CN1313453C - 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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- CN1313453C CN1313453C CNB2004100517298A CN200410051729A CN1313453C CN 1313453 C CN1313453 C CN 1313453C CN B2004100517298 A CNB2004100517298 A CN B2004100517298A CN 200410051729 A CN200410051729 A CN 200410051729A CN 1313453 C CN1313453 C CN 1313453C
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 43
- 239000011701 zinc Substances 0.000 title claims abstract description 43
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 41
- 150000001875 compounds Chemical class 0.000 title claims abstract description 31
- 239000000344 soap Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002253 acid Substances 0.000 title claims description 8
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 39
- 239000000194 fatty acid Substances 0.000 claims abstract description 39
- 229930195729 fatty acid Natural products 0.000 claims abstract description 39
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 38
- 238000007127 saponification reaction Methods 0.000 claims abstract description 36
- 150000007524 organic acids Chemical class 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 12
- 229920006395 saturated elastomer Polymers 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- RWZYAGGXGHYGMB-UHFFFAOYSA-N anthranilic acid Chemical compound NC1=CC=CC=C1C(O)=O RWZYAGGXGHYGMB-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000005649 metathesis reaction Methods 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- WBHHMMIMDMUBKC-QJWNTBNXSA-N ricinoleic acid Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(O)=O WBHHMMIMDMUBKC-QJWNTBNXSA-N 0.000 claims description 5
- 229960003656 ricinoleic acid Drugs 0.000 claims description 5
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims description 5
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- 239000005639 Lauric acid Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 claims description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 229940098695 palmitic acid Drugs 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 2
- 150000003751 zinc Chemical class 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000012266 salt solution Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- 239000003381 stabilizer Substances 0.000 description 12
- 238000013019 agitation Methods 0.000 description 7
- IMYZYCNQZDBZBQ-SJORKVTESA-N (9S,10R)-epoxyoctadecanoic acid Chemical compound CCCCCCCC[C@H]1O[C@H]1CCCCCCCC(O)=O IMYZYCNQZDBZBQ-SJORKVTESA-N 0.000 description 6
- 210000003298 dental enamel Anatomy 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 238000005070 sampling Methods 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229940095696 soap product Drugs 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 208000003351 Melanosis Diseases 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- ZRXHQNQYIKVKNQ-UHFFFAOYSA-N 2-ethylhexanoic acid;zinc Chemical compound [Zn].CCCCC(CC)C(O)=O ZRXHQNQYIKVKNQ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000237502 Ostreidae Species 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- MFGZXPGKKJMZIY-UHFFFAOYSA-N ethyl 5-amino-1-(4-sulfamoylphenyl)pyrazole-4-carboxylate Chemical compound NC1=C(C(=O)OCC)C=NN1C1=CC=C(S(N)(=O)=O)C=C1 MFGZXPGKKJMZIY-UHFFFAOYSA-N 0.000 description 1
- -1 fatty acid rare earth Chemical class 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- 229940012185 zinc palmitate Drugs 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
- GJAPSKMAVXDBIU-UHFFFAOYSA-L zinc;hexadecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O GJAPSKMAVXDBIU-UHFFFAOYSA-L 0.000 description 1
Abstract
The present invention relates to a preparation method of epoxy unsaturated higher fatty acid compound zinc soaps. Epoxy unsaturated higher fatty acid saponification liquid and at least one another two or three kinds of organic acid saponification liquid are mixed according to a certain molar ratio; then, the mixture carries out double decomposition reaction with a zinc salt solution; after the steps of washing and drying, the epoxy unsaturated higher fatty acid compound zinc soaps are obtained. The thermal stability time, particularly the dynamic blackening time of the epoxy unsaturated higher fatty acid compound zinc soaps prepared by the present invention is obviously superior to that of the existing product, and the epoxy unsaturated higher fatty acid compound zinc soaps prepared by the present invention can be widely used in various PVC atoxic products and are beneficial to the human body health and the environmental protection.
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 the 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 2.7g0/100g, 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 2.9g0/100g, 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 3.0g0/100g, 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 test-results with the comparison of type thermal stabilizing agent resistance toheat are 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 the GB2917-82A method and 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 the 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.
Priority Applications (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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| CNB2004100517298A CN1313453C (en) | 2004-10-08 | 2004-10-08 | Preparation method of epoxy unsaturuted higher futty acid compound zinc soap |
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| CN1618793A CN1618793A (en) | 2005-05-25 |
| CN1313453C true CN1313453C (en) | 2007-05-02 |
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Families Citing this family (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 |
| CN102492235B (en) * | 2011-11-22 | 2013-08-28 | 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 |
| CN113457416B (en) * | 2021-07-05 | 2023-03-31 | 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3459776A (en) * | 1960-06-03 | 1969-08-05 | Hoesch Chemie Gmbh Duren Chemi | Process for the production of metal soaps of epoxydized fatty acids |
| CN1089968A (en) * | 1993-12-09 | 1994-07-27 | 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 not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3459776A (en) * | 1960-06-03 | 1969-08-05 | Hoesch Chemie Gmbh Duren Chemi | Process for the production of metal soaps of epoxydized fatty acids |
| CN1089968A (en) * | 1993-12-09 | 1994-07-27 | 浙江大学 | Epoxy unsaturated high-grade fatty acid rare earth non-toxic stabilizing agent |
Non-Patent Citations (4)
| Title |
|---|
| 新型 高效 无毒的钙皂 锌皂热稳定剂的研究 林美娟 章文贡，聚氯乙稀，第1期 2000 * |
| 热稳定剂研究进展 张亨，合成材料老化与应用，第4期 2001 * |
| 热稳定剂研究进展 张亨，合成材料老化与应用，第4期 2001;新型 高效 无毒的钙皂 锌皂热稳定剂的研究 林美娟 章文贡，聚氯乙稀，第1期 2000;由环氧大豆油合成环氧金属皂的研究 吴茂英 吴雅红，化工科技，第9卷第6期 2001 * |
| 由环氧大豆油合成环氧金属皂的研究 吴茂英 吴雅红，化工科技，第9卷第6期 2001 * |
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