CN101016396A - Method of preparing polyvinylchloride composite processing auxiliary agent - Google Patents
Method of preparing polyvinylchloride composite processing auxiliary agent Download PDFInfo
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- CN101016396A CN101016396A CN 200710020377 CN200710020377A CN101016396A CN 101016396 A CN101016396 A CN 101016396A CN 200710020377 CN200710020377 CN 200710020377 CN 200710020377 A CN200710020377 A CN 200710020377A CN 101016396 A CN101016396 A CN 101016396A
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Abstract
The invention discloses a preparing method of polyvinyl chloride composite processing aids, which comprises the following steps: choosing unsaturated fatty acid as raw material; reacting with hydrogen dioxide solution with acid catalysis under 40-80 deg.c; adding into 2-10% ethylene octadecanamide; stirring; reacting with nontoxic metallic element oxide or hydroxide composition under 70-110 deg.c at 1-3 h; cooling; getting end product; testing with national standard/ GB8815-88. The thermo stable time is higher than 110 min.
Description
Technical field
The present invention relates to a kind of working method of industrial chemicals, specifically a kind of preparation method of polyvinylchloride composite processing auxiliary agent.
Background technology
Polyvinyl chloride is one of broad-spectrum macromolecular material, and China's annual production surpasses 4,000,000 tons, is widely used in fields such as chemical building material, cable, plastic sheeting for farm use, toy.
The polyvinyl chloride processing heat stability is poor, must add processing aids such as thermo-stabilizer, lubricant in the polyvinyl chloride molding process.Polyvinyl chloride processing at present mainly contains kinds such as lead salt stabilizer, organic tin thermo-stabilizer, metal soap thermal stabilizers, one package stabilizer, organic stabilizer, rare earth metal thermo-stabilizer with thermo-stabilizer.
Lead salt stabilizer is the general name of the inorganic lead plumbate of alkali formula and organic lead plumbate (except the lead stearate), as dibasic lead phosphite, lead sulfate tribasic, many alkali fumaric acid lead etc.Because this series products is a powder, leaded dust is poisoned bigger to human body, and the transparency is poor, has during use and emits white phenomenon, is not suitable for processing transparent article, and the existing market consumption reduces gradually.
The organic tin thermo-stabilizer transparency, good weatherability, light is stable, thermal stability is all good, is used widely, be particularly useful for transparent article, such stablizer price is higher, has limited its range of application, and normal and other stablizer such as metallic soap class, epoxy compounds etc. are used.
Metal soap thermal stabilizers is the general name of higher fatty acid salt, soap salt such as the lead that lipid acid is arranged commonly used, barium, calcium, cadmium, zinc, antimony, aluminium, the initial coloring of calcium stearate is poor, the drawback that Zinic stearas has zinc to burn when large usage quantity, every kind of soap salt primary stability is different with permanent stability, and oilness is different, often is used, use excessive meeting to cause and separate out, influence product performance.
One package stabilizer is fast-developing in recent years stablizer kind, it utilizes various stablizers synergy, with the stablizer of multiple difference in functionality and other auxiliary agents are compound by a certain percentage is mixed " packet mode ", has not only improved stabilization efficiency, and easy to use, reduced dust pollution.Development abroad is rapid in recent years, is domesticly applied at CABLE MATERIALS, PVC building materials field, also is not used in the one package stabilizer of shape memory polyvinyl chloride processing at present.
Organic stabilizer mainly contains epoxies, phosphorous acid esters, nitrogenous compound and high boiling polyol etc., and how such stablizer is as auxiliary stabilizer.
The rare earth metal thermo-stabilizer is the distinctive stablizer of China, and comprehensive superiority of effectiveness is not outstanding, the marketing difficulty.
Polyvinyl chloride thermo-stabilizer new product development trend low toxicity, nontoxic, pollution-freeization development, calcium/zinc system, calcium/aluminium/stablizers such as zinc system will be rapidly developed as the stablizer substitute plumbous, that cadmium toxicity is bigger, be expected to become the substitute of organotin.Particularly the ROHS of European Union instruction is after implementing on July 1st, 2006, to bring tremendous influence to China's electric equipment products, must not adopt the lead salts stablizer as the refrigerator door envelope with PVC adhesive tape, supply lead, Board material for box etc., so research and development are also applied the practical non-toxic heat stabilizer of industry, replace traditional poisonous kind, become the important topic that current China faces.
Summary of the invention
Goal of the invention: purpose of the present invention, provide a kind of preparation method of non-toxic polyvinyl chloride composite auxiliary for processing, the polyvinylchloride composite processing auxiliary agent that utilizes this method to make has the advantage of metallic soap class and epoxies stablizer concurrently, and is good with the polyvinyl chloride consistency, thermally-stabilised efficient height.
Technical scheme: the preparation method who gets polyvinylchloride composite processing auxiliary agent of the present invention may further comprise the steps:
1, under 40～80 ℃, be that the acid or glacial acetic acid of unsaturated fatty acids 10～20% mixes with unsaturated fatty acids and weight ratio, dripping weight ratio is the hydrogen peroxide (amounting to 100% hydrogen peroxide calculates) of unsaturated fatty acids 10～30%, reacts 4～12 hours;
2, be washed to neutrality, vacuum hydro-extraction gets epoxyfatty acid;
3, under 70～110 ℃, epoxyfatty acid and nontoxic metallic element oxide compound or hydroxide combinations thing were mixed in 1: 1.0 in molar ratio～1: 1.5, add weight ratio and be the ethylene bis stearamide stirring reaction 1～3 hour of epoxyfatty acid 2～10%;
4, after reaction finished, cooling got the non-toxic polyvinyl chloride composite auxiliary for processing.
Wherein the unsaturated fatty acids described in the step 1 is an epoxyfatty acid, preferred soybean oleic acid, oleic acid, linolenic acid or Zoomeric acid.
Hydrogen peroxide concentration described in the step 1 accounts for 20～100% of total solution weight for hydrogen peroxide weight, and is preferred 20～50%, drips flow rate control and drips off at 1 hour.
Metallic element oxide compound described in the step 3 or oxyhydroxide are calcium oxide, calcium hydroxide, zinc oxide, magnesium oxide or magnesium hydroxide
The non-toxic polyvinyl chloride composite auxiliary for processing is tested by national standard/GB8815-88, and heat-stable time was greater than 110 minutes (standard was greater than 60 minutes).
Beneficial effect: this preparation method is simple to operate, is easy to realize that the non-toxic polyvinyl chloride composite auxiliary for processing that makes has the advantage of metallic soap class and epoxies stablizer concurrently, and thermally-stabilised efficient is greatly improved.
Embodiment
The invention will be further described below by embodiment.
Embodiment 1:
200 kilograms of soybean oleic acid slowly heat up under at the uniform velocity stirring.When temperature is raised to 55 ℃, stop heating, add 40 kilograms of Glacial acetic acid (account for soybean oleic acid weight 20%), and to begin to drip concentration be that 100 kilograms (amounting to 100% hydrogen peroxide calculates for 27% hydrogen peroxide, account for soybean oleic acid weight 13%), control rate of addition, about 1h dropwises, continue stirring reaction 3h, temperature of reaction is no more than 65 ℃.The epoxy soybean oleic acid that generates washes with water to neutrality, dewaters under the vacuum.Be heated to 80 ℃, this moment add 15 kilograms in calcium hydroxide (with the oleic mol ratio of soybean be 1: 0.57), 26 kilograms in zinc oxide (with the oleic mol ratio of soybean be 1: 0.9), 10 kilograms of ethylene bis stearamides (account for epoxy soybean oleic acid weight 5%), be warming up to 110 ℃, stirring reaction 2h under stirring.Be uniformly dispersed, section is the non-toxic polyvinyl chloride composite auxiliary for processing.Test according to national standard/GB8815-88, heat-stable time is 105 minutes (standard is greater than 60 minutes), and all the other every indexs all can reach standard-required.
Embodiment 2:
200 kilograms of Zoomeric acids slowly heat up under at the uniform velocity stirring.When temperature is raised to 45 ℃, stop heating, add 10 kilograms of Glacial acetic acid (account for Zoomeric acid weight 10%), and the hydrogen peroxide of beginning Dropwise 5 0% (is amounted to the calculating of 100% hydrogen peroxide for 100 kilograms, account for Zoomeric acid weight 25%), control rate of addition, about 1h dropwises, continue stirring reaction 11h, temperature of reaction is no more than 65 ℃.The epoxy palm oil acid that generates washes with water to neutrality, dewaters under the vacuum.Be heated to 90 ℃, add 15 kilograms in calcium oxide (with the mol ratio of Zoomeric acid 1: 0.57) this moment, 10 kilograms in zinc oxide (with the mol ratio of Zoomeric acid be 1: 0.35), 4 kilograms of magnesium hydroxides (with the mol ratio of Zoomeric acid be 1: 0.29), 4 kilograms of ethylene bis stearamides (account for epoxy palm oil acid weight 2%), be warming up to 110 ℃, stirring reaction 2h under stirring.Be uniformly dispersed, section is the non-toxic polyvinyl chloride composite auxiliary for processing.Test according to national standard/GB8815-88, heat-stable time is 112 minutes (standard is greater than 60 minutes), and all the other every indexs all can reach standard-required.
Embodiment 3:
200 kilograms of linolenic acids slowly heat up under at the uniform velocity stirring.When temperature is raised to 40 ℃, stop heating, add 30 kilograms of formic acid (account for linolenic acid weight 15%), and 150 kilograms (amounting to 100% hydrogen peroxide calculates to begin to drip 30% hydrogen peroxide, account for linolenic acid weight 22.5%), control rate of addition, about 1h dropwises, continue stirring reaction 8h, temperature of reaction is no more than 65 ℃.Resultant washes with water to neutrality, dewaters under the vacuum.Be heated to 90 ℃, add 10 kilograms in calcium oxide this moment, 15 kilograms in zinc oxide, and 4 kilograms in magnesium oxide, 20 kilograms of ethylene bis stearamides (account for epoxy linolenic acid weight 10%) are warming up to 110 ℃, stirring reaction 3h under stirring.Be uniformly dispersed, section is the non-toxic polyvinyl chloride composite auxiliary for processing.Test according to national standard/GB8815-88, heat-stable time is 130 minutes (standard is greater than 60 minutes), and all the other every indexs all can reach standard-required.
Embodiment 4:
200 kilograms of oleic acids slowly heat up under at the uniform velocity stirring.When temperature is raised to 60 ℃, stop heating, add 20 kilograms of formic acid (account for oleic acid weight 10%), and 80 kilograms (amounting to 100% hydrogen peroxide calculates to begin to drip 70% hydrogen peroxide, account for oleic acid weight 28%), control rate of addition, about 2h dropwises, continue stirring reaction 6h, temperature of reaction is no more than 65 ℃.Resultant washes with water to neutrality, dewaters under the vacuum.Be heated to 90 ℃, add 15 kilograms in calcium oxide this moment, 10 kilograms in zinc oxide, and 5 kilograms of magnesium hydroxides, 14 kilograms of ethylene bis stearamides (account for epoxy oleic acid weight 7%) are warming up to 110 ℃, stirring reaction 2h under stirring.Be uniformly dispersed, section is the non-toxic polyvinyl chloride composite auxiliary for processing.Test according to national standard/GB8815-88, heat-stable time is 115 minutes (standard is greater than 60 minutes), and all the other every indexs all can reach standard-required.
Embodiment 5:
200 kilograms of soybean oleic acid slowly heat up under at the uniform velocity stirring.When temperature is raised to 65 ℃, stop heating, add 40 kilograms of Glacial acetic acid (account for soybean oleic acid weight 20%), and to begin to drip concentration be that 100 kilograms (amounting to 100% hydrogen peroxide calculates for 20% hydrogen peroxide, account for soybean oleic acid weight 10%), control rate of addition, about 1h dropwises, continue stirring reaction 3h, temperature of reaction is no more than 80 ℃.The epoxy soybean oleic acid that generates washes with water to neutrality, dewaters under the vacuum.Be heated to 70 ℃, add 15 kilograms in calcium hydroxide this moment, 26 kilograms in zinc oxide, and 10 kilograms of ethylene bis stearamides (account for epoxy soybean oleic acid weight 5%) are warming up to 110 ℃, stirring reaction 1h under stirring.Be uniformly dispersed, section is the non-toxic polyvinyl chloride composite auxiliary for processing.Test according to national standard/GB8815-88, heat-stable time is 110 minutes (standard is greater than 60 minutes), and all the other every indexs all can reach standard-required.
Embodiment 6:
With embodiment 2 described preparation methods, different is that hydrogen peroxide concentration is 100%, weight is 60 kilograms, and (amounting to 100% hydrogen peroxide calculates, account for Zoomeric acid weight 30%), and nontoxic metallic element oxide compound or hydroxide combinations thing selective oxidation zinc, the mol ratio of zinc oxide and Zoomeric acid is 1: 1.0.
Embodiment 7:
With embodiment 2 described preparation methods, different is that the nontoxic metallic element oxide compound or the hydroxide combinations thing that add are selected magnesium hydroxide, and the mol ratio of magnesium hydroxide and Zoomeric acid is 1: 1.5.
Claims (6)
1, a kind of preparation method of polyvinylchloride composite processing auxiliary agent is characterized in that this method may further comprise the steps:
(1) under 40～80 ℃, be that the acid or glacial acetic acid of unsaturated fatty acids 10～20% mixes with unsaturated fatty acids and weight ratio, dripping weight ratio is the hydrogen peroxide of unsaturated fatty acids 10～30%, reacts 4～12 hours;
(2) be washed to neutrality, vacuum hydro-extraction gets epoxyfatty acid;
(3) under 70～110 ℃, epoxyfatty acid and nontoxic metallic element oxide compound or hydroxide combinations thing were mixed in 1: 1.0 in molar ratio～1: 1.5, add weight ratio and be the ethylene bis stearamide stirring reaction 1～3 hour of epoxyfatty acid 2～10%;
(4) after reaction finished, cooling got the non-toxic polyvinyl chloride composite auxiliary for processing.
2, the preparation method of polyvinylchloride composite processing auxiliary agent according to claim 1 is characterized in that step
(1) unsaturated fatty acids described in is an epoxyfatty acid.
3, the preparation method of polyvinylchloride composite processing auxiliary agent according to claim 1 is characterized in that step
(1) unsaturated fatty acids described in is soybean oleic acid, oleic acid, linolenic acid or Zoomeric acid.
4, the preparation method of polyvinylchloride composite processing auxiliary agent according to claim 1 is characterized in that step
(1) hydrogen peroxide concentration described in accounts for 20～100% of total solution weight for hydrogen peroxide weight.
5, the preparation method of polyvinylchloride composite processing auxiliary agent according to claim 4 is characterized in that described hydrogen peroxide concentration accounts for 20～50% of total solution weight for hydrogen peroxide weight.
6, the preparation method of polyvinylchloride composite processing auxiliary agent according to claim 1 is characterized in that nontoxic metallic element oxide compound described in the step (3) or hydroxide combinations thing are calcium oxide, calcium hydroxide, zinc oxide, magnesium oxide or magnesium hydroxide.
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| CNB2007100203773A CN100469833C (en) | 2007-02-15 | 2007-02-15 | Method of preparing polyvinylchloride composite processing auxiliary agent |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504443A (en) * | 2011-11-22 | 2012-06-20 | 山东瑞丰高分子材料股份有限公司 | Epoxidized calcium-zinc oleate compound stabilizer and preparation method thereof |
| CN102617888A (en) * | 2011-12-09 | 2012-08-01 | 江南大学 | Preparation of environment friendly calcium-zinc composite heat stabilizer and its application in PVC (polrvinyl chloride) |
| CN102775698A (en) * | 2012-08-07 | 2012-11-14 | 浙江传化华洋化工有限公司 | Production process of environment-friendly liquid PVC (polyvinyl chloride) heat stabilizer |
| CN103374187A (en) * | 2012-04-25 | 2013-10-30 | 吴旅良 | One-kettle continuously step-by-step synthesized calcium zinc composite stabilizer |
| CN103382415A (en) * | 2013-01-14 | 2013-11-06 | 江苏卡特新能源有限公司 | Production method of epoxidized fatty acid methyl ester/epoxidized soybean oil |
| CN107189258A (en) * | 2017-06-15 | 2017-09-22 | 苏州莱特复合材料有限公司 | A kind of preparation method of metal-based compound polychloroethylene heat stabilizer |
| CN114907750A (en) * | 2022-04-15 | 2022-08-16 | 书香门地集团股份有限公司 | Flame retardant, preparation method thereof and application of flame retardant in preparation of flame-retardant floor |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033913C (en) * | 1993-12-09 | 1997-01-29 | 浙江大学 | Epoxy unsaturated high-grade fatty acid rare earth non-toxic stabilizing agent |
| CN100497467C (en) * | 2005-09-02 | 2009-06-10 | 广东联塑科技实业有限公司 | Epoxy-zinc soap compound as heat stabilizer for polyvinyl chloride plastic formula |
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2007
- 2007-02-15 CN CNB2007100203773A patent/CN100469833C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504443A (en) * | 2011-11-22 | 2012-06-20 | 山东瑞丰高分子材料股份有限公司 | Epoxidized calcium-zinc oleate compound stabilizer and preparation method thereof |
| CN102617888A (en) * | 2011-12-09 | 2012-08-01 | 江南大学 | Preparation of environment friendly calcium-zinc composite heat stabilizer and its application in PVC (polrvinyl chloride) |
| CN103374187A (en) * | 2012-04-25 | 2013-10-30 | 吴旅良 | One-kettle continuously step-by-step synthesized calcium zinc composite stabilizer |
| CN103374187B (en) * | 2012-04-25 | 2015-12-16 | 吴旅良 | The preparation method of calcium-zinc composite stabilizing agent is produced in one still contiguous segmentation synthesis |
| CN102775698A (en) * | 2012-08-07 | 2012-11-14 | 浙江传化华洋化工有限公司 | Production process of environment-friendly liquid PVC (polyvinyl chloride) heat stabilizer |
| CN103382415A (en) * | 2013-01-14 | 2013-11-06 | 江苏卡特新能源有限公司 | Production method of epoxidized fatty acid methyl ester/epoxidized soybean oil |
| CN103382415B (en) * | 2013-01-14 | 2014-09-03 | 江苏卡特新能源有限公司 | Production method of epoxidized fatty acid methyl ester/epoxidized soybean oil |
| CN107189258A (en) * | 2017-06-15 | 2017-09-22 | 苏州莱特复合材料有限公司 | A kind of preparation method of metal-based compound polychloroethylene heat stabilizer |
| CN114907750A (en) * | 2022-04-15 | 2022-08-16 | 书香门地集团股份有限公司 | Flame retardant, preparation method thereof and application of flame retardant in preparation of flame-retardant floor |
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| CN100469833C (en) | 2009-03-18 |
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