CN103819718A - Preparation method for samarium-group multiple-ligand thiofide - Google Patents

Preparation method for samarium-group multiple-ligand thiofide Download PDF

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CN103819718A
CN103819718A CN201410075269.6A CN201410075269A CN103819718A CN 103819718 A CN103819718 A CN 103819718A CN 201410075269 A CN201410075269 A CN 201410075269A CN 103819718 A CN103819718 A CN 103819718A
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ligand
samarium
thiofide
sma
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CN103819718B (en
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刘力
杜一诗
摆音娜
胡水
温世鹏
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Abstract

The invention discloses a samarium-group multiple-ligand thiofide and a preparation method thereof. According to the preparation method, during synthesis, a rare earth element is a samarium element comprising four ligands. The ligand 1 and the ligand 2 are accelerating agent groups with an excellent vulcanization accelerating effect, the ligand 3 is acrylic acid capable of improving the dissolubility of an accelerator in a sizing material, and the ligand 4 is triethanolamine capable of forming strong coordination with the rare earth element. The preparation method for the samarium-group multiple-ligand thiofide is simple, convenient and feasible, and does not need inert gas for protection, conditions in the preparing process are mild, and production of harmful gas is prevented. The multiple-ligand rare earth thiofide has good dissolubility in rubber, and is long in sulfidation and scorching times, good in flatness of a sulfidation curve, nontoxic, odorless and free from contamination. The thiofide can substitute a conventionally frequently-used simultaneous-use system of zinc oxide, stearic acid and an accelerator, and is applied to high-performance tires and other rubber products.

Description

The preparation method of a kind of samarium Quito part thiofide
Technical field
What the present invention relates to is the research of synthetic method and the sulfuration facilitation effect thereof of a kind of samarium Quito part vulcanization accelerator.This promotor without zinc oxide, stearic acid as activator, there is saving charging process, cleanliness without any pollution, sulfuration flatness is good, in rubber, be easy to the advantages such as dispersed, apply rubber composite prepared by this promotor and there is good performance homogeneity.
Background technology
The vulcanization system of rubber is a complete vulcanization system being made up of promotor, activator, vulcanizing agent.Wherein promotor is that one can shorten curing time, reduces curing temperature, reduces vulcanizing agent consumption, improves and improve the physical and mechanical properties of cross-linked rubber and the chemical substance of chemical stability.Just because of promotor can be improved the sulfuration efficiency of rubber, enhance productivity, lower energy consumption, improve the quality of goods, development of new thiofide is a study hotspot in rubber industry always.
The complete vulcanization system being made up of Sulfur, activator, three kinds of components of promotor, in vulcanization reaction process, has all played an active part in reaction.In traditional zinc oxide, lipid acid and promotor 2-mercaptobenzothiazole paralled system, this three has formed the zinc salt of intermediate product benzothiazole-2-mercaptan with greater activity in rubber, but because the shearing action of two rollers is limited, in addition zinc oxide belongs to inorganic particulate, make the solvability of this vulcanization accelerator in rubber bad, cause adjuvant system to be disperseed in sizing material inhomogeneous, cause rubber composite each point performance heterogeneity, affect the life-span of elastomeric material.
Summary of the invention
The object of the invention is to the sulfur sulfide system of zinc oxide, lipid acid, accelerator combination to make the improvement of substitutability.This kind of promotor has been improved the solvability bad shortcoming of traditional sulfuration Promotion system in rubber effectively, simplifies charging process, cleanliness without any pollution.This multiple ligand rare earth vulcanization accelerator has good sulfuration facilitation effect under high temperature vulcanized condition, and anti-incipient scorch ability is strong, and the smooth phase is long, and promotor is dissolved well in sizing material simultaneously, has guaranteed the homogeneity of elastomeric material or quality of item.
Promotor of the present invention is a kind ofly by rare earth samarium element and 4 kinds of parts, the title complex that coordination reaction produces to occur in solvent, and its general structure is as follows:
[Sm xA yB zC mD n]
In formula:
Sm is rare earth samarium element.
Organic ligand A is dimethyl dithiocarbamic acid, has following structure:
Figure BDA0000472280530000021
Organic ligand B is 2-mercaptobenzothiazole, has following structure:
Figure BDA0000472280530000022
Organic ligand C is α-methacrylic acid, has following structure:
Organic ligand D is trolamine, has following structure:
Figure BDA0000472280530000024
x=1；
y=0.01～2；
z=0～2；
m=0～3；
n=0～1。
The preparation method of described a kind of multiple ligand vulcanization acceralator for rare earth rubber, comprises the following steps:
(1) samarium trichloride is dissolved in the dehydrated alcohol of 60～80 ℃, an alkali metal salt of the dimethyl dithiocarbamic acid that contains A part is dissolved in the dehydrated alcohol of 60～80 ℃.The 2-mercaptobenzothiazole that contains B part is dissolved in the dehydrated alcohol of 60～80 ℃ that contains NaOH, again the α-methacrylic acid that contains C part and the trolamine that contains D part are dissolved in respectively in the dehydrated alcohol of 60～80 ℃, prepare five kinds of ethanol solutions.
(2) ethanol solution that contains four kinds of parts is fully mixed.Under the oil baths of 60～80 ℃ are stirred, the ethanol solution of mixed ligand is added drop-wise in the ethanol solution of samarium trichloride, after stirring 4～8h, filter, precipitation, after absolute ethanol washing, is dried to permanent quality in moisture eliminator, is the vulcanization acceralator for rare earth rubber of multiple ligand.
Described samarium trichloride is the muriate of rare earth samarium element.
Donor water for fear of oxygen preferentially reacts with samarium trichloride, and it is reaction solvent that the present invention adopts dehydrated alcohol.
In order to prevent that, because the organic composition in excess Temperature samarium complex decomposes and samarium complex moisture absorption in air, the present invention adopts in the sealed environment at 20～30 ℃ dry, siccative is selected Calcium Chloride Powder Anhydrous.
The multiple ligand vulcanization acceralator for rare earth rubber the present invention relates to has good sulfuration facilitation effect, can obtain better facilitation effect with under further cooperation of vulcanizing agent and filler.
The present invention can substitute the system of traditional zinc oxide, lipid acid, accelerator combination effectively, has saved the consumption of auxiliary agent, has simplified the technique in rubber composite preparation process, has greatly improved the solvability of vulcanization system in rubber.
The present invention has made up the defect of prior art, and the organic promoter that has overcome some kinds exists reversion and the easy shortcoming such as incipient scorch while use separately.This kind of multiple ligand rare earth compounding has good sulfuration flatness, improved the homogeneity of properties of rubber, is a kind of novel environment friendly rubber ingredients of high efficiency and multi-function.
The present invention, compared with domestic and international prior art, has following advantage:
1. multiple ligand vulcanization acceralator for rare earth rubber preparation method of the present invention is simple and easy to do, can prepare without protection of inert gas, and mild condition, does not produce obnoxious flavour in building-up process.
2. samarium of the present invention Quito part vulcanization accelerator is a kind of new type rubber auxiliary agent of clean environment firendly, does not produce toxic gas in Vulcanization Process of Rubber, and when reinforced, airborne dust is little, simplifies charging process, meets the national standard of environmental protection auxiliary agent.
3. samarium of the present invention Quito part vulcanization accelerator not only has certain sulfuration facilitation effect at low temperatures, at high temperature vulcanizes facilitation effect remarkable, has improved scorch safety, and vulcanization curve flatness is good, has good reversion resistance in high temperature vulcanized.
4. samarium of the present invention Quito part vulcanization accelerator can make the cross-linking density of cross-linked rubber increase, and forms better three-dimensional net structure, improves homogeneity and the stability of cured properties, has reached the effect of potion multipotency.Accompanying drawing explanation
Fig. 1 is promotor SmA in embodiment 1 2b 0c 0d 1infrared spectrum, Fig. 2 is promotor SmA in embodiment 2 0.01b 2c 3d 0infrared spectrum, Fig. 3 is promotor SmA in embodiment 3 1b 1c 1.5d 0.5infrared spectrum.
Fig. 4 is the rubber unvulcanizate prepared of the listed formula of table 2 at the vulcanization curve figure of 170 ℃.
Fig. 5 is the transparence photo of the cross-linked rubber prepared under 170 ℃ of curing temperatures of the listed formula 2-mercaptobenzothiazole of table 2.
Fig. 6 is the listed formula of table 2 SmA 2b 0c 0d 1the transparence photo of the cross-linked rubber of preparing under 170 ℃ of curing temperatures, Fig. 7 is the listed formula of table 2 SmA 0.01b 2c 3d 0the transparence photo of the cross-linked rubber of preparing under 170 ℃ of curing temperatures, Fig. 8 is the listed formula of table 2 SmA 1b 1c 1.5d 0.5the transparence photo of the cross-linked rubber of preparing under 170 ℃ of curing temperatures.
Embodiment
Below in conjunction with specific examples, the present invention will be described in detail, and protection scope of the present invention includes but not limited to following instance.
The rubber unvulcanizate of preparation is to vulcanize compressing tablet under 170 ℃ of conditions.
Embodiment 1
The preparation method of promotor:
By 0.01molSmCl 3be dissolved in the dehydrated alcohol of 60 ℃, 0.02mol Sodium dimethyldithiocarbamate 40min be dissolved in the ethanol solution of 60 ℃, 0.01mol trolamine is dissolved in the ethanol solution of 60 ℃.The ethanolic soln of the ethanolic soln of Sodium dimethyldithiocarbamate 40min and trolamine is fully mixed, obtain mixing solutions.Then above-mentioned mixing solutions is added drop-wise to SmCl 3ethanol solution in, oil bath is filtered after stirring 6h at 80 ℃, precipitation, after absolute ethanol washing, is being placed with CaCl 2in the moisture eliminator of siccative, be dried to permanent quality in 20 ℃, obtain a kind of white powder, i.e. target product SmA 2b 0c 0d 1.
Embodiment 2
The preparation method of promotor:
By 0.01molSmCl 3be dissolved in the dehydrated alcohol of 60 ℃, 0.02mol2-mercaptobenzothiazole is dissolved in the ethanol solution of 60 ℃ that contains 0.02mol NaOH, 0.0001mol Sodium dimethyldithiocarbamate 40min is dissolved in the ethanol solution of 60 ℃, 0.03mol α-methacrylic acid is dissolved in the ethanol solution of 60 ℃.The ethanolic soln of Sodium dimethyldithiocarbamate 40min, the ethanolic soln of Vencide salt and the ethanolic soln of α-methacrylic acid are fully mixed, obtain mixing solutions.Then above-mentioned mixing solutions is added drop-wise to SmCl 3ethanol solution in, oil bath is filtered after stirring 6h at 80 ℃, precipitation, after absolute ethanol washing, is being placed with CaCl 2in the moisture eliminator of siccative, be dried to permanent quality in 20 ℃, obtain a kind of pale yellow powder, i.e. target product SmA 0.01b 2c 3d 0.
Embodiment 3
The preparation method of promotor:
By 0.01molSmCl 3be dissolved in the dehydrated alcohol of 60 ℃, 0.01mol Sodium dimethyldithiocarbamate 40min is dissolved in the ethanol solution of 60 ℃, 0.01mol2-mercaptobenzothiazole is dissolved in the ethanol solution of 60 ℃ that contains 0.01mol NaOH, 0.015mol α-methacrylic acid is dissolved in the ethanol solution of 60 ℃, 0.005mol trolamine is dissolved in the ethanol solution of 60 ℃.The ethanolic soln of the ethanolic soln of Sodium dimethyldithiocarbamate 40min, Vencide salt, the ethanolic soln of α-methacrylic acid and the ethanolic soln of trolamine are fully mixed, obtain mixing solutions.Then above-mentioned mixing solutions is added drop-wise to SmCl 3ethanol solution in, oil bath is filtered after stirring 6h at 80 ℃, precipitation, after absolute ethanol washing, is being placed with CaCl 2in the moisture eliminator of siccative, be dried to permanent quality in 20 ℃, obtain a kind of pale yellow powder, i.e. target product SmA 1b 1c 1.5d 0.5.
Embodiment 4
To the promotor SmA making in embodiment 1～3 2b 0c 0d 1, SmA 0.01b 2c 3d 0and SmA 1b 1c 1.5d 0.5carry out ultimate analysis, result sees table 1.
Table 1
Figure BDA0000472280530000051
Can be drawn the promotor SmA making in embodiment 1～3 by table 1 2b 0c 0d 1, SmA 0.01b 2c 3d 0and SmA 1b 1c 1.5d 0.5in have difference between the theoretical value of each element and measured value, be speculated as in accelerant powder and contain due to a small amount of crystal water and instrumental error.
Embodiment 5
To the promotor SmA making in embodiment 1～3 2b 0c 0d 1, SmA 0.01b 2c 3d 0and SmA 1b 1c 1.5d 0.5carry out Infrared Characterization, result sees Fig. 1～3.
From Fig. 1～3, the promotor SmA making in embodiment 1～3 2b 0c 0d 1, SmA 0.01b 2c 3d 0and SmA 1b 1c 1.5d 0.5all at 1143cm – 1, 994cm -1near there is respectively the similar absorption peak of C=S and C-S.To SmA 0.01b 2c 3d 0and SmA 1b 1c 1.5d 0.5, although there is not obvious displacement in the stretching vibration ν (C-S) of sulfydryl, intensity enhancing, has shown that the outer sulfydryl of ring of part has participated in Cheng Jian; Visible part is to encircle the double coordination that the N atom on outer S atom and ring carries out.SmA 2b 0c 0d 1and SmA 1b 1c 1.5d 0.5at 3600-3200,1450-1400,1092-1060cm – 1all there is absorption peak in interval, these peaks result from N-H, the CH on trolamine part 2and CH 2-OH structure.For the SmA that contains α-methacrylic acid part 0.01b 2c 3d 0and SmA 1b 1c 1.5d 0.5, the C=O absorption peak in carboxyl occurs in 1705cm – 1near.SmA 2b 0c 0d 1, SmA 0.01b 2c 3d 0and SmA 1b 1c 1.5d 0.5at 3500cm -1near all there is wider hydroxyl stretching vibration absorption peak, illustrate and in title complex, contain crystal water.
Embodiment 6
Use the promotor SmA making in embodiment 1～3 2b 0c 0d 1, SmA 0.01b 2c 3d 0, SmA 1b 1c 1.5d 0.5and zinc oxide/stearic acid/2-mercaptobenzothiazole (a kind of conventional promotor) is prepared styrene-butadiene rubber(SBR)/promotor matrix material.The formula of rubber unvulcanizate is as shown in table 1, adopts two roller mills to prepare according to a conventional method rubber unvulcanizate, is abbreviated as SmA in sample number into spectrum 2b 0c 0d 1, SmA 0.01b 2c 3d 0and SmA 1b 1c 1.5d 0.5.
Table 2
Figure BDA0000472280530000061
The curability test of rubber unvulcanizate adopts rheometer test.The vulcanization curve of rubber unvulcanizate at 170 ℃ as shown in Figure 4.From figure, can draw samarium Quito ligand-complexes vulcanization accelerator SmA 2b 0c 0d 1, SmA 0.01b 2c 3d 0and SmA 1b 1c 1.5d 0.5at 170 ℃, have remarkable sulfuration facilitation effect, and the smooth phase of curve is long.
According to the cross-linked rubber that in table 2, listed formula 2-mercaptobenzothiazole is prepared under 170 ℃ of curing temperatures, adopt the DSC-W670 of Sony digital camera to take, transparence photo is as shown in Figure 5.According to listed formula SmA in table 2 2b 0c 0d 1, SmA 0.01b 2c 3d 0and SmA 1b 1c 1.5d 0.5the cross-linked rubber of preparing under 170 ℃ of curing temperatures, adopts the DSC-W670 of Sony digital camera to take, and transparence photo is as shown in Fig. 6～8.Comparison diagram 5 and Fig. 6～8 can be found out, SmA 2b 0c 0d 1, SmA 0.01b 2c 3d 0and SmA 1b 1c 1.5d 0.5transparence be obviously better than traditional promotor 2-mercaptobenzothiazole, illustrate that samarium Quito ligand-complexes vulcanization accelerator can dissolve better in rubber, thereby promoted the homogeneity of rubber composite performance.

Claims (3)

1. samarium Quito part thiofide, it is characterized in that: it contains rare earth samarium element, dimethyl dithiocarbamic acid group and 2-mercaptobenzothiazole group are as main part, and acrylic acid groups and trolamine group are as assistant ligand, and its general molecular formula is:
Sm xA yB zC mD n
In formula: A is dimethyl dithiocarbamic acid part, B is 2-mercaptobenzothiazole part, and C is acrylic ligand, and D is trolamine part, x=1, y=0.01～2, z=0～2, m=0～3, n=0～1.
2. the preparation method of a kind of samarium according to claim 1 Quito part thiofide, is characterized in that, comprises the following steps:
(1) samarium trichloride is dissolved in the dehydrated alcohol of 60～80 ℃, the an alkali metal salt of Sodium dimethyldithiocarbamate 40min and 2-mercaptobenzothiazole is dissolved in respectively in the ethanol solution of 60～80 ℃, vinylformic acid and trolamine is dissolved in respectively in the ethanol solution of 60～80 ℃;
(2) ethanolic soln that contains Sodium dimethyldithiocarbamate 40min, the ethanolic soln, the ethanolic soln that contains acrylic acid ethanolic soln and contain trolamine of an alkali metal salt that contain 2-mercaptobenzothiazole are fully mixed, obtain mixing solutions, above-mentioned mixing solutions is added drop-wise in the ethanol solution of samarium trichloride, after stirring 4～8h at 60～80 ℃ of constant temperature, filter, precipitation, after absolute ethanol washing, is dried to permanent quality.
3. method according to claim 2, is characterized in that: in step (2), drying process is the hermetically drying at 20～30 ℃, and siccative is selected Calcium Chloride Powder Anhydrous.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101781413A (en) * 2010-03-22 2010-07-21 福建师范大学 Preparation method of rare earth coordination crosslinking rubber

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101781413A (en) * 2010-03-22 2010-07-21 福建师范大学 Preparation method of rare earth coordination crosslinking rubber

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
章伟光,等: "稀土含硫有机配体配合物的合成与应用研究进展", 《中国稀土学报》 *

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