CN103819723B - A kind of cerium Quito part vulcanization accelerator and preparation method thereof - Google Patents
A kind of cerium Quito part vulcanization accelerator and preparation method thereof Download PDFInfo
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- CN103819723B CN103819723B CN201410075284.0A CN201410075284A CN103819723B CN 103819723 B CN103819723 B CN 103819723B CN 201410075284 A CN201410075284 A CN 201410075284A CN 103819723 B CN103819723 B CN 103819723B
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- cerium
- rubber
- phenanthroline
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Abstract
The invention discloses a kind of cerium Quito part vulcanization accelerator and preparation method thereof.Rare earth element in synthesis is Ce elements, containing 4 kinds of parts.Ligand 1 and 2 is for having the promotor group of good sulfuration facilitation effect, and part 3 is for can improve promotor deliquescent methacrylic acid in sizing material, and part 4 is can form the phenanthroline of strong coordination with rare earth element.The method is simple and easy to do, without the need to protection of inert gas, and preparation process mild condition, without harmful gas generation.This multiple ligand rare earth vulcanization accelerator has good solubility in rubber, and cure scorch times is long, and vulcanization curve flatness is good, nontoxic, odorless, pollution-free.This promotor alternative conventional at present zinc oxide, stearic acid, accelerator combination system, apply in high-performance tire and other rubber items.
Description
Technical field
What the present invention relates to is the synthetic method of a kind of cerium Quito part vulcanization accelerator and the research of sulfuration facilitation effect thereof.This promotor without the need to zinc oxide, stearic acid as activator, have saving charging process, cleanliness without any pollution, sulfuration flatness is good, in rubber, be easy to the advantage such as dispersed, apply rubber composite prepared by this promotor and there is good performance uniformity.
Background technology
The vulcanization system of rubber is an intact vulcanized system be 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 improve the curing 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 intact vulcanized system be made up of Sulfur, activator, promotor three kinds of components, 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 defines the zinc salt of the intermediate product benzothiazole-2-mercaptan with greater activity in rubber, but because the shearing action of two roller is limited, in addition zinc oxide belongs to inorganic particulate, make the solvability of this vulcanization accelerator in rubber and bad, cause adjuvant system to be disperseed in sizing material uneven, 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 improvement sulfur sulfide system of zinc oxide, lipid acid, accelerator combination being made to substitutability.This kind of promotor effectively improves the bad shortcoming of the solvability of conventional vulcanized Promotion system in rubber, 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, ensure that the homogeneity of elastomeric material or quality of item.
Promotor of the present invention a kind ofly by cerium element and 4 kinds of parts, the title complex that coordination reaction produces occurs in a solvent, and its general structure is as follows:
[Ce
xA
yB
zC
mD
n]
In formula:
Ce is cerium element.
Organic ligand A is diethyldithiocar bamic acid, has following structure:
Organic ligand B is thiocarbamide, has following structure:
Organic ligand C is methacrylic acid, has following structure:
Organic ligand D is phenanthroline, has following structure:
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) Cerium II Chloride is dissolved in the dehydrated alcohol of 60 ~ 80 DEG C, Thiocarb containing A part and the thiocarbamide containing B part are dissolved in the dehydrated alcohol of 60 ~ 80 DEG C respectively, again the methacrylic acid containing C part and the phenanthroline containing D part are dissolved in the dehydrated alcohol of 60 ~ 80 DEG C respectively, prepare five kinds of ethanol solutions.
(2) ethanol solution containing four kinds of parts is fully mixed.Under the oil baths of 60 ~ 80 DEG C are stirred, the ethanol solution of mixed ligand is added drop-wise in the ethanol solution of Cerium II Chloride, filter after stirring 4 ~ 8h, precipitation, after absolute ethanol washing, is dried to permanent quality, is the vulcanization acceralator for rare earth rubber of multiple ligand in moisture eliminator.
Described Cerium II Chloride is the muriate of cerium element.
Preferential and the Cerium II Chloride of donor water in order to avoid oxygen reacts, and the present invention adopts dehydrated alcohol to be reaction solvent.
In order to prevent the organic composition in the too high cerium complexes of Yin Wendu from decomposing and the cerium complexes moisture absorption in atmosphere, the present invention adopts in the sealed environment at 20 ~ 30 DEG C dry, and Calcium Chloride Powder Anhydrous selected by siccative.
The multiple ligand vulcanization acceralator for rare earth rubber that the present invention relates to has good sulfuration facilitation effect, can obtain better facilitation effect under coordinating with vulcanizing agent and filler further.
The present invention can substitute the system of traditional zinc oxide, lipid acid, accelerator combination effectively, saves the consumption of auxiliary agent, simplifies the technique in rubber composite preparation process, substantially increases the solvability of vulcanization system in rubber.
The present invention compensate for the defect of prior art, there is the shortcoming such as reversion and easy incipient scorch when the organic promoter overcoming some kinds is used alone.This kind of multiple ligand rare earth compounding has good sulfuration flatness, improves 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, mild condition, do not produce obnoxious flavour in building-up process without the need to protection of inert gas.
2. cerium Quito of the present invention part vulcanization accelerator is a kind of new type rubber auxiliary agent of clean environment firendly, in Vulcanization Process of Rubber, do not produce toxic gas, and time reinforced, airborne dust is little, simplifies charging process, meets the national standard of environmental protection auxiliary agent.
3. cerium Quito of the present invention part vulcanization accelerator not only has certain sulfuration facilitation effect at low temperatures, and at high temperature sulfuration facilitation effect is remarkable, and improve scorch safety, vulcanization curve flatness is good, in high temperature vulcanized, have good reversion resistance.
4. cerium Quito of the present invention part vulcanization accelerator can make the cross-linking density of cross-linked rubber increase, and forms three-dimensional net structure better, improves homogeneity and the stability of cured properties, reaches the effect of potion multipotency.
Accompanying drawing explanation
Fig. 1 is accelerant C eA in embodiment 1
2b
0c
0d
1infrared spectrum, Fig. 2 is accelerant C eA in embodiment 2
0.01b
2c
3d
0infrared spectrum, Fig. 3 is accelerant C eA in embodiment 3
1b
1c
1.5d
0.5infrared spectrum.
Fig. 4 is that the listed rubber unvulcanizate prepared of filling a prescription of table 2 is at the vulcanization curve figure of 170 DEG C.
Fig. 5 is the transparence photo of the cross-linked rubber that table 2 listed formula 2-mercaptobenzothiazole is prepared under 170 DEG C of curing temperatures.
Fig. 6 is table 2 listed formula CeA
2b
0c
0d
1the transparence photo of the cross-linked rubber prepared under 170 DEG C of curing temperatures, Fig. 7 is table 2 listed formula CeA
0.01b
2c
3d
0the transparence photo of the cross-linked rubber prepared under 170 DEG C of curing temperatures, Fig. 8 is table 2 listed formula CeA
1b
1c
1.5d
0.5the transparence photo of the cross-linked rubber prepared under 170 DEG C 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 sulfuration compressing tablet under 170 DEG C of conditions.
Embodiment 1
The preparation method of promotor:
By 0.01molCeCl
3be dissolved in the dehydrated alcohol of 60 DEG C, 0.02mol Thiocarb be dissolved in the ethanol solution of 60 DEG C, 0.01mol phenanthroline be dissolved in the ethanol solution of 60 DEG C.Fully mix containing Thiocarb and the ethanol solution containing phenanthroline, obtain mixing solutions.Then above-mentioned mixing solutions is added drop-wise to CeCl
3ethanol solution in, at 80 DEG C, oil bath is stirred after 6h and is filtered, and precipitates after absolute ethanol washing, in the moisture eliminator being placed with CaCl2 siccative, is dried to permanent quality in 20 DEG C, obtain a kind of soil Red powder, i.e. target product CeA
2b
0c
0d
1.
Embodiment 2
The preparation method of promotor:
By 0.01molCeCl
3be dissolved in the dehydrated alcohol of 60 DEG C, 0.0001mol Thiocarb is dissolved in the ethanol solution of 60 DEG C, 0.02mol thiocarbamide is dissolved in the ethanol solution of 60 DEG C, 0.03mol methacrylic acid is dissolved in the ethanol solution of 60 DEG C.Ethanol solution containing Thiocarb, the ethanol solution containing thiocarbamide and the ethanol solution containing methacrylic acid are fully mixed, obtains mixing solutions.Then above-mentioned mixing solutions is added drop-wise to CeCl
3ethanol solution in, at 80 DEG C, oil bath is stirred after 6h and is filtered, and precipitates after absolute ethanol washing, is being placed with CaCl
2be dried to permanent quality in 20 DEG C in the moisture eliminator of siccative, obtain a kind of Beige powder, be i.e. target product CeA
0.01b
2c
3d
0.
Embodiment 3
The preparation method of promotor:
By 0.01molCeCl
3be dissolved in the dehydrated alcohol of 60 DEG C, 0.01mol Thiocarb is dissolved in the ethanol solution of 60 DEG C, 0.01mol thiocarbamide is dissolved in the ethanol solution of 60 DEG C, 0.015mol methacrylic acid is dissolved in the ethanol solution of 60 DEG C, 0.005mol phenanthroline is dissolved in the ethanol solution of 60 DEG C.Ethanol solution containing Thiocarb, the ethanol solution containing thiocarbamide, the ethanol solution containing methacrylic acid and the ethanol solution containing phenanthroline are fully mixed, obtains mixing solutions.Then above-mentioned mixing solutions is added drop-wise to CeCl
3ethanol solution in, at 80 DEG C, oil bath is stirred after 6h and is filtered, and precipitates after absolute ethanol washing, is being placed with CaCl
2be dried to permanent quality in 20 DEG C in the moisture eliminator of siccative, obtain a kind of light tan powder, be i.e. target product CeA
1b
1c
1.5d
0.5.
Embodiment 4
To accelerant C eA obtained in embodiment 1 ~ 3
2b
0c
0d
1, CeA
0.01b
2c
3d
0and CeA
1b
1c
1.5d
0.5carry out ultimate analysis, result sees table 1.
Table 1
Can be drawn by table 1, accelerant C eA obtained in embodiment 1 ~ 3
2b
0c
0d
1, CeA
0.01b
2c
3d
0and CeA
1b
1c
1.5d
0.5in have difference between the theoretical value of each element and measured value, be speculated as in accelerant powder containing caused by a small amount of crystal water and instrumental error.
Embodiment 5
Carry out Infrared Characterization to promotor obtained in embodiment 1 ~ 3, result sees Fig. 1 ~ 3.
From Fig. 1 ~ 3, accelerant C eA obtained in embodiment 1 ~ 3
2b
0c
0d
1, CeA
1b
1c
1.5d
0.5all at 1143cm
– 1, 994cm
-1near there is the similar absorption peak of C=S and C-S respectively, simultaneously 741,700,699cm
– 1near the peak that occurs result from hydrogen atom on phenanthroline ligand aromatic heterocycle, and 1320 and 1608cm
-1near there occurs the skeletal vibration of phenyl ring and C=C respectively.Title complex CeA
0.01b
2c
3d
0and CeA
1b
1c
1.5d
0.53380,3276,1616,1705cm
– 1these neighbouring peaks result from the skeletal vibration of thiocarbamide and methacrylic acid part.In addition, CeA
2b
0c
0d
1, CeA
0.01b
2c
3d
0and CeA
1b
1c
1.5d
0.5at 3500cm
-1near all there is wider hydroxyl stretching vibration absorption peak, illustrate in title complex containing crystal water.
Embodiment 6
Use accelerant C eA obtained in embodiment 1 ~ 3
2b
0c
0d
1, CeA
0.01b
2c
3d
0, CeA
1b
1c
1.5d
0.5styrene-butadiene rubber(SBR)/promotor matrix material is prepared with zinc oxide/stearic acid/2-mercaptobenzothiazole (a kind of conventional promotor).The formula of rubber unvulcanizate is as shown in table 1, adopts two roller mill to prepare rubber unvulcanizate according to a conventional method, is abbreviated as CeA in sample number into spectrum
2b
0c
0d
1, CeA
0.01b
2c
3d
0, CeA
1b
1c
1.5d
0.5.
Table 2
The curability test of rubber unvulcanizate adopts rheometer test.The vulcanization curve of rubber unvulcanizate at 170 DEG C as shown in Figure 2.Can draw from figure, cerium Quito ligand-complexes vulcanization accelerator CeA
2b
0c
0d
1, CeA
0.01b
2c
3d
0and CeA
1b
1c
1.5d
0.5at 170 DEG C, have remarkable sulfuration facilitation effect, and the plateau phase is long.
According to the cross-linked rubber that formula 2-mercaptobenzothiazole listed in table 1 is prepared under 170 DEG C of curing temperatures, adopt the shooting of Sony DSC-W670 digital camera, transparence photo as shown in Figure 3.According to formula CeA listed in table 1
2b
0c
0d
1, CeA
0.01b
2c
3d
0and CeA
1b
1c
1.5d
0.5the cross-linked rubber prepared under 170 DEG C of curing temperatures, adopt the shooting of Sony DSC-W670 digital camera, transparence photo as shown in figures 4-6.Comparison diagram 3 and Fig. 4 ~ 6 can be found out, CeA
2b
0c
0d
1, CeA
0.01b
2c
3d
0and CeA
1b
1c
1.5d
0.5transparence be obviously better than traditional promotor 2-mercaptobenzothiazole, illustrate that cerium Quito ligand-complexes vulcanization accelerator can dissolve better in rubber, thus improve the homogeneity of rubber composite performance.
Claims (3)
1. cerium Quito part vulcanization accelerator, is characterized in that: it contains cerium element, and diethyldithiocar bamic acid group and thiourea group are as main part, and methacrylic acid and phenanthroline are as assistant ligand, and its general molecular formula is:
Ce
xA
yB
zC
mD
n
In formula: A is diethyldithiocar bamic acid part, B is thiourea ligand, and C is methacrylic acid part, and D is phenanthroline ligand, x=1, y=0.01 ~ 2, z=0 ~ 2, m=0 ~ 3, n=0 ~ 1, and m, n and z can not be 0 simultaneously.
2. the preparation method of a kind of cerium Quito according to claim 1 part vulcanization accelerator, is characterized in that, comprise the following steps:
(1) Cerium II Chloride is dissolved in the dehydrated alcohol of 60 ~ 80 DEG C, Thiocarb and thiocarbamide are dissolved in the ethanol solution of 60 ~ 80 DEG C respectively, methacrylic acid and phenanthroline are dissolved in the ethanol solution of 60 ~ 80 DEG C respectively;
(2) ethanolic soln containing Thiocarb, the ethanolic soln containing methacrylic acid, the ethanolic soln containing thiocarbamide and the ethanolic soln containing phenanthroline are fully mixed, obtain mixing solutions, above-mentioned mixing solutions is added drop-wise in the ethanol solution of Cerium II Chloride, filter after stirring 4 ~ 8h at constant temperature 60 ~ 80 DEG C, 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 DEG C, and Calcium Chloride Powder Anhydrous selected by siccative.
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