalcite and toxilic acid and citric acid and ratio be 1:1-1.5;
(2) by formula rate, modification magnesium aluminum-hydrotalcite obtained for step (1), Mono-n-butyltin, lauric acid lanthanum, cerium stearate, annular phosphate, pentanedioic acid zinc, epoxy soybean oil are placed in high energy vibration equipment with the abundant vibration 40-50 minute of the rotating speed of 600-800 rev/min, vibration temperature 50-60 DEG C, obtains mixture A;
(3) add in stirring tank by phthalic acid polyester, be slowly warming up to 65-68 DEG C, add all the other components in the obtained mixture A of step (2) and formula, keep homo(io)thermism, fully stir 1.5-2.0 hour, cooling obtains one package stabilizer.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106633490A (en) * | 2016-11-10 | 2017-05-10 | 周荣 | Preparation method of polyvinyl chloride antistatic film |
| CN114349441A (en) * | 2022-01-24 | 2022-04-15 | 安徽耐斯特新材料科技有限公司 | Anticorrosive wear-resistant ceramic coating for cement equipment and preparation method thereof |
| CN115716933A (en) * | 2022-11-22 | 2023-02-28 | 浙江丰虹新材料股份有限公司 | Easily-dispersible hydrotalcite-based composite material for polymer and preparation method thereof |
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| CN87105970A (en) * | 1986-12-29 | 1988-08-10 | 住友化学工业株式会社 | The poly (vinyl chloride) resin composition that is used for powder molding |
| CN1590437A (en) * | 2004-04-29 | 2005-03-09 | 北京化工大学 | Hgdrotalcite base chlorine containing high polymer composite heat stabilizing agent |
| CN101492548A (en) * | 2009-02-20 | 2009-07-29 | 中南大学 | Composite heat stabilizer for PVC, preparation and application thereof |
| CN104893136A (en) * | 2014-03-03 | 2015-09-09 | 南通艾德旺化工有限公司 | Preparation method for modified composite magnesium aluminum hydrotalcite heat stabilizer |
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2015
- 2015-11-18 CN CN201510793097.0A patent/CN105295245A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN87105970A (en) * | 1986-12-29 | 1988-08-10 | 住友化学工业株式会社 | The poly (vinyl chloride) resin composition that is used for powder molding |
| CN1590437A (en) * | 2004-04-29 | 2005-03-09 | 北京化工大学 | Hgdrotalcite base chlorine containing high polymer composite heat stabilizing agent |
| CN101492548A (en) * | 2009-02-20 | 2009-07-29 | 中南大学 | Composite heat stabilizer for PVC, preparation and application thereof |
| CN104893136A (en) * | 2014-03-03 | 2015-09-09 | 南通艾德旺化工有限公司 | Preparation method for modified composite magnesium aluminum hydrotalcite heat stabilizer |
Non-Patent Citations (1)
| Title |
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| 于静: "PVC用稀土热稳定剂研究进展", 《中国塑料》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106633490A (en) * | 2016-11-10 | 2017-05-10 | 周荣 | Preparation method of polyvinyl chloride antistatic film |
| CN114349441A (en) * | 2022-01-24 | 2022-04-15 | 安徽耐斯特新材料科技有限公司 | Anticorrosive wear-resistant ceramic coating for cement equipment and preparation method thereof |
| CN115716933A (en) * | 2022-11-22 | 2023-02-28 | 浙江丰虹新材料股份有限公司 | Easily-dispersible hydrotalcite-based composite material for polymer and preparation method thereof |
| CN115716933B (en) * | 2022-11-22 | 2024-02-06 | 浙江丰虹新材料股份有限公司 | Easily-dispersible hydrotalcite-based composite material for polymer and preparation method thereof |
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Inventor after: Li Yi Inventor after: Qiu Yonggui Inventor after: Wang Shengmao Inventor after: Gao Xu Inventor after: Song Kaisheng Inventor after: Xu Ming Inventor after: Xiao Dushan Inventor before: Wang Shengmao Inventor before: Qiu Yonggui Inventor before: Song Kaisheng Inventor before: Gao Xu Inventor before: Li Yi Inventor before: Xu Ming Inventor before: Xiao Dushan Inventor before: Sun Rongxing |
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Application publication date: 20160203 |
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