CN101041728A - Preparation method for (PVC) nontoxic calcium zinc heat stabilizer and uses thereof - Google Patents
Preparation method for (PVC) nontoxic calcium zinc heat stabilizer and uses thereof Download PDFInfo
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- CN101041728A CN101041728A CN 200610065422 CN200610065422A CN101041728A CN 101041728 A CN101041728 A CN 101041728A CN 200610065422 CN200610065422 CN 200610065422 CN 200610065422 A CN200610065422 A CN 200610065422A CN 101041728 A CN101041728 A CN 101041728A
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Abstract
The invention discloses a manufacturing method of composite intoxic Ca-Zn heat stabilizer, which is characterized by the following: fusing high-level aliphatic acid and Ca-Zn oxide or hydroxide without solvent directly to synthesize integral stabilizer; complexing with sodium biphosphate, beta-diketone and bisphenol A; shortening manufacturing period from 15h to 6h; saving cost obviously.
Description
Technical field
The present invention relates to a kind of (PVC) nontoxic calcium zinc heat stabilizer preparation method and application thereof.
Background technology
Polyvinyl chloride (PVC) is to be only second to poly second largest plastics variety, and its outstanding feature is that intensity height, insulativity, the transparency are good etc., is widely used in industries such as building, electrical equipment, packing.The shortcoming of PVC maximum is, can degrade under long-term heating condition, discharges hydrogen chloride gas, thereby product properties is affected, and terms of settlement is to add thermo-stabilizer in the PVC course of processing, stops or delays this degraded.
The PVC thermo-stabilizer has experienced from the lead salt to barium, cadmium, zinc soap, and to fatty acid rare earth, to the evolution of nontoxic calcium zinc heat stabilizer, up to now, the domestic thermo-stabilizer that formed comprises more than 40 conventional variety, and about 150,000 tons of annual capacity is based on lead salt.Along with the needs of widening and replace timber, steel of plastics Application Areas, associated hot stablizer demand is just increasing with 10～15% speed, is to develop one of class faster in the additives for plastics industry.
The lead salts thermo-stabilizer is the PVC thermo-stabilizer that uses the earliest; its stabilising effect is fine; since the nineties in 20th century; because heavy metals such as lead, cadmium are to the human body murder by poisoning with to the severe contamination of environment; lead stabilizer is all used in restriction in countries in the world, and the thermo-stabilizer asepsis environment-protecting of PVC special use changes into and is trend of the times.Therefore, now equal both at home and abroad emphasis development and application non-toxic stabilizer, Ca-Zn composite heat stabilizer is a wherein most important kind.
The great advantage of Ca-Zn composite heat stabilizer is nontoxic, meets current economy, social development to environment requirement, in advanced industrial countries such as America and Europes, has substituted the lead salts thermo-stabilizer, becomes main plastic heat stabilizer product.China is main products with the lead salts stablizer still at present, but the nontoxicity thermo-stabilizer more and more draws attention, and will replace poisonous thermo-stabilizers such as lead salts, for example, rare earth thermal stabilizer is exactly a tangible example in the fast development of China in recent years, but generally speaking, the stability of rare earth thermal stabilizer can not be satisfied the demand well, and Ca-Zn composite heat stabilizer is considered to the inevitable development trend of thermo-stabilizer.So far, the main weak point of Ca-Zn composite heat stabilizer is that later stage stability is undesirable, need be composite with various auxiliary stabilizers, generally form by calcium zinc soap and various auxiliary agent.In addition, the main at present aqueous solution saponification method that adopts of the preparation method of calcium zinc soap, promptly at first lipid acid is obtained soap through replacement(metathesis)reaction, carry out saponification reaction with corresponding calcium or zinc salt again, after filtration, liquid, separation, drying, pulverizing washed, taken off and calcium soap or zinc soap obtained, the composite then Ca-Zn composite heat stabilizer that obtains.Traditional calcium soap, the zinc soap technological process of production and cycle are longer, and the energy consumption height is affected product performance thereby introduce impurity easily, and these deficiencies also are not resolved technically well.
Summary of the invention
The invention discloses a kind of new synthetic method of composite calcium zinc soap, on this basis further with the composite Ca-Zn composite heat stabilizers that obtain such as SODIUM PHOSPHATE, MONOBASIC, beta-diketon, dihydroxyphenyl propane.Compare with the old technology of tradition, novel method adopts a step scorification technology, and the zinc integrated main stabilizer of one-step synthesis calcium is then with other additive compounds.A new step melt production process is in the presence of the self-control composite catalyst, material metering is accurate, feed stock conversion is near 100%, starting material loss low (below 0.2%), labour intensity reduces greatly, with short production cyclely (reduced filtration, washing, dehydration, operations such as drying), be reduced to 4 hours by original 15 hours, plant factor improves (significantly bringing up to 85-90% by original about 10%) greatly, production energy consumption low (having reduced the dry materials link), (there are a large amount of chloride washess in old technology to three-waste free discharge, and novel process whole process of production by product only is the gaseous form of water), production cost is low, and stable and reliable product quality has tangible technology and economic advantages.Ca-Zn composite heat stabilizer preparation method of the present invention comprises the steps:
1) adds C according to a certain ratio
12～C
18Higher fatty acid, calcium zinc oxide or oxyhydroxide, composite catalyst, heating and melting and stirring reaction keep temperature～160 ℃, react about 2 hours.
2) react completely after, about 1 hour of material cooling, ageing after pulverizing, sieving, obtain the zinc integrated main stabilizer of calcium.
3) the zinc integrated main stabilizer of calcium and SODIUM PHOSPHATE, MONOBASIC, beta-diketon, dihydroxyphenyl propane etc. mix, mediate by metering and obtain Ca-Zn composite heat stabilizer after even.
Used higher fatty acid carbon number is C
12～C
18, calcium zinc mol ratio is 80: 20～50: 50, and higher fatty acid and calcium zinc mol ratio are 1.0: 1.0～1.0: 1.1, and calcium zinc source can be the oxyhydroxide of calcium, zinc, also can be the oxide compound of calcium, zinc; Auxiliary stabilizer comprises SODIUM PHOSPHATE, MONOBASIC, beta-diketon, dihydroxyphenyl propane etc., and the SODIUM PHOSPHATE, MONOBASIC consumption is 2～10%, and the consumption of beta-diketon is 10～20%, and the dihydroxyphenyl propane consumption is 1～5%; The consumption of composite catalyst is 0.05～2% of a higher fatty acid quality, is made of mineral acid mineral acid, monobasic or binary organic acid: the organic acid ratio is 1: 2; Mineral acid is sulfuric acid, hydrochloric acid, phosphoric acid, phosphorous acid etc.; Organic acid is that monobasic, binary organic acid are formic acid, acetate, propionic acid, Succinic Acid, hexanodioic acid etc.
Embodiment
Example 1: calcium zinc main stabilizer preparation
Press calcium (calcium hydroxide) zinc (zinc oxide) than (mol ratio) 70: 30, stearic acid (C
18) weigh than (mol ratio) 1.0: 1.1, composite catalyst (sulfuric acid+acetate+hexanodioic acid) consumption 0.2% (stearic acid quality) with calcium zinc, and with mixing of materials, heating and melting, stirring, keep temperature of reaction～160 ℃, reacted about 2 hours, about 1 hour of cooling, ageing, after pulverizing, sieving, obtain the zinc integrated main stabilizer A of calcium of white powder, stearic acid transformation efficiency 99.8%.
Example 2: calcium zinc main stabilizer preparation
Press calcium (calcium oxide) zinc (zinc oxide) than (mol ratio) 60: 40, lauric acid (C
12) weigh than (mol ratio) 1.0: 1.0, composite catalyst (phosphoric acid+propionic acid+hexanodioic acid) consumption 0.5% (lauric acid quality) with calcium zinc, and with mixing of materials, heating and melting, stirring, keep temperature of reaction～160 ℃, reacted about 2 hours, about 1 hour of cooling, ageing, after pulverizing, sieving, obtain the zinc integrated main stabilizer B of calcium of white powder, lauric acid transformation efficiency 99.9%.
Example 3: calcium zinc main stabilizer preparation
Press calcium (calcium hydroxide) zinc (zinc oxide) than (mol ratio) 60: 40, stearic acid (C
18) weigh than (mol ratio) 1.0: 1.0, composite catalyst (sulfuric acid+acetate+Succinic Acid) consumption 0.1% (stearic acid quality) with calcium zinc, and with mixing of materials, heating and melting, stirring, keep temperature of reaction～160 ℃, reacted about 2 hours, about 1 hour of cooling, ageing, pulverize, sieve, obtain the zinc integrated main stabilizer C of calcium of white powder, stearic acid transformation efficiency 99.9%.
Example 4: Ca-Zn composite heat stabilizer prescription and effect
The zinc integrated main stabilizer A of calcium and SODIUM PHOSPHATE, MONOBASIC, beta-diketon, dihydroxyphenyl propane etc. mix, mediate by metering and promptly obtain Ca-Zn composite heat stabilizer after even.Prescription (mass percent) and effect see the following form:
| Prescription | A | SODIUM PHOSPHATE, MONOBASIC | Beta-diketon | Dihydroxyphenyl propane | The static-aging experiment flavescence time, minute | The Congo red experiment variable color time, minute |
| 1 | 78 | 2 | 15 | 5 | 70 | 47 |
| 2 | 71 | 5 | 20 | 4 | 80 | 53 |
| 3 | 76 | 8 | 13 | 3 | 70 | 48 |
| 4 | 78 | 10 | 10 | 2 | 70 | 47 |
Illustrate: basic components: 100 parts of PVC, 15 parts in lime carbonate, ACR3 part, 3 parts of Ca-Zn composite heat stabilizers, down together.
Example 5: Ca-Zn composite heat stabilizer prescription and effect
The zinc integrated main stabilizer B of calcium and SODIUM PHOSPHATE, MONOBASIC, beta-diketon, dihydroxyphenyl propane etc. mix, mediate by metering and promptly obtain Ca-Zn composite heat stabilizer after even.Prescription (mass percent) and effect see the following form:
| Prescription | B | Beta-diketon | Dihydroxyphenyl propane | The static-aging experiment flavescence time, minute | The Congo red experiment variable color time, minute | |
| 1 | 78 | 2 | 15 | 5 | 70 | 49 |
| 2 | 71 | 5 | 20 | 4 | 70 | 51 |
| 3 | 76 | 8 | 13 | 3 | 70 | 47 |
| 4 | 78 | 10 | 10 | 2 | 70 | 47 |
Example 4: Ca-Zn composite heat stabilizer prescription and effect
The zinc integrated main stabilizer C of calcium and SODIUM PHOSPHATE, MONOBASIC, beta-diketon, dihydroxyphenyl propane etc. mix, mediate by metering and promptly obtain Ca-Zn composite heat stabilizer after even.Prescription (mass percent) and effect see the following form:
| Prescription | C | SODIUM PHOSPHATE, MONOBASIC | Beta-diketon | Dihydroxyphenyl propane | The static-aging experiment flavescence time, minute | The Congo red experiment variable color time, minute |
| 1 | 78 | 2 | 15 | 5 | 80 | 58 |
| 2 | 71 | 5 | 20 | 4 | 80 | 56 |
| 3 | 76 | 8 | 13 | 3 | 70 | 52 |
| 4 | 78 | 10 | 10 | 2 | 70 | 49 |
Claims (8)
1. (PVC) nontoxic calcium zinc heat stabilizer preparation method and application thereof is characterized in that: a step scorification prepares the zinc integrated main stabilizer of calcium, then with the composite Ca-Zn composite heat stabilizer that obtains of auxiliary stabilizer.
2. the preparation method of the zinc integrated main stabilizer of calcium as claimed in claim 1 is characterized in that: by higher fatty acid and calcium zinc oxide or oxyhydroxide, in the presence of composite catalyst, next step scorification of condition of no solvent is directly synthetic.
3. higher fatty acid carbon number as claimed in claim 2 is C
12～C
18Lipid acid.
4. as the preparation method of claim 1, the zinc integrated main stabilizer of 2 described calcium, it is characterized in that: calcium, zinc source can be the oxyhydroxide of calcium, zinc, it also can be the oxide compound of calcium, zinc, calcium zinc mol ratio is 80: 20～50: 50, and higher fatty acid and calcium zinc mol ratio are 1.0: 1.0～1.0: 1.1.
5. auxiliary stabilizer as claimed in claim 1 is characterized in that: form and comprise SODIUM PHOSPHATE, MONOBASIC, beta-diketon, dihydroxyphenyl propane etc., wherein, the SODIUM PHOSPHATE, MONOBASIC consumption is 2～10%, and the consumption of beta-diketon is 10～20%, and the dihydroxyphenyl propane consumption is 1～5%.
6. composite catalyst as claimed in claim 2 is characterized in that: be made of mineral acid mineral acid, monobasic or binary organic acid: the organic acid ratio is 1: 2, and consumption is 0.05～2% of a higher fatty acid quality.
7. composite catalyst as claimed in claim 6 is characterized in that: mineral acid is sulfuric acid, hydrochloric acid, phosphoric acid, phosphorous acid etc.; Organic acid is formic acid, acetate, propionic acid, Succinic Acid, hexanodioic acid etc.
8. as claim 1,2,3,4,5,6 described nontoxic calcium zinc composite thermal stabilizers and preparation method thereof, it is characterized in that: the synthetic higher fatty acid calcium zinc complexes of a step fusion, transformation efficiency is near 100%, plant factor is brought up to 85-90%, reduced filtration, washing, dehydration, operations such as drying, production link is short, production energy consumption is low, production cycle was reduced to about 4 hours by original 15 hours, production cost is low, stable and reliable product quality, have tangible technology and economic advantages, the Ca-Zn composite heat stabilizer static-aging experiment flavescence time after composite can reach more than 70 minutes, and the Congo red experiment variable color time can reach more than 47 minutes.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967253A (en) * | 2010-10-26 | 2011-02-09 | 湘乡市贝特尔塑胶有限公司 | Environmentally-friendly PVC calcium zinc composite stabilizer |
| CN102086271A (en) * | 2010-12-15 | 2011-06-08 | 浙江传化华洋化工有限公司 | Preparation method of high-transparent high heat resistance liquid calcium-zinc heat stabilizer |
| CN101747529B (en) * | 2009-12-16 | 2011-09-21 | 杭州三叶新材料股份有限公司 | Ca-Zn liquid composite stabilizing agent and application thereof |
| CN102321312A (en) * | 2011-07-29 | 2012-01-18 | 广东若天新材料科技有限公司 | Environment-friendly calcium zinc stabilizer for PVC pipe and preparation method thereof |
| CN101712771B (en) * | 2009-10-16 | 2012-05-02 | 常州嘉仁禾化学有限公司 | Sodium-zinc PVC stabilizer and preparation method thereof |
| CN102838819A (en) * | 2012-09-21 | 2012-12-26 | 中国林业科学研究院林产化学工业研究所 | Preparation method of oil/rosin base liquid calcium-zinc composite stabilizing agent used for PVC (Polyvinyl Chloride) |
| CN103923346A (en) * | 2013-01-11 | 2014-07-16 | 中山华明泰化工股份有限公司 | Composite plastic auxiliary agent |
| CN105949667A (en) * | 2016-06-20 | 2016-09-21 | 河南师范大学 | Beta-diketone organic barium-zinc PVC heat stabilizer and preparation method thereof |
| CN107118454A (en) * | 2017-04-10 | 2017-09-01 | 河源市鑫达科技有限公司 | PVC cable special-purpose anti-flaming heat endurance auxiliary agent and preparation method thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712771B (en) * | 2009-10-16 | 2012-05-02 | 常州嘉仁禾化学有限公司 | Sodium-zinc PVC stabilizer and preparation method thereof |
| CN101747529B (en) * | 2009-12-16 | 2011-09-21 | 杭州三叶新材料股份有限公司 | Ca-Zn liquid composite stabilizing agent and application thereof |
| CN101967253A (en) * | 2010-10-26 | 2011-02-09 | 湘乡市贝特尔塑胶有限公司 | Environmentally-friendly PVC calcium zinc composite stabilizer |
| CN102086271A (en) * | 2010-12-15 | 2011-06-08 | 浙江传化华洋化工有限公司 | Preparation method of high-transparent high heat resistance liquid calcium-zinc heat stabilizer |
| CN102086271B (en) * | 2010-12-15 | 2012-10-10 | 浙江传化华洋化工有限公司 | Preparation method of high-transparent high heat resistance liquid calcium-zinc heat stabilizer |
| CN102321312A (en) * | 2011-07-29 | 2012-01-18 | 广东若天新材料科技有限公司 | Environment-friendly calcium zinc stabilizer for PVC pipe and preparation method thereof |
| CN102838819A (en) * | 2012-09-21 | 2012-12-26 | 中国林业科学研究院林产化学工业研究所 | Preparation method of oil/rosin base liquid calcium-zinc composite stabilizing agent used for PVC (Polyvinyl Chloride) |
| CN102838819B (en) * | 2012-09-21 | 2014-08-20 | 中国林业科学研究院林产化学工业研究所 | Preparation method of oil/rosin base liquid calcium-zinc composite stabilizing agent used for PVC (Polyvinyl Chloride) |
| CN103923346A (en) * | 2013-01-11 | 2014-07-16 | 中山华明泰化工股份有限公司 | Composite plastic auxiliary agent |
| CN103923346B (en) * | 2013-01-11 | 2016-08-03 | 中山华明泰化工股份有限公司 | Complex plastic auxiliary agent |
| CN105949667A (en) * | 2016-06-20 | 2016-09-21 | 河南师范大学 | Beta-diketone organic barium-zinc PVC heat stabilizer and preparation method thereof |
| CN105949667B (en) * | 2016-06-20 | 2017-12-08 | 河南师范大学 | A kind of organic barium of beta diketone class/zinc PVC heat stabilizer and preparation method thereof |
| CN107118454A (en) * | 2017-04-10 | 2017-09-01 | 河源市鑫达科技有限公司 | PVC cable special-purpose anti-flaming heat endurance auxiliary agent and preparation method thereof |
| CN107118454B (en) * | 2017-04-10 | 2020-05-12 | 河源市鑫达科技有限公司 | Special flame-retardant heat-stability auxiliary agent for PVC (polyvinyl chloride) wires and cables and preparation method thereof |
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Open date: 20070926 |