CN105295218A - Hydrotalcite and lanthanum ricinoleate composite environmental-protection stabilizer for PVC and preparation method thereof - Google Patents
Hydrotalcite and lanthanum ricinoleate composite environmental-protection stabilizer for PVC and preparation method thereof Download PDFInfo
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- CN105295218A CN105295218A CN201510792975.7A CN201510792975A CN105295218A CN 105295218 A CN105295218 A CN 105295218A CN 201510792975 A CN201510792975 A CN 201510792975A CN 105295218 A CN105295218 A CN 105295218A
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Abstract
The invention provides a hydrotalcite and lanthanum ricinoleate composite environmental-protection stabilizer for PVC. The hydrotalcite and lanthanum ricinoleate composite environmental-protection stabilizer for PVC is prepared from the following raw materials (by weight): 20-30 parts of modified Mg-Al hydrotalcite, 10-12 parts of tin dilaurate, 6-9 parts of lanthanum ricinoleate, 1-3 parts of triethyl phosphate, 3-6 parts of barium stearate, 2-4 parts of epoxidized soybean oil, 10-13 parts of propanediol sebacate polyester, 5-6 parts of zinc stearate, 2-4 parts of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 2-4 parts of ethylene bis-stearamide and 10-14 parts of potassium feldspar powder. The PVC stabilizer of the invention has good heat stability and processability, is environmentally-friendly, nontoxic and low-cost, has good plasticity during processing of PVC, can reduce balance torque and has good transparency.
Description
Technical field
The present invention relates to PVC auxiliary agent field, be specifically related to a kind of PVC hydrotalcite ricinolic acid lanthanum composite environmental-friendly stablizer 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 ricinolic acid lanthanum 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 ricinolic acid lanthanum 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, tin dilaurate tin 10-12, ricinolic acid lanthanum 6-9, triethyl phosphate 1-3, barium stearate 3-6, epoxy soybean oil 2-4, sebacic acid propanediol polyester 10-13, Zinic stearas 5-6,4-benzoyloxy-2,2,6,6-tetramethyl piperidine 2-4, ethylene bis stearamide 2-4, feldspar in powder 10-14.
The preparation method of described PVC hydrotalcite ricinolic acid lanthanum 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), tin dilaurate tin, ricinolic acid lanthanum, triethyl phosphate, barium stearate, 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 sebacic acid propanediol 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
The application is by modified hydrotalcite, tin dilaurate tin, ricinolic acid lanthanum, the one package stabilizer that triethyl phosphate and other additive compound obtain, there is between raw material fine synergistic stability effect, traditional hydrotalcite can absorb the HCl gas that PVC degraded is deviate from, play heat-staple effect, but primary stability is bad, the application adopts toxilic acid and citric acid to carry out modification to hydrotalcite LDH, the modified primary stability of hydrotalcite LDH to PVC improves a lot, modified hydrotalcite LDH is carrying out composite with organotin and rare earth and other auxiliary addition agent agent, obtain the one package stabilizer of the application, it has synergistic stability effect to PVC, while improving stability, reduce goods cost, the ligand complex ability that rare earth is stronger, with the unstable chlorine effect in PVC, thus heat stabilization is played to PVC, rare earth has initial stage anti-zinc and burns ability and long-term thermal stability, good effect is had to the resistance toheat and mechanical property that improve PVC plastic, have nontoxic, radioprotective, efficiently, environmental protection good characteristic, and cost is low.
Modified hydrotalcite, rare earth thermal stabilizer, organotin 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 often better than traditional lead salt and metal soap stablizer, in some applications, rare earth composite stabilizer partly or entirely can replace organotin, reduces goods cost, and this one package stabilizer is novel, compound, High-efficient Water talcum rare earth composite environmental-friendly thermo-stabilizer.
Embodiment
A kind of PVC hydrotalcite ricinolic acid lanthanum composite environmental-friendly stablizer, it is prepared by the component raw material of following weight (kg) and obtains: modification magnesium aluminum-hydrotalcite 26, tin dilaurate tin 12, ricinolic acid lanthanum 6, triethyl phosphate 2, barium stearate 5, epoxy soybean oil 3, sebacic acid propanediol polyester 12, Zinic stearas 6,4-benzoyloxy-2,2,6,6-tetramethyl piperidine 3, ethylene bis stearamide 3, feldspar in powder 13
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), tin dilaurate tin, ricinolic acid lanthanum, triethyl phosphate, barium stearate, 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 sebacic acid propanediol 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.
The mensuration of thermal stability
1, static heat stability measures:
By 3.5:100 ratio of quality and the number of copies, the composite thermal stabilizer produce the present embodiment and Ga/Zn one package stabilizer add in PVC respectively, and adopt congo-red test paper method to determine static heat stability, result is as follows:
Static heat steady time of Ga/Zn one package stabilizer is 60min, composite thermal stabilizer static heat steady time that the present embodiment is produced is 1,19min, can find out that composite thermal stabilizer static heat stability that the present embodiment is produced obviously is better than the static heat stability of Ga/Zn one package stabilizer.
2, dynamic thermal stability measures:
Add the condition of 3.5 parts of thermo-stabilizers in 100 parts of PVC under, measure Ga/Zn one package stabilizer respectively, the dynamic thermal stability energy of the composite thermal stabilizer that the present embodiment is produced, result is: the heat-stable time of Ga/Zn one package stabilizer is 35.6min, plasticizing torque and balancing moment are 52Nm and 31.0Nm, the heat-stable time of the composite thermal stabilizer that the present embodiment is produced is 45min, plasticizing torque and balance torque drop are 46.6Nm and 24.4Nm, compared with Ga/Zn one package stabilizer, steady time obviously extends, plasticizing torque and balancing moment obviously decline, can find out that stablizer of the present invention more effectively can improve PVC dynamic thermal stability energy, reduce power consumption of polymer processing.
Claims (2)
1. a PVC hydrotalcite ricinolic acid lanthanum 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, tin dilaurate tin 10-12, ricinolic acid lanthanum 6-9, triethyl phosphate 1-3, barium stearate 3-6, epoxy soybean oil 2-4, sebacic acid propanediol polyester 10-13, Zinic stearas 5-6,4-benzoyloxy-2,2,6,6-tetramethyl piperidine 2-4, ethylene bis stearamide 2-4, feldspar in powder 10-14.
2. the preparation method of PVC hydrotalcite ricinolic acid lanthanum 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), tin dilaurate tin, ricinolic acid lanthanum, triethyl phosphate, barium stearate, 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 sebacic acid propanediol 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 |
|---|---|---|---|---|
| CN106565993A (en) * | 2016-11-10 | 2017-04-19 | 周荣 | Preparation method of environment-friendly composite heat stabilizer |
| CN106566128A (en) * | 2016-10-28 | 2017-04-19 | 祖兴保 | Triethyl phosphate composite environment-friendly stabilizer for PVC and preparation method thereof |
| CN106633490A (en) * | 2016-11-10 | 2017-05-10 | 周荣 | Preparation method of polyvinyl chloride antistatic film |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1590437A (en) * | 2004-04-29 | 2005-03-09 | 北京化工大学 | Hgdrotalcite base chlorine containing high polymer composite heat stabilizing agent |
| CN101007878A (en) * | 2006-01-25 | 2007-08-01 | 扬州科宇化工有限公司 | Hydrotalcite-rare earth-calcium zinc stablizer for PVC and its preparation method |
| CN101492548A (en) * | 2009-02-20 | 2009-07-29 | 中南大学 | Composite heat stabilizer for PVC, preparation and application thereof |
| CN103194005A (en) * | 2013-04-01 | 2013-07-10 | 石河子大学 | Method for preparing novel polyvinyl chloride (PVC) rare-earth heat stabilizer |
| 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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- 2015-11-18 CN CN201510792975.7A patent/CN105295218A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1590437A (en) * | 2004-04-29 | 2005-03-09 | 北京化工大学 | Hgdrotalcite base chlorine containing high polymer composite heat stabilizing agent |
| CN101007878A (en) * | 2006-01-25 | 2007-08-01 | 扬州科宇化工有限公司 | Hydrotalcite-rare earth-calcium zinc stablizer for PVC and its preparation method |
| CN101492548A (en) * | 2009-02-20 | 2009-07-29 | 中南大学 | Composite heat stabilizer for PVC, preparation and application thereof |
| CN103194005A (en) * | 2013-04-01 | 2013-07-10 | 石河子大学 | Method for preparing novel polyvinyl chloride (PVC) rare-earth heat stabilizer |
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106566128A (en) * | 2016-10-28 | 2017-04-19 | 祖兴保 | Triethyl phosphate composite environment-friendly stabilizer for PVC and preparation method thereof |
| CN106565993A (en) * | 2016-11-10 | 2017-04-19 | 周荣 | Preparation method of environment-friendly composite heat stabilizer |
| CN106633490A (en) * | 2016-11-10 | 2017-05-10 | 周荣 | Preparation method of polyvinyl chloride antistatic film |
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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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