CN101343389B - Low-plumbum high-efficiency compound stabilizer for polyvinyl chloride and preparation thereof - Google Patents
Low-plumbum high-efficiency compound stabilizer for polyvinyl chloride and preparation thereof Download PDFInfo
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- CN101343389B CN101343389B CN2008101392387A CN200810139238A CN101343389B CN 101343389 B CN101343389 B CN 101343389B CN 2008101392387 A CN2008101392387 A CN 2008101392387A CN 200810139238 A CN200810139238 A CN 200810139238A CN 101343389 B CN101343389 B CN 101343389B
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Abstract
The invention relates to a low-lead and efficient compound stabilizer used for polyvinyl chloride. The weight composition adopts 10 parts to 15 parts of tribasic lead sulfate, 5 parts to 10 parts of dibasic lead phosphite, 5 parts of mono-glyceride, 5 parts of polyethylene wax, 35 parts to 40 parts of calcium and zinc stearate compound, 25 parts of epoxy soybean oil and 10 parts of light calcium carbonate. Wherein, the calcium and zinc stearate compound is the compound formed through high temperature processing of calcium stearate and zinc stearate with the mole proportion which is 1:1. Compared with other lead salt compound stabilizer, the low-lead and efficient compound stabilizer is a novel compound stabilizer compounded between the calcium and zinc stearate compound and the lead salt,thus the lead content is reduced and the problem that the instability of the calcium and zinc compound stabilizer at later stage is solved. The stabilizer has the advantages that the performance is good, and the stabilizer is low poisonous, highly efficient, pollution-free and has low energy consumption.
Description
Technical field
The present invention relates to a kind of one package stabilizer that is used for polyvinyl chloride.
Background technology
Polyvinyl chloride (PVC) is one of the most frequently used plastics, and its advantage is that intensity height, insulativity and the transparency are good etc.Its disadvantage is to be heated for a long time down at the processing temperature conditioned disjunction, easily decomposes, and terms of settlement is to add thermo-stabilizer in the PVC course of processing, stops or delays this process.In addition, polyvinyl chloride is heated or when being subjected to ultraviolet radiation, also can causing the degraded of polymkeric substance and take off HCl.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.
Existing many about PVC with the patent of one package stabilizer, as " PVC profiled material preparation method of rare earth composite stabilizer special and application (patent No. 200510116791.5) ", " polyvinyl-chloride use Ca-Zn-Sn one package stabilizer and preparation method thereof (patent No. 200410081233.5) " etc., though the product of these patents has nontoxic advantage, cost an arm and a leg but exist, there are shortcomings such as smell difference in poor stability and some, therefore, domestic most of PVC section bar producer tends to the higher lead salt stabilizer of usability price ratio, and using more now is the complex lead salt stabilizer of excellent property.
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 toxicity height, coloring plastic difficulty, 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 harm to operator and environment.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.But complex lead salt stabilizer is owing to the lead content height, and environmental pollution is serious, and PVC has been trend of the times with the one package stabilizer low toxic and environment-friendlyization.Therefore, all at exploitation low toxicity or non-toxic stabilizer, calcium-zinc composite stabilizing agent is a wherein most important kind both at home and abroad.
The calcium-zinc composite stabilizing agent great advantage is nontoxic, and its main deficiency is that later stage stability is undesirable, needs composite with various auxiliary stabilizers.
Summary of the invention
Technical problem to be solved by this invention provides a kind of low-plumbum high-efficiency compound stabilizer for polyvinyl chloride and preparation method thereof, to reduce the later stage unstable of plumbous content and solution calcium-zinc composite stabilizing agent.
Low-plumbum high-efficiency compound stabilizer for polyvinyl chloride of the present invention is characterized in that its weight consists of:
10 parts of 10～15 parts of tribasic lead sulfates, 5～10 parts of dibasic Lead Phosphites, 5 parts of mono-glyceridess and 5 parts of polyethylene waxs, 35～40 parts of calcium stearate zinc complexes, 25 parts of epoxy soybean oils and light calcium carbonates.
Wherein said calcium stearate zinc complexes is to be that calcium stearate and the Zinic stearas of 1:1 at high temperature handled the mixture that forms by molar ratio.Its preparation method can be by following dual mode:
First kind: after calcium stearate, Zinic stearas fully ground in molar ratio 1:1 mix, 5% stearic acid that adds calcium stearate and Zinic stearas weight is done the catalysis dispersion agent, stir, elevated temperature to 160～170 ℃, insulation 30min, be cooled to room temperature, fully grind, obtain the calcium stearate zinc complexes.
Second kind: 74kg calcium hydroxide and 81kg zinc oxide are mixed, add the 245kg stearic acid, after stirring, add the catalyzer (mixture of sulfuric acid and Glacial acetic acid, mass ratio is 1:3) 1.0kg, slowly be warming up to 145～150 ℃, insulation 3h, elevated temperature to 160～170 ℃ again, insulation 30min is cooled to room temperature (20～30 ℃), ageing 1h, pulverize to grind, sieve white powder calcium stearate zinc complexes.
The preparation method of low-plumbum high-efficiency compound stabilizer is: in reactor, add the calcium stearate zinc complexes, be warmed up to 110～115 ℃, slowly add epoxy soybean oil, the back that stirs adds Tegin 55G, polyethylene wax and light calcium carbonate, continues to add three salt and disalt after fully stirring again, 110 ℃ of insulations down, after treating that material stirs, material is emitted, get product.
The prepared low-plumbum high-efficiency compound stabilizer of the present invention can be powder, particle, sheet or paste.
Advantage of the present invention:
Stablizer of the present invention is the complex body of multiple stablizer and lubricant, has good synergisticing stable effect, needn't add other stablizer or lubricant in use, easy to use, can reduce the batching program, save the labor force and reduce the batching error, reach efficient operation.
Low-plumbum high-efficiency compound stabilizer of the present invention is by the calcium stearate zinc complexes and lead salt is composite forms, and has both solved the unfavorable drawback of calcium-zinc composite stabilizing agent later stage stabilising effect, has reduced the content of stablizer lead salt again, thereby has reduced the harm of lead salt to environment.
By GB GB2113-82 " plastics whiteness experimental technique ", the low-plumbum high-efficiency compound stabilizer of the present invention's preparation is compared with traditional stablizer, has outstanding thermostability.Also can find by the dynamic thermal stability simultaneous test, use the low-plumbum high-efficiency compound stabilizer of the present invention's preparation that the dynamic thermal stability time of PVC plastics is obviously prolonged.
Embodiment
Below in conjunction with embodiment the present invention is described, but does not limit the present invention.
Embodiment 1: the preparation of calcium stearate zinc complexes
Get commercially available calcium stearate, Zinic stearas is even by 1.0:1.0 (mol ratio) mixed, add 5% the stearic acid account for calcium stearate and Zinic stearas gross weight, after stirring, elevated temperature to 160～170 ℃ slowly, insulation 30min, be cooled to room temperature, fully grind, obtain the calcium stearate zinc complexes.
Embodiment 2: the preparation of calcium stearate zinc complexes
74kg calcium hydroxide and 81kg zinc oxide are mixed, add the 245kg stearic acid, after stirring, add catalyzer (sulfuric acid and Glacial acetic acid mass ratio are 1:3) 1.0kg, slowly be warming up to 135～145 ℃, insulation 3h, elevated temperature to 160～170 ℃ again, insulation 30min, be cooled to room temperature (20～30 ℃), ageing 1h pulverize to grind, sieve white powder calcium stearate zinc complexes.
Embodiment 3: the preparation of low-plumbum high-efficiency compound stabilizer
In that being housed, agitator, temperature take into account the 2m of heating jacket
3In the stainless steel cauldron, add 800kg calcium stearate zinc complexes (embodiment 1 preparation), be warmed up to 110～115 ℃, slowly add the 500kg epoxy soybean oil.After stirring insulation 30min, add 100kg Tegin 55G, 100kg polyethylene wax and 200kg light calcium carbonate more successively.Continue to add 200kg three salt and 100kg disalt again.110 ℃ of down insulations, treat that material stirs after, material is emitted, product, also further granulation (or compressing tablet) moulding gets granular (or sheet) product.Prescription is seen formula table 1, formula number DQ-101 in detail.
Embodiment 4: the preparation of low-plumbum high-efficiency compound stabilizer
In that being housed, agitator, temperature take into account the 2m of heating jacket
3In the stainless steel cauldron, add 700kg calcium stearate zinc complexes (embodiment 2 preparations), be warmed up to 110～115 ℃, slowly add the 500kg epoxy soybean oil.After stirring insulation 30min, add 100kg Tegin 55G, 100kg polyethylene wax and 200kg light calcium carbonate more successively.Continue to add 300kg three salt and 200kg disalt again.110 ℃ of down insulations, treat that material stirs after, material is emitted, product, also further granulation (or compressing tablet) moulding gets granular (or sheet) product.Prescription is seen formula table 1, formula number DQ-102 in detail.
Table 1
Table 2
Three kinds of PVC plastics by table 2 preparation are carried out heat-resisting whiteness experiment, and table 3 is that being placed on test piece with whiteness is the relative whiteness value of testing in the whiteness instrument checked of 85% standard white body.Can find that from table 3 prepared low-plumbum high-efficiency compound stabilizer is compared with traditional stablizer, has outstanding thermostability.
Also can find by the dynamic thermal stability simultaneous test, use low-plumbum high-efficiency compound stabilizer prescription DQ-101 and DQ-102 can make the dynamic thermal stability time of PVC plastics obviously prolong (seeing Table 4).
Table 3
Table 4
Claims (4)
1. low-plumbum high-efficiency compound stabilizer for polyvinyl chloride is characterized in that its weight consists of:
25 parts of 10～15 parts of tribasic lead sulfates, 5～10 parts of dibasic Lead Phosphites, 5 parts of mono-glyceridess, 5 parts of polyethylene waxs, 10 parts of light calcium carbonates, 35～40 parts of calcium stearate zinc complexes and epoxy soybean oils.
2. low-plumbum high-efficiency compound stabilizer for polyvinyl chloride according to claim 1 is characterized in that described calcium stearate zinc complexes prepares in accordance with the following methods:
After calcium stearate, Zinic stearas fully ground in molar ratio 1:1 mix, add 5% stearic acid that accounts for calcium stearate and Zinic stearas gross weight and do the catalysis dispersion agent, stir, elevated temperature to 160～170 ℃, insulation 30min, be cooled to room temperature, fully grind, obtain calcium stearate-Zinic stearas mixture.
3. low-plumbum high-efficiency compound stabilizer for polyvinyl chloride according to claim 1, it is characterized in that described calcium stearate zinc complexes prepares in accordance with the following methods: 74kg calcium hydroxide and 81kg zinc oxide are mixed, add the 245kg stearic acid, after stirring, the mixture that adds mass ratio and be the sulfuric acid of 1:3 and Glacial acetic acid is as catalyzer 1.0kg, slowly be warming up to 145～150 ℃, insulation 3h, elevated temperature to 160～170 ℃ again, insulation 30min is cooled to room temperature, ageing 1h, pulverize to grind, sieve white powder calcium stearate zinc complexes.
4. method for preparing the described low-plumbum high-efficiency compound stabilizer for polyvinyl chloride of claim 1, it is characterized in that in reactor, add the calcium stearate zinc complexes, be warmed up to 110～115 ℃, slowly add epoxy soybean oil, back adding Tegin 55G, polyethylene wax and light calcium carbonate stir, continue to add tribasic lead sulfate and dibasic Lead Phosphite after fully stirring again, 110 ℃ of insulations down, treat that material stirs after, material is emitted, get product.
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| CN101935406B (en) * | 2010-09-06 | 2012-05-30 | 芜湖海螺型材科技股份有限公司 | Composite stabilizer for plastic sections |
| CN102807687B (en) * | 2012-08-24 | 2013-08-07 | 康泰塑胶科技集团有限公司 | Compound stabilizer for plastic pipe and preparation method thereof |
| CN103951849A (en) * | 2014-05-04 | 2014-07-30 | 江苏联盟化学有限公司 | Natural inorganic salt composite heat stabilizer and preparation method thereof |
| CN105295091B (en) * | 2015-11-25 | 2018-09-18 | 甄曰菊 | A kind of calcium zinc flame-retardant smoke inhibition material and preparation method, composite flame-proof suppression cigarette material and preparation method thereof |
| CN105670164B (en) * | 2016-01-22 | 2018-02-06 | 南京施瓦乐新材料科技有限公司 | A kind of compound bio capital construction building mould material and system |
| CN112694693A (en) * | 2020-12-25 | 2021-04-23 | 东莞市悠悠美居家居制造有限公司 | Lightweight cloth-imitated lace sheet, preparation method thereof and cloth-handfeel lace tablecloth |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1827699A (en) * | 2006-04-03 | 2006-09-06 | 中国科学院广州化学研究所 | Bamboo powder-polyvinyl chloride composite materials and process for preparing same |
| CN101041729A (en) * | 2006-03-23 | 2007-09-26 | 汕头市高科达有限公司 | (PVC) nontoxic calcium zinc heat stabilizer composition and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101041729A (en) * | 2006-03-23 | 2007-09-26 | 汕头市高科达有限公司 | (PVC) nontoxic calcium zinc heat stabilizer composition and preparation method thereof |
| CN1827699A (en) * | 2006-04-03 | 2006-09-06 | 中国科学院广州化学研究所 | Bamboo powder-polyvinyl chloride composite materials and process for preparing same |
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