CN102477196A - Novel molecular sieve PVC composite stabilizing agent and its preparation method - Google Patents

Novel molecular sieve PVC composite stabilizing agent and its preparation method Download PDF

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CN102477196A
CN102477196A CN2010105655853A CN201010565585A CN102477196A CN 102477196 A CN102477196 A CN 102477196A CN 2010105655853 A CN2010105655853 A CN 2010105655853A CN 201010565585 A CN201010565585 A CN 201010565585A CN 102477196 A CN102477196 A CN 102477196A
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molecular sieve
pvc
novel molecular
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stabilizer
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CN102477196B (en
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唐守余
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Huike High Tech Co.,Ltd.
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SHANDONG HUIKE ADDITIVES CO Ltd
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Abstract

The invention relates to a novel molecular sieve PVC (polyvinyl chloride) composite stabilizing agent and its preparation method. The stabilizing agent is characterized by comprising the following raw materials by mass percent: 20-40% of calcium stearate; 15-25% of zinc stearate; 5-15% of a molecular sieve; 8-20% of a lubricating agent; 8-15% of a surface modification agent; and 5-15% of an auxiliary heat stabilizing agent. The preparation method has no pollution and low energy consumption. According to the national standard GB2113-82 ''test for whiteness of plastics'', the prepared novel modification composite stabilizing agent, compared with traditional stabilizing agents, has excellent thermal stability. And the prepared molecular sieve in the invention has a micropore structure, and diameters of the pores are uniform in size.

Description

Novel molecular sieve PVC one package stabilizer and preparation method thereof
Technical field
The invention belongs to the PVC manufacture field, particularly a kind of novel molecular sieve PVC one package stabilizer and preparation method thereof.
Background technology
As everyone knows, PVC easy the decomposition, must add stablizer and just can make its smooth processing under the processing temperature condition.In addition, SE is heated or when receiving ultraviolet radiation, also can causes the degraded of polymkeric substance and take off HCl.Therefore, PVC's uses and processes and must use stablizer.Stablizer is a kind of chemical assistant, and it can suppress degraded and the variable color that PVC causes owing to heat, light action in machine-shaping and use.Stablizer can be divided into base lead salt stablizer, metallic soap class, organo-tin compound, organic stabilizer and one package stabilizer five big classes by its chemical structure.
Because advantages such as the lead salt stabilizer raw material is easy to get, production technique is simple, cheap, performance is outstanding are still most widely used kind so far, output accounts for 65% of China's stablizer output.The shortcoming of lead salt stabilizer is that toxicity is high, coloring plastic is difficult, the bad dispersibility in plastics etc., and particularly the powdery lead compound produces a large amount of lead salt dust in batching, stirring or plasticizing process, can produce greatly operator and environment to endanger.In order to overcome these shortcomings, adopt complex lead salt stabilizer mostly.Complex lead salt stabilizer is compared with traditional three salt, disalt, and performance improves a lot, and it with strong points, simple to operate reduced the processing technology that is mixed, thereby reduced dust pollution, reduced cost.In a word, complex lead salt stabilizer is celebrated with its excellent combination property.The complex lead salt stabilizer part that also comes with some shortcomings, poor like bad dispersibility with PVC base-material consistency, produce white point in the finished product of being everlasting, have a strong impact on section quality.Problems such as also there is painted ability in complex lead salt stabilizer, and versatility is not high.
Molecular sieve is a kind of silico-aluminate compound with cubic(al)grating.Molecular sieve has uniform microvoid structure, and its hole diameter is even, and the molecular adsorption littler than its diameter can be arrived the inside of vestibule in these holes; And polar molecule and saturated molecule had the preferentially adsorbed ability; Thereby can be different polarity degree, degree of saturation is different, and the different molsep of molecular size difference and boiling point comes; The effect that promptly has " screening " molecule is so claim molecular sieve.Because molecular sieve has the adsorptive power height, thermostability waits the unexistent advantage of other sorbent material by force, makes that molecular sieve obtains to use widely.Molecular sieve is Powdered crystal, and metalluster is arranged, and hardness is 3~5, and specific density is 2~2.8, and natural zeolite has color, and synthetic zeolite is a white, and water insoluble, thermostability and acid resistance improve along with the increase of SiO2/Al2O3 ratio of components.Molecular sieve has very big specific surface area, reaches 300~1000m2/g, and interior brilliant surface elevation polarization is one type of high-efficiency adsorbent, also is one type of solid acid, and there are very high acid concentration and strength of acid in the surface, can cause the catalyzed reaction of carbonium ion type.When other ions exchange in metals ion in forming and the solution, can adjust the aperture, change its adsorption property and catalytic property, thereby make the sieve catalyst of different performance.
Summary of the invention
Not enough according to prior art, technical problem to be solved by this invention is: a kind of novel molecular sieve PVC one package stabilizer is provided, has the strong and outstanding thermostability of adsorptivity.
The technical solution adopted for the present invention to solve the technical problems is: a kind of novel molecular sieve PVC one package stabilizer is provided, it is characterized in that being made up of the raw material of following mass percent:
Calcium stearate 20~40%;
Zinic stearas 15~25%;
Molecular sieve 5~15%;
Lubricant 8~20%;
Surface modifier 8~15%;
Auxiliary heat stabilizer 5~15%.
Described lubricant is polyethylene wax, Tegin 55G or Triple Pressed Stearic Acid.
Described surface modifier is pentaerythritol ester or triphenyl phosphite.
Described auxiliary heat stabilizer is epoxy soybean oil or diphenylpropane-1,3-dione(DPPO).
Said molecular sieve makes according to following steps:
(1) with kaolin at 550~650 ℃ of following roasting 2~3h;
(2) mix with soda ash, make the component mol ratio in the solution be controlled at n (H 2O)/n (Na 2O)/n (SiO 2)=1: 1.5: 2.5 is then at 60 ℃ of following ageing 2h;
(3) crystallization 4h under 90 ℃ of hydrothermal conditions;
(4) last warp filters and separates, and promptly gets molecular sieve with deionized water wash to neutral after drying.
The preparation method of described novel molecular sieve PVC one package stabilizer is characterized in that adding thorough mixing in the reaction kettle to calcium stearate, Zinic stearas and lubricant earlier, gets mixture; Add heating and stirring in the kneader; Add surface modifier, mediate 20min down, in kneader, add the composite thermal stabilizer kneading then and stir 30min at 100~110 ℃; Discharging compressing tablet, screening back are mixed composite with molecular sieve, packing.
The present invention adopts composite method, and calcium stearate, Zinic stearas are mixed, and adds lubricant, surface modifier and auxiliary stabilizer again and processes the stable composition system, again with the composite novel molecular sieve PVC one package stabilizer of processing of molecular sieve.
The invention has the beneficial effects as follows: (1) preparation method is pollution-free, energy consumption is low; By GB GB2113-82 " plastics whiteness experimental technique ", can find that from embodiment table 3 prepared new modified one package stabilizer is compared with traditional stablizer, has outstanding thermostability.
(2) the prepared molecular sieve of the present invention; Microvoid structure; Its hole diameter is even, and the molecular adsorption littler than its diameter can be arrived the inside of vestibule in these holes, as the stablizer of plastic workings such as PVC; Can the HCL molecular adsorption be arrived the cavity inside of molecular sieve, thereby reach stable effect.The molecular sieve that adds the present invention's preparation can reduce the consumption of stablizer, reduces cost.Through the PVC that adds molecular sieve being carried out the static-aging experiment, the result shows, adds the thermostability that one package stabilizer of the present invention can obviously improve PVC.Under 180 ± 1 ℃ of conditions, PVC not only has good initial coloring, and its heat-stable time has also reached more than 120~200min.
Embodiment
According to embodiment the present invention is described further below.
Embodiment 1
(1) with kaolin at 550~650 ℃ of following roasting 2~3h;
(2) mix with soda ash, make the component mol ratio in the solution be controlled at n (H 2O)/n (Na 2O)/n (SiO 2)=1: 1.5: 2.5 is then at 60 ℃ of following ageing 2h;
(3) crystallization 4h under 90 ℃ of hydrothermal conditions;
(4) last warp filters and separates, and promptly gets synthetic product with deionized water wash to neutral after drying.
The calcium stearate of preparation, Zinic stearas, lubricant, surface modifier and auxiliary heat stabilizer mix, and be composite with molecular sieve again, and concrete hybrid mode is following:
Earlier thorough mixing in 30 parts of calcium stearates, 25 parts of adding reaction kettles of Zinic stearas.Get mixture, add heating and stirring in the kneader, add 15 parts of pentaerythritol esters; Mediate 20min down at 100~110 ℃, in kneader, add 10 parts of polyethylene waxs, 15 parts of epoxy soybean oils then; Mediate and stir 30min, discharging compressing tablet, screening add in the mixer again and mix 30min for 5 parts with molecular sieve; The discharging packing had both got the finished product.
The foregoing description and two kinds of thermo-stabilizer 3 mass parts that do not add molecular sieve are added respectively among the 100 mass parts PVC; Add 60 mass parts dimixo-octyl phthalates (DOP) again; 140 ℃ mixing 10 minutes down, 100 ℃ press down and process the thin slice that thickness is 1mm, are cut into the test piece of 1cm * 1cm; Under 180 ± 1 ℃ of conditions, do the static-aging experiment, experimental result is seen table 1.Wherein embodiment 3 is a Comparative Examples.
Table 1
Figure BDA0000035182380000031
Embodiment 2,3
Above-mentioned molecular sieve stablizer is added among 100 parts of PVC by same amount, add 60 parts of dimixo-octyl phthalates (DOP) again,, carry out heat-resisting whiteness experiment to three kinds of PVC plastics of preparation then by GB GB2113-82 " plastics whiteness experimental technique ".Can find that from table 3 prepared novel molecular sieve PVC one package stabilizer is compared with traditional stablizer, has outstanding thermostability.
Table 2: composite thermal stabilizer compositing formula
Figure BDA0000035182380000041
Wherein: lubricant is selected from polyethylene wax, Tegin 55G or Triple Pressed Stearic Acid; Surface modifier is selected pentaerythritol ester or triphenyl phosphite; Auxiliary heat stabilizer is selected epoxy soybean oil or diphenylpropane-1,3-dione(DPPO).
Table 3: test piece is placed on and uses whiteness is the relative whiteness value of testing in the whiteness appearance checked of 85% standard white body (%)
Figure BDA0000035182380000042

Claims (6)

1. novel molecular sieve PVC one package stabilizer is characterized in that being made up of the raw material of following mass percent:
Calcium stearate 20~40%;
Zinic stearas 15~25%;
Molecular sieve 5~15%;
Lubricant 8~20%;
Surface modifier 8~15%;
Auxiliary heat stabilizer 5~15%.
2. novel molecular sieve PVC one package stabilizer according to claim 1 is characterized in that described lubricant is polyethylene wax, Tegin 55G or Triple Pressed Stearic Acid.
3. novel molecular sieve PVC one package stabilizer according to claim 1 is characterized in that described surface modifier is pentaerythritol ester or triphenyl phosphite.
4. novel molecular sieve PVC one package stabilizer according to claim 1 is characterized in that described auxiliary heat stabilizer is epoxy soybean oil or diphenylpropane-1,3-dione(DPPO).
5. novel molecular sieve PVC one package stabilizer according to claim 1 is characterized in that said molecular sieve makes according to following steps:
(1) with kaolin at 550~650 ℃ of following roasting 2~3h;
(2) mix with soda ash, make the component mol ratio in the solution be controlled at n (H 2O)/n (Na 2O)/n (SiO 2)=1: 1.5: 2.5 is then at 60 ℃ of following ageing 2h;
(3) crystallization 4h under 90 ℃ of hydrothermal conditions;
(4) last warp filters and separates, and promptly gets molecular sieve with deionized water wash to neutral after drying.
6. the preparation method of a novel molecular sieve PVC one package stabilizer according to claim 1 is characterized in that adding thorough mixing in the reaction kettle to calcium stearate, Zinic stearas and lubricant earlier, gets mixture; Add heating and stirring in the kneader; Add surface modifier, mediate 20min down, in kneader, add the composite thermal stabilizer kneading then and stir 30min at 100~110 ℃; Discharging compressing tablet, screening back are mixed composite with molecular sieve, packing.
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Cited By (17)

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CN102964744A (en) * 2012-12-10 2013-03-13 山东慧科助剂股份有限公司 Thermal stabilizer for aluminate modified molecular sieve PVC and preparation method thereof
CN103497448A (en) * 2013-09-30 2014-01-08 中国科学院长春应用化学研究所 Polyvinyl chloride slush moulding powder material and preparation method and application thereof
CN103613884A (en) * 2013-12-05 2014-03-05 山东慧科助剂股份有限公司 Efficient zinc-based composite heat stabilizer for PVC (polyvinyl chloride) and preparation method thereof
CN103665666A (en) * 2013-11-29 2014-03-26 山东国塑慧科高分子材料有限公司 Production method of novel molecular sieve PVC (polyvinyl chloride) composite stabilizer
CN103965565A (en) * 2013-12-05 2014-08-06 广西大学 Supported PVC (polyvinyl chloride) heat stabilizer and preparation method thereof
CN105199256A (en) * 2014-06-11 2015-12-30 中国石油化工股份有限公司 PVC wood-plastic foam material composition and preparation method thereof
CN105419130A (en) * 2015-12-31 2016-03-23 山东慧科助剂股份有限公司 Molecular sieve impact modification flexibilizer for polyvinyl chloride and preparing method thereof
CN104558987B (en) * 2013-10-22 2016-08-17 中国石油化工股份有限公司 A kind of environment-friendly type high thermal stability CPVC compositions
CN106280065A (en) * 2015-06-03 2017-01-04 常州嘉仁禾化学有限公司 A kind of mesoporous silicon load P VC heat stabilizer and preparation method thereof
CN106280066A (en) * 2015-06-08 2017-01-04 常州嘉仁禾化学有限公司 Mesoporous TiO 2 auxiliary PVC heat stabilizer and preparation method thereof
CN106432962A (en) * 2016-10-08 2017-02-22 台州联成化工有限公司 Moisture-proof calcium-zinc composite heat stabilizer and preparation method thereof
CN106519481A (en) * 2016-10-14 2017-03-22 瑞安市顺丰塑料助剂有限公司 Polyvinyl chloride light, soft and thermally-stable component for shoes, and preparation method thereof
CN106519304A (en) * 2016-10-14 2017-03-22 九江天盛塑料助剂有限公司 Molecular sieve supported polyvinyl chloride thermal stabilizer and preparation method thereof
CN106589687A (en) * 2016-12-09 2017-04-26 郑州搜趣信息技术有限公司 Heat stabilizer for polyvinyl chloride and preparation method of heat stabilizer
CN107245212A (en) * 2017-06-23 2017-10-13 巢湖市兰天大诚门窗幕墙有限公司 A kind of aluminum alloy doors and windows rubber weather strip is processed with dust-proof weather-proof additive
CN109054405A (en) * 2018-06-08 2018-12-21 江苏嘉仁禾科技有限公司 A kind of dedicated calcium zinc stabilizer of fruit freshness preserving film and preparation method thereof
CN109867882A (en) * 2019-03-05 2019-06-11 河源市鑫达科技有限公司 It is a kind of based on the PVC plastic of modified molecular screen heat stabilizer preparation process

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Cited By (22)

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Publication number Priority date Publication date Assignee Title
CN102964744A (en) * 2012-12-10 2013-03-13 山东慧科助剂股份有限公司 Thermal stabilizer for aluminate modified molecular sieve PVC and preparation method thereof
CN102964744B (en) * 2012-12-10 2016-06-01 山东慧科助剂股份有限公司 Thermal stabilizer for aluminate modified molecular sieve PVC and preparation method thereof
CN103497448A (en) * 2013-09-30 2014-01-08 中国科学院长春应用化学研究所 Polyvinyl chloride slush moulding powder material and preparation method and application thereof
CN103497448B (en) * 2013-09-30 2016-10-12 中国科学院长春应用化学研究所 A kind of polrvinyl chloride slush moulding powder material and preparation method thereof and application thereof
CN104558987B (en) * 2013-10-22 2016-08-17 中国石油化工股份有限公司 A kind of environment-friendly type high thermal stability CPVC compositions
CN103665666A (en) * 2013-11-29 2014-03-26 山东国塑慧科高分子材料有限公司 Production method of novel molecular sieve PVC (polyvinyl chloride) composite stabilizer
CN103613884A (en) * 2013-12-05 2014-03-05 山东慧科助剂股份有限公司 Efficient zinc-based composite heat stabilizer for PVC (polyvinyl chloride) and preparation method thereof
CN103965565A (en) * 2013-12-05 2014-08-06 广西大学 Supported PVC (polyvinyl chloride) heat stabilizer and preparation method thereof
CN103965565B (en) * 2013-12-05 2017-01-04 广西大学 A kind of support type PVC heat stabilizer and preparation method thereof
CN105199256A (en) * 2014-06-11 2015-12-30 中国石油化工股份有限公司 PVC wood-plastic foam material composition and preparation method thereof
CN106280065A (en) * 2015-06-03 2017-01-04 常州嘉仁禾化学有限公司 A kind of mesoporous silicon load P VC heat stabilizer and preparation method thereof
CN106280066A (en) * 2015-06-08 2017-01-04 常州嘉仁禾化学有限公司 Mesoporous TiO 2 auxiliary PVC heat stabilizer and preparation method thereof
CN105419130A (en) * 2015-12-31 2016-03-23 山东慧科助剂股份有限公司 Molecular sieve impact modification flexibilizer for polyvinyl chloride and preparing method thereof
CN106432962A (en) * 2016-10-08 2017-02-22 台州联成化工有限公司 Moisture-proof calcium-zinc composite heat stabilizer and preparation method thereof
CN106432962B (en) * 2016-10-08 2018-08-17 台州联成化工有限公司 Moisture-proof calcium-zinc composite heat stabilizer and preparation method thereof
CN106519481A (en) * 2016-10-14 2017-03-22 瑞安市顺丰塑料助剂有限公司 Polyvinyl chloride light, soft and thermally-stable component for shoes, and preparation method thereof
CN106519304A (en) * 2016-10-14 2017-03-22 九江天盛塑料助剂有限公司 Molecular sieve supported polyvinyl chloride thermal stabilizer and preparation method thereof
CN106519304B (en) * 2016-10-14 2018-11-09 九江天盛塑料助剂有限公司 A kind of molecular sieve carried type polychloroethylene heat stabilizer and preparation method thereof
CN106589687A (en) * 2016-12-09 2017-04-26 郑州搜趣信息技术有限公司 Heat stabilizer for polyvinyl chloride and preparation method of heat stabilizer
CN107245212A (en) * 2017-06-23 2017-10-13 巢湖市兰天大诚门窗幕墙有限公司 A kind of aluminum alloy doors and windows rubber weather strip is processed with dust-proof weather-proof additive
CN109054405A (en) * 2018-06-08 2018-12-21 江苏嘉仁禾科技有限公司 A kind of dedicated calcium zinc stabilizer of fruit freshness preserving film and preparation method thereof
CN109867882A (en) * 2019-03-05 2019-06-11 河源市鑫达科技有限公司 It is a kind of based on the PVC plastic of modified molecular screen heat stabilizer preparation process

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Address before: 256100 Yiyuan Economic Development Zone, Zibo City, Shandong Province

Patentee before: SHANDONG HUIKE ADDITIVES Co.,Ltd.

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Denomination of invention: New molecular sieve PVC composite stabilizer and its preparation method

Effective date of registration: 20220519

Granted publication date: 20140129

Pledgee: Yiyuan Shandong rural commercial bank Limited by Share Ltd.

Pledgor: Huike High Tech Co.,Ltd.

Registration number: Y2022980005817

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