CN103819725B - The preparation method of a kind of samarium Quito part vulcanization accelerator - Google Patents

The preparation method of a kind of samarium Quito part vulcanization accelerator Download PDF

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CN103819725B
CN103819725B CN201410075286.XA CN201410075286A CN103819725B CN 103819725 B CN103819725 B CN 103819725B CN 201410075286 A CN201410075286 A CN 201410075286A CN 103819725 B CN103819725 B CN 103819725B
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samarium
promotor
rubber
sma
vulcanization accelerator
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CN103819725A (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 kind of samarium Quito part vulcanization accelerator and preparation method thereof.Rare earth element in synthesis is samarium element, 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 α-methacrylic acid in sizing material, and part 4 is can form the Dopamine HCL 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

The preparation method of a kind of samarium Quito part vulcanization accelerator
Technical field
What the present invention relates to is the synthetic method of a kind of samarium 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 rare earth samarium element and 4 kinds of parts, the title complex that coordination reaction produces occurs in a 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 thiocarbamide, has following structure:
Organic ligand B is xanthogenic acid, has following structure:
Organic ligand C is α-methacrylic acid, has following structure:
Organic ligand D is Dopamine HCL, 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) samarium trichloride is dissolved in the dehydrated alcohol of 60 ~ 80 DEG C, the thiocarbamide containing A part is dissolved in the dehydrated alcohol of 60 ~ 80 DEG C.An alkali metal salt of the xanthogenic acid containing B part is dissolved in the dehydrated alcohol of 60 ~ 80 DEG C, then the α-methacrylic acid containing C part and the Dopamine HCL 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 samarium trichloride, 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 samarium trichloride is the muriate of rare earth samarium element.
Preferential and the samarium trichloride 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 samarium complex of Yin Wendu from decomposing and the samarium complex 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. samarium 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. samarium 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. samarium 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 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 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 SmA 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 SmA 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 SmA 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 0.01molSmCl 3be dissolved in the dehydrated alcohol of 60 DEG C, 0.02mol thiocarbamide be dissolved in the ethanol solution of 60 DEG C, 0.01mol Dopamine HCL be dissolved in the ethanol solution of 60 DEG C.The ethanolic soln of thiocarbamide and the ethanolic soln of Dopamine HCL are fully mixed, obtains mixing solutions.Then above-mentioned mixing solutions is added drop-wise to SmCl 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 white powder, be 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 DEG C, 0.0001mol thiocarbamide be dissolved in the ethanol solution of 60 DEG C, 0.02mol potassium ethyl xanthonate is dissolved in the ethanol solution of 60 DEG C, 0.03mol α-methacrylic acid is dissolved in the ethanol solution of 60 DEG C.The ethanolic soln of the ethanolic soln of thiocarbamide, the ethanolic soln of potassium ethyl xanthonate and α-methacrylic acid is fully mixed, obtains mixing solutions.Then above-mentioned mixing solutions is added drop-wise to SmCl 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 pale yellow powder, be 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 DEG C, 0.01mol thiocarbamide is dissolved in the ethanol solution of 60 DEG C, 0.01mol potassium ethyl xanthonate is dissolved in the ethanol solution of 60 DEG C, 0.015mol α-methacrylic acid is dissolved in the ethanol solution of 60 DEG C, 0.005mol Dopamine HCL is dissolved in the ethanol solution of 60 DEG C.The ethanolic soln of the ethanolic soln of the ethanolic soln of thiocarbamide, potassium ethyl xanthonate, the ethanolic soln of α-methacrylic acid and Dopamine HCL is fully mixed, obtains mixing solutions.Then above-mentioned mixing solutions is added drop-wise to SmCl 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 pale yellow powder, be i.e. target product SmA 1b 1c 1.5d 0.5.
Embodiment 4
To promotor SmA obtained 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
Can be drawn by table 1, promotor SmA obtained in embodiment 1 ~ 3 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 containing caused by a small amount of crystal water and instrumental error.
Embodiment 5
To promotor SmA obtained 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, promotor SmA obtained in embodiment 1 ~ 3 2b 0c 0d 1, SmA 0.01b 2c 3d 0and SmA 1b 1c 1.5d 0.53380,3276,1616cm -1these neighbouring peaks result from the skeletal vibration of thiourea ligand.SmA 0.01b 2c 3d 0and SmA 1b 1c 1.5d 0.5all at 1143cm – 1, 994cm -1near there is the similar absorption peak of C=S and C-S respectively.For the SmA containing 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.In addition, title complex is at 1128cm -1near there is the flexural vibration absorption peak of hydroxo.At 3500cm -1near all there is wider hydroxyl stretching vibration absorption peak, illustrate in title complex containing crystal water.
Embodiment 6
Use promotor SmA obtained in embodiment 1 ~ 3 2b 0c 0d 1, SmA 0.01b 2c 3d 0, SmA 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 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
The curability test of rubber unvulcanizate adopts rheometer test.The vulcanization curve of rubber unvulcanizate at 170 DEG C as shown in Figure 4.Can draw from figure, 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 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 2 is prepared under 170 DEG C of curing temperatures, adopt the shooting of Sony DSC-W670 digital camera, transparence photo as shown in Figure 5.According to formula SmA listed in table 2 2b 0c 0d 1, SmA 0.01b 2c 3d 0and SmA 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 can be seen from figures 6 to 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, thus improve the homogeneity of rubber composite performance.

Claims (3)

1. samarium Quito part vulcanization accelerator, is characterized in that: it contains rare earth samarium element, and thiourea group and xanthogenic acid group are as main part, and α-methacrylic acid and Dopamine HCL are as assistant ligand, and its general molecular formula is:
Sm xA yB zC mD n
In formula: A is thiourea ligand, B is xanthogenic acid part, and C is α-methacrylic acid part, and D is Dopamine HCL part, 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 samarium Quito according to claim 1 part vulcanization accelerator, is characterized in that, comprise the following steps:
(1) samarium trichloride is dissolved in the dehydrated alcohol of 60 ~ 80 DEG C, thiocarbamide and potassium ethyl xanthonate are dissolved in the ethanol solution of 60 ~ 80 DEG C respectively, α-methacrylic acid and Dopamine HCL are dissolved in the ethanol solution of 60 ~ 80 DEG C respectively;
(2) ethanolic soln containing thiocarbamide, the ethanolic soln containing potassium ethyl xanthonate, the ethanolic soln containing α-methacrylic acid and the ethanolic soln containing Dopamine HCL are fully mixed, obtain mixing solutions, above-mentioned mixing solutions is added drop-wise in the ethanol solution of samarium trichloride, 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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