CN1618793A - Preparation method of epoxy unsaturuted higher futty acid compound zinc soap - Google Patents
Preparation method of epoxy unsaturuted higher futty acid compound zinc soap Download PDFInfo
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- CN1618793A CN1618793A CN 200410051729 CN200410051729A CN1618793A CN 1618793 A CN1618793 A CN 1618793A CN 200410051729 CN200410051729 CN 200410051729 CN 200410051729 A CN200410051729 A CN 200410051729A CN 1618793 A CN1618793 A CN 1618793A
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Abstract
A composite zinc soap used for the non-toxic PVC products is prepared through proportionally mixing the saponified liquid of unsaturated high-grade epoxy fatty acid with the saponified liquid of at least one or two organic acids, metathetical reaction on the solution of zinc salt, washing and drying. Its advantage is high thermal stability.
Description
Technical field
The present invention relates to a kind of technology of preparing of compound zinc soap thermo-stabilizer.
Background technology
Existing zinc soap type thermal stabilizing agent mainly is Zinic stearas, zinc laurate, zinc ricinate, zinc palmitate, zinc salicylate, 2 ethyl hexanoic acid zinc etc.As the PVC thermo-stabilizer, these zinc salts and hcl reaction are fast, be difficult for to generate long polyenoid sequence, thus initial stage easy coloring not, but " zinc burning " generation halochromism can take place suddenly after being heated to certain temperature and certain hour; Add epoxy compounds in the prescription,, need the amount of adding excessive, obviously be unsuitable for the processing of PVC boardy product though heat-stable time is obviously prolonged.These drawbacks limit they application in PVC.
The Chinese patent publication number is CN1089968A, the patent No. is that 93120487.9 patent of invention discloses a kind of epoxy unsaturated high-grade fatty acid rare earth non-toxic stabilizing agent, be to be raw material with the unsaturated high-grade fatty acid, through epoxidation, after the saponification, carry out replacement(metathesis)reaction with rare earths salt and obtain finished product, the advantage of this invention is, products obtained therefrom combines the stable mechanism of epoxy compounds and higher fatty acid metallic soap, its long-term thermal stability is better than the physical mixed of epoxidized vegetable oil and higher fatty acid metallic soap, but should invention also exist not enough, mainly be that technological process is easily carried epoxy unsaturated high-grade fatty acid sodium secretly and target product is formed one, influence quality product, and/or make and comprise washing, dry, broken, pulverizing waits the aftertreatment technology flow process to prolong, and increases process cost.
Summary of the invention
Purpose of the present invention is just in order to overcome above-mentioned weak point, and proposes the preparation method of compound zinc soap of a kind of epoxy unsaturated high-grade fatty acid and compound zinc soap.
Purpose of the present invention is achieved through the following technical solutions:
The preparation method of the compound zinc soap of a kind of epoxy unsaturated high-grade fatty acid is divided into following steps:
(1), epoxy unsaturated high-grade fatty acid and alkali generation saponification reaction, preparation epoxy unsaturated high-grade fatty acid saponification liquor;
(2), C
6～C
18Monobasic or binary is saturated or unsaturated organic acid and alkali generation saponification reaction, the preparation C
6～C
18Monobasic or binary is saturated or the saponification liquor of unsaturated organic acid;
(3), epoxy unsaturated high-grade fatty acid saponification liquor and the step (2) with step (1) preparation prepares C
6～C
18Monobasic or binary is saturated or the saponification liquor of unsaturated organic acid mixes, form to mix saponification liquor;
(4), mixing saponification liquor and the zinc solution that step (3) is formed carries out replacement(metathesis)reaction, the compound zinc soap of formation epoxy unsaturated high-grade fatty acid;
(5), with the product of step (4) through washing, drying, the fine powder form finished product of the compound zinc soap of epoxy unsaturated high-grade fatty acid.
Among the above-mentioned preparation method, the described epoxy unsaturated high-grade fatty acid of step (1) is selected epoxyoleic acid or epoxy ricinolic acid for use; The described C of step (2)
6～C
18Monobasic or binary is saturated or unsaturated organic acid adopts lauric acid or Palmiticacid or stearic acid or 12-oxystearic acid or oleic acid or ricinolic acid or Whitfield's ointment or anthranilic acid or hexanodioic acid or sebacic acid; Described epoxy unsaturated high-grade fatty acid saponification liquor of step (3) and C
6～C
18Monobasic binary is saturated or the saponification liquor of unsaturated organic acid by 3: 17～19: 1 mixed in molar ratio, the described zinc solution employing of step (4) mass percent is 10～25% zinc sulfate or zinc nitrate aqueous solution, and zinc sulfate or zinc nitrate aqueous solution account for 10%～38% of reactant weight in the replacement(metathesis)reaction, mix saponification liquor and then account for 62%～90% of reactant weight accordingly.
Step of the present invention (1) and the described alkali of step (2) are that mass percent is 4～12% sodium hydroxide or potassium hydroxide aqueous solution, the temperature of described saponification reaction is 45～80 ℃, 15～40 minutes reaction times, and the temperature of the described replacement(metathesis)reaction of step (4) is 50～60 ℃.
Preparation method of the present invention, the C of described step (2)
6～C
18Monobasic or binary is saturated or unsaturated organic acid also can adopt the deionized water or the dilution of 1: 1 aqueous ethanolic solution of 1.5～2 times of weight before saponification reaction.
Compared with prior art, the present invention has following advantage:
1, synthetic product good heat stability can be applied to the thermo-stabilizer prescription that the PVC boardy product is processed well;
2, the seed effect of technological process, making synthetic product is the fine powder form that directly generates, and is convenient to following process and uses, and does not increase process cost, and have good dispersiveness in PVC;
3, make the thermo-stabilizer prescription of PVC boardy product processing have adjustable oilness flexibly.
Embodiment
The present invention is further illustrated with specific embodiment below, and enforcement of the present invention is not limited only to the following examples.
Embodiment one:
Be equipped with agitator, temperature is taken into account in the 500L enamel reaction still of heating jacket, the stearic acid that adds 68.5kg, 1: 1 aqueous ethanolic solution of 137kg, heat temperature raising under agitation condition, in 70～80 ℃ of downhill reaction stills, add 8～10% alkali lye feed liquid to the still at a slow speed and be weakly alkaline, the control pH value continues insulation reaction half an hour, saponification liquor is cooled off standby.
Another be equipped with agitator, temperature is taken into account in the 1000L enamel reaction still of heating jacket, the epoxyoleic acid that adds 83.6kg, under agitation condition, 1: 1 aqueous ethanolic solution that adds 126kg, warming while stirring, in 45～55 ℃ of downhill reaction stills, add 8～10% alkali lye feed liquid to the still at a slow speed and be weakly alkaline, the control pH value continues insulation reaction half an hour, under same temperature, add foregoing stearic acid saponification liquid 150kg, after mixing, add excessive slightly zinc solution more at a slow speed, add follow-up continuation of insurance temperature reaction 30～40 minutes.
After reaction finished, decompress filter was removed water, and precipitate with deionized water washing 3～4 times promptly gets the compound zinc soap product of epoxyoleic acid after 50～60 ℃ of dryings.Sampling analysis, oxirane value are 2.7gO/100g, contain 2.7 gram oxygen in promptly per 100 gram products, and free acid is 0.1%.
Embodiment two:
Be equipped with agitator, temperature is taken into account in the 500L enamel reaction still of heating jacket, the lauric acid that adds 48kg, 1: 1 aqueous ethanolic solution of 96kg, heat temperature raising under agitation condition, in 70～80 ℃ of downhill reaction stills, add 8～10% alkali lye feed liquid to the still at a slow speed and be weakly alkaline, the control pH value continues insulation reaction half an hour, saponification liquor is cooled off standby.
Another be equipped with agitator, temperature is taken into account in the 1000L enamel reaction still of heating jacket, the epoxyoleic acid that adds 83.6kg, under agitation condition, 1: 1 aqueous ethanolic solution that adds 126kg, warming while stirring, in 45～55 ℃ of downhill reaction stills, add 8～10% alkali lye feed liquid to the still at a slow speed and be weakly alkaline, the control pH value continues insulation reaction half an hour, under same temperature, add foregoing stearic acid saponification liquid 150kg, after mixing, add excessive slightly zinc solution more at a slow speed, add follow-up continuation of insurance temperature reaction 30～40 minutes.
After reaction finished, decompress filter was removed water, and precipitate with deionized water washing 3～4 times promptly gets the compound zinc soap product of epoxyoleic acid after 50～60 ℃ of dryings.Sampling analysis, oxirane value are 2.9gO/100g, contain 2.9 gram oxygen in per 100 gram products, and free acid is 0.1%.
Embodiment three:
Be equipped with agitator, temperature is taken into account in the 500L enamel reaction still of heating jacket, the anthranilic acid that adds 41.1kg, the 82kg deionized water, heat temperature raising under agitation condition, in 70～80 ℃ of downhill reaction stills, add 8～10% alkali lye feed liquid to the still at a slow speed and be weakly alkaline, the control pH value continues insulation reaction half an hour, saponification liquor is cooled off standby.
Be equipped with agitator at another, temperature is taken into account in the 1000L enamel reaction still of heating jacket, the epoxy ricinolic acid that adds 94.3kg, under agitation condition, add the 142kg deionized water, warming while stirring, in 45～55 ℃ of downhill reaction stills, add 8～10% alkali lye feed liquid to the still at a slow speed and be weakly alkaline, the control pH value continues insulation reaction half an hour, in same temperature, under the agitation condition, add the stearic acid saponification liquid 62.7kg that makes as embodiment one same recipe and operational condition, add foregoing anthranilic acid saponification liquor 40.6kg, after mixing, add excessive slightly zinc solution more at a slow speed, add follow-up continuation of insurance temperature reaction 30～40 minutes.
After reaction finished, decompress filter was removed water, and precipitate with deionized water washing 3～4 times promptly gets the compound zinc soap product of epoxyoleic acid after 50～60 ℃ of dryings.Sampling analysis, oxirane value are 3.0gO/100g, contain 3.0 gram oxygen in promptly per 100 gram products, and free acid is 0.1%.
The compound zinc soap of epoxyoleic acid and other are with type thermal stabilizing agent resistance toheat test-results relatively
As shown in the table:
| Thermotolerance relatively | |||||||||||||
| Thermo-stabilizer | Steady stability time/min. | Dynamic melanism time/min. | Roll extrusion variable color situation | ||||||||||
| ?5 | ??10 | ??15 | ??20 | ??25 | ??30 | ??35 | ??40 | ??45 | ??50 | ||||
| Dry state | Hygrometric state | Test period/min. | |||||||||||
| Embodiment three/Ca (St) 2(3 parts) | ??56 | ?93 | ??50 | ?1 | ?2 | ?3 | ?4 | ?5 | ?6 | ?7 | ?8 | ?9 | ?10 |
| Embodiment two/Ca (St) 2(3 parts) | ??51 | ??88 | ??45 | ?1 | ?2 | ?3 | ?5 | ?6 | ?7 | ?8 | ?9 | ?10 | |
| Embodiment one/Ca (St) 2(3 parts) | ??48 | ??85 | ??43 | ?1 | ?2 | ?3 | ?5 | ?6 | ?7 | ?8 | ?9 | ?10 | |
| Ca(St) 2/Zn(St) 2(3 parts) | ??14 | ??17 | ??15 | ?2 | ?4 | ?10 | |||||||
| 3 parts of Ca (St) 2/Zn(St) 2+ 3 parts of epoxy soybean oils | ??63 | ?89 | ??26 | ?2 | ?3 | ?3 | ?4 | ?4 | ?10 | ||||
Annotate: dry state: 100 parts of PVC, thermo-stabilizer, grind mixing, press GB2917-82 A method
Test;
Hygrometric state: 100 parts of PVC, 60 parts of DBP, thermo-stabilizer, other are tested with dry state;
Dynamically: 100 parts of PVC, 40 parts of DBP, thermo-stabilizer, miniature high-speed mixing machine mixing, 145 ± 5 ℃ of roller temperature, roll spacing 1mm twin-screw extruder are plasticated in flakes, make 3cm * 3cm test piece, and in 180 ± 2 ℃ of baking ovens, timing sampling is observed test piece variable color situation;
Roll extrusion: 100 parts of PVC, 40 parts of DBP, thermo-stabilizer, miniature high-speed mixing machine mixing, 170 ± 3 ℃ of roller temperature, roll spacing 0.8～1mm twin-screw extruder are plasticated, and timing sampling is observed sample variable color situation.
Test-results shows, the heat-stable time of the compound zinc soap of epoxy unsaturated high-grade fatty acid of the present invention, obviously is better than the physical mixed of corresponding higher fatty acid zinc soap and epoxy soybean oil at especially dynamic melanism time; This compound zinc soap outward appearance is white or oyster white fine powder, can not influence the color of goods, and is nontoxic, and heavy metal free pollutes, and can be widely used in the nontoxic goods of various PVC useful HUMAN HEALTH and environment protection.
Claims (9)
1, a kind of method for preparing the compound zinc soap of epoxy unsaturated high-grade fatty acid is characterized in that being divided into following steps:
(1), with epoxy unsaturated high-grade fatty acid and alkali generation saponification reaction, preparation epoxy unsaturated high-grade fatty acid saponification liquor;
(2), with C
6～C
18Monobasic or binary is saturated or unsaturated organic acid and alkali generation saponification reaction, the preparation C
6～C
18Monobasic or binary is saturated or the saponification liquor of unsaturated organic acid;
(3), epoxy unsaturated high-grade fatty acid saponification liquor and the step (2) with step (1) preparation prepares C
6～C
18Monobasic or binary is saturated or the saponification liquor of unsaturated organic acid mixes, form to mix saponification liquor;
(4), mixing saponification liquor and the zinc solution that step (3) is formed carries out replacement(metathesis)reaction, the compound zinc soap of formation epoxy unsaturated high-grade fatty acid;
(5), with the product of step (4) through washing, drying, make the formation product of the compound zinc soap of epoxy unsaturated high-grade fatty acid.
2, the preparation method of the compound zinc soap of epoxy unsaturated high-grade fatty acid according to claim 1 is characterized in that the temperature of step (1) and the described saponification reaction of step (2) is 45～80 ℃, 15～40 minutes reaction times.
3, the preparation method of the compound zinc soap of epoxy unsaturated high-grade fatty acid according to claim 1 and 2 is characterized in that the described epoxy unsaturated high-grade fatty acid of step (1) selects epoxyoleic acid or epoxy ricinolic acid for use; The described C of step (2)
6～C
18Monobasic or binary is saturated or unsaturated organic acid adopts lauric acid or Palmiticacid or stearic acid or 12-oxystearic acid or oleic acid or ricinolic acid or Whitfield's ointment or anthranilic acid or hexanodioic acid or sebacic acid.
4, the preparation method of the compound zinc soap of epoxy unsaturated high-grade fatty acid according to claim 3 is characterized in that described epoxy unsaturated high-grade fatty acid saponification liquor of step (3) and C
6～C
18Monobasic binary is saturated or the saponification liquor of unsaturated organic acid by 3: 17～19: 1 mixed in molar ratio.
5, the preparation method of the compound zinc soap of epoxy unsaturated high-grade fatty acid according to claim 4 is characterized in that the described zinc solution of step (4) is that mass percent is 10～25% zinc sulfate or zinc nitrate aqueous solution.
6, the preparation method of the compound zinc soap of epoxy unsaturated high-grade fatty acid according to claim 5, it is characterized in that the described mixing saponification liquor of step (4) accounts for 62%～90% of reactant weight in the replacement(metathesis)reaction, described zinc solution accounts for 10%～38% of reactant weight.
7, the preparation method of the compound zinc soap of epoxy unsaturated high-grade fatty acid according to claim 6 is characterized in that the temperature of the described replacement(metathesis)reaction of step (4) is 50～60 ℃.
8, the preparation method of the compound zinc soap of epoxy unsaturated high-grade fatty acid according to claim 7 is characterized in that step (1) and the described alkali of step (2) are that mass percent is 4～12% sodium hydroxide or potassium hydroxide aqueous solution.
9, the preparation method of the compound zinc soap of epoxy unsaturated high-grade fatty acid according to claim 8 is characterized in that the epoxy unsaturated high-grade fatty acid of described step (1) and the C of step (2)
6～C
18Monobasic or binary is saturated or unsaturated organic acid can adopt the deionized water of 1.5～2 times of weight or aqueous ethanolic solution dilution before saponification reaction.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100517298A CN1313453C (en) | 2004-10-08 | 2004-10-08 | Preparation method of epoxy unsaturuted higher futty acid compound zinc soap |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100517298A CN1313453C (en) | 2004-10-08 | 2004-10-08 | Preparation method of epoxy unsaturuted higher futty acid compound zinc soap |
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| Publication Number | Publication Date |
|---|---|
| CN1618793A true CN1618793A (en) | 2005-05-25 |
| CN1313453C CN1313453C (en) | 2007-05-02 |
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|---|---|---|---|
| CNB2004100517298A Active CN1313453C (en) | 2004-10-08 | 2004-10-08 | Preparation method of epoxy unsaturuted higher futty acid compound zinc soap |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102492235A (en) * | 2011-11-22 | 2012-06-13 | 山东瑞丰高分子材料股份有限公司 | Epoxidized soybean oleic acid calcium zinc composite stabilizing agent for PVC (polyvinyl chloride) and its preparation method |
| CN104479248A (en) * | 2014-12-12 | 2015-04-01 | 江南大学 | C22 plant oil base PVC solid heat stabilizer and preparation method thereof |
| CN113457416A (en) * | 2021-07-05 | 2021-10-01 | 生态环境部华南环境科学研究所 | Broad-spectrum efficient peculiar smell purifying agent and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL265503A (en) * | 1960-06-03 | |||
| CN1033913C (en) * | 1993-12-09 | 1997-01-29 | 浙江大学 | Epoxy unsaturated high-grade fatty acid rare earth non-toxic stabilizing agent |
-
2004
- 2004-10-08 CN CNB2004100517298A patent/CN1313453C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102492235A (en) * | 2011-11-22 | 2012-06-13 | 山东瑞丰高分子材料股份有限公司 | Epoxidized soybean oleic acid calcium zinc composite stabilizing agent for PVC (polyvinyl chloride) and its preparation method |
| CN104479248A (en) * | 2014-12-12 | 2015-04-01 | 江南大学 | C22 plant oil base PVC solid heat stabilizer and preparation method thereof |
| CN113457416A (en) * | 2021-07-05 | 2021-10-01 | 生态环境部华南环境科学研究所 | Broad-spectrum efficient peculiar smell purifying agent and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1313453C (en) | 2007-05-02 |
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