CN102898300A - C21 dibasic acid rare earth salt, preparation method and applications thereof - Google Patents
C21 dibasic acid rare earth salt, preparation method and applications thereof Download PDFInfo
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Abstract
The present invention discloses a C21 dibasic acid rare earth salt, a preparation method and applications thereof, wherein TMAA, sodium hydroxide and a soluble rare earth inorganic salt are added to a solvent to dissolve, a double decomposition reaction is performed, and after completing the reaction, the product is subjected to suction filtration, washing, drying and grinding to obtain the C21 dibasic acid rare earth salt, and the C21 dibasic acid rare earth salt can be separately used as a PVC heat stabilizer, and can further be used through compounding. According to the C21 dibasic acid rare earth salt, the molecular structure contains a six-membered cyclic structure, characteristics of no toxicity and environment protection are provided, and long term thermal stability of the PVC can be improved. According to the preparation method, a preparation process route is simple, conditions are mild, raw materials adopt an environmentally friendly renewable tung oil resource, and the product has a high performance price ratio.
Description
Technical field
The present invention relates to a kind ofly prepare C by methyl eleostearate
21The method of diprotic acid rare-earth salts and as the application of PVC thermo-stabilizer belongs to PVC thermo-stabilizer technical field.
Background technology
In the world, the demand of polyvinyl chloride resin occupies the 3rd after listing in polyethylene, polypropylene, and has risen to first at its consumption of China.But, there is defective in the PVC structure, the thermal destruction phenomenon occurs in the PVC course of processing easily, therefore, usually add thermo-stabilizer to promote the plasticizing of polyvinyl chloride resin, improve melt strength, reduce processing temperature, improve the visual appearance of goods, improve simultaneously the property indices of PVC goods, enlarge its Application Areas.
The main Shi Ge ∕ lead salt Re Wen that generally uses on the Vehicles Collected from Market is Dinged Ji ﹑ Gai ∕ Xin Re Wen and is Dinged Ji ﹑ You machine Xi Lei ﹑ rare earth class etc.But because there is the toxicity problem to human body and environment in the heavy metallic salts such as lead salt and barium cadmium salt, many countries and tissue have been put into effect some and have been limited the laws and regulations that You Du ﹑ You Hai ﹑ have pollution substance.European Parliament required Green Book in 2000 by environmental protection bill 76/769/EEC-PVC material environment friendly.Ban use of lead salt in August, 2003 in the electric type material, comprehensive forbidding Lead salt thermal stabilizer in 2015.Under the overall background of environmental law Laws ﹠ Regulations, the plastics of China and Auxiliaries Industry produced also brought challenge and opportunity when impacting, also, environmental protection nontoxic towards exploitation of the research of PVC thermo-stabilizer, direction efficient, multi-functional, thermo-stabilizer that cost performance is good are carried out.
The rare earth carboxylate thermo-stabilizer can not only improve the long-term thermal stability of PVC, can also greatly promote the plasticizing of PVC.The reserves of China's rare earth account for 80% of world saving at present, and this is for exploitation and utilize rare earth resources to be significant.Present existing diprotic acid rare earth carboxylate thermo-stabilizer has dimeracid rare-earth salts, hexanodioic acid rare-earth salts.Wherein dimeracid rare-earth salts thermostable effect is better than the hexanodioic acid rare-earth salts.
It is to adopt oleic acid to divide polymerization at catalyzer and high-temperature lower part that prior art prepares the dimeracid rare-earth salts, steams the unpolymerized lipid acid of part and obtain C under high vacuum
36Dimeracid prepares the dimeracid rare-earth salts with dimeracid and rare earth nitrate, sodium hydroxide 60-80 ℃ of replacement(metathesis)reaction again, and polyreaction requires about 300 ℃ high temperature, consumes a large amount of energy.
Summary of the invention
The objective of the invention is to overcome the present situation that existing thermo-stabilizer environmental pollution is serious, thermo-stabilizer preparation technology energy consumption is large, thermal stability is not high enough, the invention provides a kind of C
21Diprotic acid rare-earth salts and its preparation method and application is that starting raw material prepares by methyl eleostearate.
Technical scheme of the present invention is: a kind of C
21The diprotic acid rare-earth salts, general structure is:
Any one in RE lanthanum, cerium, praseodymium, neodymium, Po ﹑ samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, scandium, the yttrium wherein.
A kind ofly prepare C claimed in claim 1
21The method of diprotic acid rare-earth salts, C
21Diprotic acid mono-methyl, sodium hydroxide, soluble ree inorganic salt with dissolution with solvents after, in solvent, carry out replacement(metathesis)reaction, obtain C after the product suction filtration that obtains, washing, oven dry, the pulverizing
21The diprotic acid rare-earth salts; Described soluble ree inorganic salt are any one in rare earth nitrate, hydrochloride or the vitriol in lanthanum, cerium, praseodymium, neodymium, Po ﹑ samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, scandium, the yttrium.
Described C
21The diprotic acid mono-methyl carries out the Diels-Alder addition reaction by methyl eleostearate and vinylformic acid and obtains in the presence of stopper.
Described C
21Diprotic acid mono-methyl, sodium hydroxide, soluble ree inorganic salt are that 0.5 ~ 1.5 ︰, 3 ︰ 1 throw in according to molar ratio.
The temperature of described replacement(metathesis)reaction is 40 ℃ ~ 80 ℃.
In the described solvent Wei Shui ﹑ Yi Chun ﹑ butanols any one or any several mixture.
Described C
21The diprotic acid rare-earth salts is as the application of PVC thermo-stabilizer.
Described C
21The composite rear application as the PVC thermo-stabilizer of diprotic acid rare-earth salts is with any two kinds of C that contain different rare earth elements
21The diprotic acid rare-earth salts mixes use according to the ratio of mass ratio 0.1:0.2 ~ 1.6.
Beneficial effect:
(1) and C
36The dimer (fatty acid) yl rare earth thermal stabilizer is compared, in the situation that the metallic element addition is identical in the thermo-stabilizer, and the C of the present invention's preparation
21The diprotic acid rare earth thermal stabilizer has better initial stage thermostability and long-term thermal stability.
(2) C
21Diprotic acid compares C
36Few 15 carbon atoms of dimeracid.Short carbochain has reduced the viscosity of diprotic acid rare-earth salts, has improved the consistency with PVC.While C
21Diprotic acid does not contain non-ring structure, and the C of industrial preparation
36Contain approximately 40% non-ring structure dimer in the dimeracid.According to polymer principle of science, the increase composition of ring texture can improve the thermostability of polymer materials.
(3) adopting the fatty acid methyl ester biomass resource is basic raw material, has enlarged the added value of biomass material, has reduced the consumption to petroleum resources, is conducive to save petroleum resources.Methyl eleostearate contains alpha-eleostearic acid methyl esters and the β-methyl eleostearate of 80%-85%, has the structure of conjugated triene key, and the synthetic diprotic acid of Diels-Alder addition reaction occurs under lower temperature easy and different dienophiles, and energy consumption is low, preparation technology's environmental protection.
(4) preparation method's technique of the present invention is simple, and reaction conditions is gentle.
(5) discharge without toxic substance in the preparation process, operational path has environment friendly.
Description of drawings
Fig. 1. C
21Diprotic acid rare-earth salts infrared spectrum.
Fig. 2. the C of embodiment 1 and embodiment 2
21The XRD spectra of diprotic acid rare-earth salts.
Embodiment
The C that the present invention is used
21Diprotic acid mono-methyl (TMAA) is according to " synthesizing C by methyl eleostearate
21The research of diprotic acid mono-methyl and Characterization of The Products ", chemical reagent, 2008,30(10), the method in 725 ~ 728,775 prepares.
A kind ofly prepare C by methyl eleostearate
21The method of diprotic acid rare-earth salts is made by following steps:
Be 0.5 ~ 1.5 ︰, 3 ︰ 1 with TMAA ︰ Qing Yangization Na ︰ soluble ree inorganic salt according to molar ratio, at 40 ℃ ~ 80 ℃ replacement(metathesis)reactions occur after adding dissolution with solvents.React complete after, product is through suction filtration, washing, oven dry, grinds, and obtains C
21Diprotic acid rare-earth salts (RE
2(to)
3).General structure is:
Any one in RE lanthanum, cerium, praseodymium, neodymium, Po ﹑ samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, scandium, the yttrium wherein.
Described solvent is any one or two kinds that are selected from the Shui ﹑ Yi Chun ﹑ butanols.
Described soluble ree inorganic salt comprise Xi soil Xiao Suan Yan ﹑ Xi soil Liu Suan Yan ﹑ rare-earth salts hydrochlorate etc.
Preparation C
21In the process of diprotic acid rare-earth salts, the molar ratio of TMAA, sodium hydroxide, rare earth nitrate is 3 ︰, 6 ︰ 2 or 1 ︰, 3 ︰ 1 or 1 ︰, 6 ︰ 2.
Prepared C
21The diprotic acid rare-earth salts can be separately uses as the PVC thermo-stabilizer, also can composite rear use, and the effect of composite rear use is better than independent use.
C
21The diprotic acid rare-earth salts is composite: with any two kinds of C that contain different rare earth elements
21Diprotic acid rare-earth salts in mass ratio 0.1 ︰ 0.2 ~ 1.6 is composite, after mixing with high-speed mixer, after the milled processed and get final product.
Embodiment 1
C
21Synthesizing of diprotic acid lanthanum salt
(1) in the there-necked flask that magnetic stirring apparatus, thermometer and reflux condensing tube are housed, adds methyl eleostearate 100 g, vinylformic acid 24.7 g and Resorcinol 0.25 g, be warming up to 180 ℃, be incubated 3 h, underpressure distillation under the vacuum condition of ﹣ 0.08 ~ ﹣ 0.1 MPa, remove first excessive vinylformic acid and do not participate in the fatty acid methyl ester of reaction, intercept again the cut between 254 ~ 260 ℃, obtain light yellow liquid 106 g, be TMAA.
(2) in the four-hole boiling flask that magnetic stirring apparatus, thermometer, dropping funnel are housed, add
32.5 the g lanthanum nitrate is used anhydrous alcohol solution, then respectively with 54.8 g TMAA, 12 g sodium hydroxide equal-volume anhydrous alcohol solutions, pack in two dropping funnels, heating in water bath to 65 ℃ starts stirring, drip TMAA and sodium hydroxide, after dropwising, continue insulation reaction 0.5 h.Product is through suction filtration, washing, and oven dry gets 81.4 g C
21Diprotic acid lanthanum salt.
Embodiment 2
C
21Synthesizing of diprotic acid cerium salt
(1) in the there-necked flask that magnetic stirring apparatus, thermometer and reflux condensing tube are housed, adds methyl eleostearate 100 g, vinylformic acid 24.7 g and Resorcinol 0.25 g, be warming up to 180 ℃, be incubated 3 h, underpressure distillation under the vacuum condition of ﹣ 0.08 ~ ﹣ 0.1 MPa, remove first excessive vinylformic acid and do not participate in the fatty acid methyl ester of reaction, intercept again the cut between 254 ~ 260 ℃, obtain light yellow liquid 106 g, be TMAA.
(2) in the four-hole boiling flask that magnetic stirring apparatus, thermometer, dropping funnel are housed, add
32.6 the g cerous nitrate is used anhydrous alcohol solution, then respectively with 54.8 g TMAA, 12 g sodium hydroxide equal-volume anhydrous alcohol solutions, pack in two dropping funnels, heating in water bath to 65 ℃ starts stirring, drip TMAA and sodium hydroxide, after dropwising, continue insulation reaction 0.5 h.Product is through suction filtration, washing, and oven dry gets 82.7 g C
21Diprotic acid lanthanum salt.
C
21Synthesizing of diprotic acid lanthanum salt
(1) in the there-necked flask that magnetic stirring apparatus, thermometer and reflux condensing tube are housed, adds methyl eleostearate 100 g, vinylformic acid 24.7 g and Resorcinol 0.25 g, be warming up to 180 ℃, be incubated 3 h, underpressure distillation under the vacuum condition of ﹣ 0.08 ~ ﹣ 0.1 MPa, remove first excessive vinylformic acid and do not participate in the fatty acid methyl ester of reaction, intercept again the cut between 254 ~ 260 ℃, obtain light yellow liquid 106 g, be TMAA.
(2) in the four-hole boiling flask that magnetic stirring apparatus, thermometer, dropping funnel are housed, add
32.5 the g lanthanum nitrate is used anhydrous alcohol solution, then respectively with 54.8 g TMAA, 12 g sodium hydroxide equal-volume anhydrous alcohol solutions, pack in two dropping funnels, heating in water bath to 65 ℃ starts stirring, drip TMAA and sodium hydroxide, after dropwising, continue insulation reaction 0.5 h.Product is through suction filtration, washing, and oven dry gets 81.6 g C
21Diprotic acid lanthanum salt.
Embodiment 4
C
21Synthesizing of diprotic acid cerium salt
(1) in the there-necked flask that magnetic stirring apparatus, thermometer and reflux condensing tube are housed, adds methyl eleostearate 100 g, vinylformic acid 24.7 g and Resorcinol 0.25 g, be warming up to 180 ℃, be incubated 3 h, underpressure distillation under the vacuum condition of ﹣ 0.08 ~ ﹣ 0.1 MPa, remove first excessive vinylformic acid and do not participate in the fatty acid methyl ester of reaction, intercept again the cut between 254 ~ 260 ℃, obtain light yellow liquid 106 g, be TMAA.
(2) in the four-hole boiling flask that magnetic stirring apparatus, thermometer, dropping funnel are housed, add
32.6 the g cerous nitrate is used anhydrous alcohol solution, then respectively with 54.8 g TMAA, 12 g sodium hydroxide equal-volume anhydrous alcohol solutions, pack in two dropping funnels, heating in water bath to 65 ℃ starts stirring, drip TMAA and sodium hydroxide, after dropwising, continue insulation reaction 0.5 h.Product is through suction filtration, washing, and oven dry gets 82.9 g C
21Diprotic acid lanthanum salt.
Embodiment 5
0.8 ︰ 3.2 is with the C of embodiment 1 in mass ratio
21The C of diprotic acid lanthanum salt and embodiment 2
21After diprotic acid cerium salt mixes with high-speed mixer, both got C after the milled processed
21The diprotic acid rare earth complex heat stabilizer.
Embodiment 6
1.6 ︰ 2.4 are with the C of embodiment 1 in mass ratio
21The C of diprotic acid lanthanum salt and embodiment 2
21After diprotic acid cerium salt mixes with high-speed mixer, both got C after the milled processed
21The diprotic acid rare earth complex heat stabilizer.
Embodiment 7
2.4 ︰ 1.6 are with the C of embodiment 3 in mass ratio
21The C of diprotic acid lanthanum salt and embodiment 4
21After diprotic acid cerium salt mixes with high-speed mixer, both got C after the milled processed
21The diprotic acid rare earth complex heat stabilizer.
Embodiment 8
3.2 ︰ 0.8 are with the C of embodiment 1 in mass ratio
21The C of diprotic acid lanthanum salt and embodiment 2
21After diprotic acid cerium salt mixes with high-speed mixer, both got C after the milled processed
21The diprotic acid rare earth complex heat stabilizer.
Embodiment 9
4 ︰ 0 are with the C of embodiment 3 in mass ratio
21The C of diprotic acid lanthanum salt and embodiment 4
21After diprotic acid cerium salt mixes with high-speed mixer, both got C after the milled processed
21The diprotic acid rare earth complex heat stabilizer.
Change the soluble ree inorganic salt among the embodiment 1 into corresponding praseodymium salt or neodymium salt obtains C
21Diprotic acid praseodymium salt and C
21Diprotic acid neodymium salt.
3.2 ︰ 0.8 are with C in mass ratio
21Diprotic acid praseodymium salt and C
21After diprotic acid neodymium salt mixes with high-speed mixer, both got C after the milled processed
21The diprotic acid rare earth complex heat stabilizer.
Embodiment 11
Change the soluble ree inorganic salt among the embodiment 1 into corresponding promethium salt or samarium salt obtains C
21Diprotic acid promethium salt and C
21Diprotic acid samarium salt.
2.4 ︰ 1.6 are with C in mass ratio
21Diprotic acid promethium salt and C
21After diprotic acid samarium salt mixes with high-speed mixer, both got C after the milled processed
21The diprotic acid rare earth complex heat stabilizer.
Embodiment 12
Accompanying drawing 1 is C
21Diprotic acid rare-earth salts infrared spectrum, wherein a is the C of embodiment 1
21Diprotic acid lanthanum salt, b are the C of embodiment 2
21Diprotic acid cerium salt.Analytical instrument: Nicolet 550 type infrared spectrometers.
As shown in Figure 1, C
21The maximum characteristics of the infrared spectrum of diprotic acid rare-earth salts (a, b) are 1700 ~ 1800cm
-1The place does not have absorption peak, and 1741 cm are described
-1The stretching vibration absorption peak of the fatty acid ester C=O of place disappears 1705 cm
-1The stretching vibration absorption peak of the C=O of place's carboxyl disappears.2924 cm
-1About and 2854 cm
-1About be respectively the asymmetric of methylene radical C-H and symmetrical stretching vibration absorption peak.ν in the carboxyl
OHAt 3000 ~ 2500 cm
-1The charateristic avsorption band of Qiang Erkuan disappears, simultaneously 1533 cm
-1About the antisymmetric stretching vibration absorption peak of carboxylate ion, 1400 cm appear
-1About the symmetrical stretching vibration absorption peak of carboxylate ion appears.
Embodiment 13
Accompanying drawing 2 is the C of embodiment 1 and embodiment 2
21The XRD spectra of diprotic acid rare-earth salts.Analytical instrument: XRD powder diffractometer (D8FOCUS), German BRUKER company.
The XRD figure spectrum all presents sharp-pointed diffraction peak as seen from Figure 2, and C is described
21The diprotic acid rare-earth salts is crystallization.Three larger diffraction peaks occurred, do not found the diffraction peak of other impurity, synthetic C has been described
21Diprotic acid lanthanum salt and C
21Diprotic acid cerium salt product are mutually single, crystalline structure is complete.The XRD spectra baseline is low flat, and diffraction peak-to-peak type point is alarmmed, and illustrates that the order degree of crystal face growth is higher, and degree of crystallinity is better.
Embodiment 14
Experimental group 1:
C with embodiment 1
21The C of diprotic acid lanthanum salt and embodiment 2
21Diprotic acid cerium salt is pressed certain mass than adding among the PVC, and it is as follows to fill a prescription:
Table 1. plastic shaping prescription
| Raw material | Mass ratio |
| PVC | 200 |
| DOP | 80 |
| La 2(to) 3 | 0.8 |
| Ce 2(to) 3 | 3.2 |
Experimental group 2:
C with embodiment 3
21The C of diprotic acid lanthanum salt and embodiment 4
21Diprotic acid cerium salt is pressed certain mass than adding among the PVC, and it is as follows to fill a prescription:
Table 2. plastic shaping prescription
| Raw material | Mass ratio |
| PVC | 200 |
| DOP | 80 |
| La 2(to) 3 | 1.6 |
| Ce 2(to) 3 | 2.4 |
Experimental group 3:
C with embodiment 1
21The C of diprotic acid lanthanum salt and embodiment 2
21Diprotic acid cerium salt is pressed certain mass than adding among the PVC, and it is as follows to fill a prescription:
Table 3. plastic shaping prescription
| Raw material | Mass ratio |
| PVC | 200 |
| DOP | 80 |
| La 2(to) 3 | 2.4 |
| Ce 2(to) 3 | 1.6 |
Experimental group 4:
C with embodiment 1
21The C of diprotic acid lanthanum salt and embodiment 2
21Diprotic acid cerium salt is pressed certain mass than adding among the PVC, and it is as follows to fill a prescription:
Table 4. plastic shaping prescription
| Raw material | Mass ratio |
| PVC | 200 |
| DOP | 80 |
| La 2(to) 3 | 3.2 |
| Ce 2(to) 3 | 0.8 |
Experimental group 5:
C with embodiment 1
21The C of diprotic acid lanthanum salt and embodiment 2
21Diprotic acid cerium salt is pressed certain mass than adding among the PVC, and it is as follows to fill a prescription:
Table 5. plastic shaping prescription
| Raw material | Mass ratio |
| PVC | 200 |
| DOP | 80 |
| La 2(to) 3 | 4.0 |
Comparative group 1:
Dimeracid lanthanum salt is pressed certain mass than adding among the PVC, and it is as follows to fill a prescription:
Table 6. plastic shaping prescription
| Raw material | Mass ratio |
| PVC | 200 |
| DOP | 80 |
| Dimeracid lanthanum salt | 4.0 |
Comparative group 2:
Dimeracid lanthanum salt is pressed certain mass than adding among the PVC, and it is as follows to fill a prescription:
Table 7. plastic shaping prescription
| Raw material | Mass ratio |
| PVC | 200 |
| DOP | 80 |
| Dimeracid lanthanum salt | 6.0 |
Comparative group 3:
Lanthanum Stearate salt and cerium stearate salt are pressed certain mass than adding among the PVC, and it is as follows to fill a prescription:
Table 8. plastic shaping prescription
| Raw material | Mass ratio |
| PVC | 200 |
| DOP | 80 |
| Lanthanum Stearate salt | 4.0 |
Comparative group 4:
Lanthanum Stearate salt and cerium stearate salt are pressed certain mass than adding among the PVC, and it is as follows to fill a prescription:
Table 9. plastic shaping prescription
| Raw material | Mass ratio |
| PVC | 200 |
| DOP | 80 |
| Lanthanum Stearate salt | 0.8 |
| Cerium stearate salt | 3.2 |
(1) carry out the static heat stability test, test result such as table 10 to above-mentioned 7 groups:
Table 10 is got the static heat stability test comparison of each group at random
| Group name | Experimental group 1 | Experimental group 2 | |
Experimental group 4 | Experimental group 5 | Comparative group 1 | Comparative group 2 | |
Comparative group 4 |
| Static heat steady time (min) | 68 | 60 | 62 | 49 | 41 | 28 | 28 | 35 | 45 |
Annotate: Congo red laboratory method is adopted in the static heat stability test, with reference to GB/T2917.1-2002.
(2) experimental group 1 and comparative group 4 are carried out the dynamic thermal stability test, test result such as table 11:
Table 11 is got the dynamic thermal stability test comparison of each group at random
| Group name | Experimental group 1 | Comparative group 4 |
| Dynamic Thermal steady time (min) | 20 | 17 |
Annotate: adopt the torque rheometer method.Get the 60g sample and test at rheometer, initial value rotating speed: 30.0r/min; Milling device test point: T
1=180.5 ℃, T
2=180.9 ℃, T
3=182.3 ℃.
From above test result as can be known, compare C with the dimeracid rare earth with the rare-earth stearate thermo-stabilizer
21The diprotic acid rare earth thermal stabilizer has better static heat stability and dynamic thermal stability in the PVC material, and two kinds of composite effects of rare-earth salts are better than alone a kind of effect, is a kind of PVC thermo-stabilizer with certain marketable value.
Claims (8)
1. C
21The diprotic acid rare-earth salts is characterized in that, general structure is:
Wherein RE is any one in lanthanum, cerium, praseodymium, neodymium, Po ﹑ samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, scandium, the yttrium.
2. one kind prepares C claimed in claim 1
21The method of diprotic acid rare-earth salts is characterized in that, C
21Diprotic acid mono-methyl, sodium hydroxide, soluble ree inorganic salt with dissolution with solvents after, in solvent, carry out replacement(metathesis)reaction, obtain C after the product suction filtration that obtains, washing, oven dry, the pulverizing
21The diprotic acid rare-earth salts; Described soluble ree inorganic salt are any one in rare earth nitrate, hydrochloride or the vitriol in lanthanum, cerium, praseodymium, neodymium, Po ﹑ samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, scandium, the yttrium.
3. preparation C as claimed in claim 2
21The method of diprotic acid rare-earth salts is characterized in that, described C
21The diprotic acid mono-methyl carries out the Diels-Alder addition reaction by methyl eleostearate and vinylformic acid and obtains in the presence of stopper.
4. preparation C as claimed in claim 2
21The method of diprotic acid rare-earth salts is characterized in that, described C
21Diprotic acid mono-methyl, sodium hydroxide, soluble ree inorganic salt are that 0.5 ~ 1.5 ︰, 3 ︰ 1 throw in according to molar ratio.
5. such as claim 2 or 4 described preparation C
21The method of diprotic acid rare-earth salts is characterized in that, the temperature of described replacement(metathesis)reaction is 40 ℃ ~ 80 ℃.
6. preparation C as claimed in claim 5
21The method of diprotic acid rare-earth salts is characterized in that, any one in the described solvent Wei Shui ﹑ Yi Chun ﹑ butanols or any several mixture.
7. C claimed in claim 1
21The diprotic acid rare-earth salts is as the application of PVC thermo-stabilizer.
8. C claimed in claim 1
21The composite rear application as the PVC thermo-stabilizer of diprotic acid rare-earth salts is characterized in that, with any two kinds of C that contain different rare earth elements
21The diprotic acid rare-earth salts mixes use according to the ratio of mass ratio 0.1:0.2 ~ 1.6.
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| CN111153793A (en) * | 2019-11-21 | 2020-05-15 | 池州瑞亚特新材料有限公司 | Toughening agent and preparation and use methods thereof |
| CN113477241A (en) * | 2021-09-07 | 2021-10-08 | 华南理工大学 | Ternary composite photocatalyst and preparation method and application thereof |
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| CN105482286A (en) * | 2014-09-17 | 2016-04-13 | 河北大学 | Polybasic carboxylic acid rare earth heat stabilizer preparation method |
| CN105482286B (en) * | 2014-09-17 | 2017-05-31 | 河北大学 | The preparation method of polybasic carboxylic acid class rare earth thermal stabilizer |
| CN104672703A (en) * | 2015-02-07 | 2015-06-03 | 山东天汇防水材料有限公司 | Organic rear earth polymer ultraviolet crosslinked exposed waterproof roll and preparation method thereof |
| CN106187743A (en) * | 2016-07-15 | 2016-12-07 | 山东源根石油化工有限公司 | The preparation of a kind of dimeric dibasic acid lanthanum extreme pressure anti-wear additives and the energy saving wear-resistant hydraulic oil containing this dimeric dibasic acid lanthanum extreme pressure anti-wear additives |
| CN111153793A (en) * | 2019-11-21 | 2020-05-15 | 池州瑞亚特新材料有限公司 | Toughening agent and preparation and use methods thereof |
| CN111153793B (en) * | 2019-11-21 | 2022-08-30 | 重庆集凯科技服务有限公司 | Toughening agent and preparation and use methods thereof |
| CN113477241A (en) * | 2021-09-07 | 2021-10-08 | 华南理工大学 | Ternary composite photocatalyst and preparation method and application thereof |
| CN113477241B (en) * | 2021-09-07 | 2021-12-17 | 华南理工大学 | Ternary composite photocatalyst and preparation method and application thereof |
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