CN103819720B - The preparation method of a kind of gadolinium Quito part vulcanization accelerator - Google Patents

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

Info

Publication number
CN103819720B
CN103819720B CN201410075275.1A CN201410075275A CN103819720B CN 103819720 B CN103819720 B CN 103819720B CN 201410075275 A CN201410075275 A CN 201410075275A CN 103819720 B CN103819720 B CN 103819720B
Authority
CN
China
Prior art keywords
gadolinium
gda
promotor
trolamine
rubber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201410075275.1A
Other languages
Chinese (zh)
Other versions
CN103819720A (en
Inventor
刘力
杜一诗
摆音娜
胡水
温世鹏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing University of Chemical Technology
Original Assignee
Beijing University of Chemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing University of Chemical Technology filed Critical Beijing University of Chemical Technology
Priority to CN201410075275.1A priority Critical patent/CN103819720B/en
Publication of CN103819720A publication Critical patent/CN103819720A/en
Application granted granted Critical
Publication of CN103819720B publication Critical patent/CN103819720B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of gadolinium Quito part vulcanization accelerator and preparation method thereof.Rare earth element in synthesis is gadolinium 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 longer chain fatty acid in sizing material, and part 4 is can form the trolamine 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 gadolinium Quito part vulcanization accelerator
Technical field
What the present invention relates to is the synthetic method of a kind of gadolinium 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 gadolinium element and 4 kinds of parts, the title complex that coordination reaction produces occurs in a solvent, and its general structure is as follows:
[Gd xA yB zC mD n]
In formula:
Gd is rare earth gadolinium element.
Organic ligand A is diethyldithiocar bamic acid, has following structure:
Organic ligand B is thiocarbamide, has following structure:
Organic ligand C is stearic acid, has following structure:
Organic ligand D is trolamine, 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) Gadolinium trichloride is dissolved in the dehydrated alcohol of 60 ~ 80 DEG C, the Thiocarb containing A part is dissolved in the dehydrated alcohol of 60 ~ 80 DEG C.Thiocarbamide containing B part is dissolved in the dehydrated alcohol of 60 ~ 80 DEG C, then the stearic acid containing C part and the trolamine 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 Gadolinium 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 Gadolinium trichloride is the muriate of rare earth gadolinium element.
Preferential and the Gadolinium 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 Gd coordination compound of Yin Wendu from decomposing and the Gd coordination compound 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. gadolinium 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. gadolinium 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. gadolinium 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 GdA in embodiment 1 2b 0c 0d 1infrared spectrum, Fig. 2 is promotor GdA in embodiment 2 0.01b 2c 3d 0infrared spectrum, Fig. 3 is promotor GdA 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 GdA 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 GdA 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 GdA 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 0.01molGdCl 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 trolamine be dissolved in the ethanol solution of 60 DEG C.The ethanolic soln of Thiocarb and the ethanolic soln of trolamine are fully mixed, obtains mixing solutions.Then above-mentioned mixing solutions is added drop-wise to GdCl 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 native white powder, i.e. target product GdA 2b 0c 0d 1.
Embodiment 2
The preparation method of promotor:
By 0.01molGdCl 3be dissolved in the dehydrated alcohol of 60 DEG C, 0.0001mol Thiocarb be dissolved in the ethanol solution of 60 DEG C, 0.02mol thiocarbamide is dissolved in the ethanol solution of 60 DEG C, 0.03mol stearic acid is dissolved in the ethanol solution of 60 DEG C.The ethanolic soln of Thiocarb, the ethanolic soln of thiocarbamide and stearic ethanolic soln are fully mixed, obtains mixing solutions.Then above-mentioned mixing solutions is added drop-wise to GdCl 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 GdA 0.01b 2c 3d 0.
Embodiment 3
The preparation method of promotor:
By 0.01molGdCl 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 stearic acid is dissolved in the ethanol solution of 60 DEG C, 0.005mol trolamine is dissolved in the ethanol solution of 60 DEG C.The ethanolic soln of the ethanolic soln of the ethanolic soln of Thiocarb, thiocarbamide, stearic ethanolic soln and trolamine is fully mixed, obtains mixing solutions.Then above-mentioned mixing solutions is added drop-wise to GdCl 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 GdA 1b 1c 1.5d 0.5.
Embodiment 4
To promotor GdA obtained in embodiment 1 ~ 3 2b 0c 0d 1, GdA 0.01b 2c 3d 0and GdA 1b 1c 1.5d 0.5carry out ultimate analysis, result sees table 1.
Table 1
Can be drawn by table 1, promotor GdA obtained in embodiment 1 ~ 3 2b 0c 0d 1, GdA 0.01b 2c 3d 0and GdA 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 GdA obtained in embodiment 1 ~ 3 2b 0c 0d 1, GdA 0.01b 2c 3d 0and GdA 1b 1c 1.5d 0.5carry out Infrared Characterization, result sees Fig. 1 ~ 3.
From Fig. 1 ~ 3, promotor GdA obtained in embodiment 1 ~ 3 2b 0c 0d 1, GdA 0.01b 2c 3d 0and GdA 1b 1c 1.5d 0.5all at 1143cm – 1, 994cm -1near there is the similar absorption peak of C=S and C-S respectively.GdA 2b 0c 0d 1and GdA 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, CH on trolamine part 2and CH 2-OH structure.GdA 0.01b 2c 3d 0and GdA 1b 1c 1.5d 0.53380,3276,1616,1705cm – 1these neighbouring peaks result from the skeletal vibration of thiourea ligand.Title complex GdA 0.01b 2c 3d 0and GdA 1b 1c 1.5d 0.5at 3550-3200cm -1near there is the flexural vibration absorption peak of hydroxo, 2960,1870,1465,1380cm -1near peak represent the vibration of methyl, and 2915,2850,1460cm -1neighbouring peak represents the vibration of methylene radical.In addition, GdA 2b 0c 0d 1, GdA 0.01b 2c 3d 0and GdA 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 promotor GdA obtained in embodiment 1 ~ 3 2b 0c 0d 1, GdA 0.01b 2c 3d 0, GdA 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 GdA in sample number into spectrum 2b 0c 0d 1, GdA 0.01b 2c 3d 0and GdA 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, gadolinium Quito ligand-complexes vulcanization accelerator GdA 2b 0c 0d 1, GdA 0.01b 2c 3d 0and GdA 1b 1c 1.5d 0.5at 170 DEG C, have remarkable sulfuration facilitation effect, and the plateau phase is long.
The transparence photo of the cross-linked rubber prepared under 170 DEG C of curing temperatures according to formula 2-mercaptobenzothiazole listed in table 1 adopts the shooting of Sony DSC-W670 digital camera, and transparence photo as shown in Figure 3.According to formula GdA listed in table 1 2b 0c 0d 1, GdA 0.01b 2c 3d 0and GdA 1b 1c 1.5d 0.5the transparence photo of the cross-linked rubber prepared under 170 DEG C of curing temperatures adopts the shooting of Sony DSC-W670 digital camera, and transparence photo as shown in figures 4-6.Comparison diagram 3 and Fig. 4 ~ 6 can draw, GdA 2b 0c 0d 1, GdA 0.01b 2c 3d 0and GdA 1b 1c 1.5d 0.5transparence be better than 2-mercaptobenzothiazole, gadolinium Quito ligand-complexes vulcanization accelerator GdA is described 2b 0c 0d 1, GdA 0.01b 2c 3d 0and GdA 1b 1c 1.5d 0.5can dissolve in rubber better, thus improve the homogeneity of rubber composite performance.

Claims (3)

1. gadolinium Quito part vulcanization accelerator, is characterized in that: it contains rare earth gadolinium element, and diethyldithiocar bamic acid group and thiourea group are as main part, and stearic acid and trolamine are as assistant ligand, and its general molecular formula is:
Gd xA yB zC mD n
In formula: A is diethyldithiocar bamic acid part, B is thiourea ligand, and C is stearic acid part, and D is trolamine 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 gadolinium Quito according to claim 1 part vulcanization accelerator, is characterized in that, comprise the following steps:
(1) Gadolinium trichloride 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, stearic acid and trolamine are dissolved in the ethanol solution of 60 ~ 80 DEG C respectively;
(2) by the ethanolic soln containing Thiocarb, ethanolic soln containing thiocarbamide, fully mix containing stearic ethanolic soln and the ethanolic soln containing trolamine, obtain mixing solutions, above-mentioned mixing solutions is added drop-wise in the ethanol solution of Gadolinium 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.
CN201410075275.1A 2014-03-03 2014-03-03 The preparation method of a kind of gadolinium Quito part vulcanization accelerator Active CN103819720B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410075275.1A CN103819720B (en) 2014-03-03 2014-03-03 The preparation method of a kind of gadolinium Quito part vulcanization accelerator

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410075275.1A CN103819720B (en) 2014-03-03 2014-03-03 The preparation method of a kind of gadolinium Quito part vulcanization accelerator

Publications (2)

Publication Number Publication Date
CN103819720A CN103819720A (en) 2014-05-28
CN103819720B true CN103819720B (en) 2016-01-20

Family

ID=50755032

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410075275.1A Active CN103819720B (en) 2014-03-03 2014-03-03 The preparation method of a kind of gadolinium Quito part vulcanization accelerator

Country Status (1)

Country Link
CN (1) CN103819720B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10179479B2 (en) 2015-05-19 2019-01-15 Bridgestone Americas Tire Operations, Llc Plant oil-containing rubber compositions, tread thereof and race tires containing the tread

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"N,N-Diethyldithiocarbamate Complexes of Certain Tervalent Lanthanide and Actinide Elements";Brow D, Holah D G;《JCS Chem Comm》;19681231;1545-1547 *
"稀土配合物促进剂在天然橡胶中的硫化性能";张启交等;《合成橡胶工业》;20030315;第26卷(第2期);108-110页 *

Also Published As

Publication number Publication date
CN103819720A (en) 2014-05-28

Similar Documents

Publication Publication Date Title
CN107828381A (en) A kind of natural environmental-protective surface dust suppression curing agent and preparation method thereof
CN103819716B (en) The preparation method of a kind of neodymium Quito part thiofide
CN103834059B (en) Lanthanum Quito part vulcanization accelerator and preparation method thereof
CN109486038A (en) A kind of low smell ethylene propylene diene rubber and preparation method for cable accessory
CN103819720B (en) The preparation method of a kind of gadolinium Quito part vulcanization accelerator
CN103613523A (en) Thiocarbamic acid derivative and preparation method thereof
CN103819726B (en) The preparation method of a kind of lanthanum Quito part vulcanization accelerator
CN103819713B (en) A kind of ytterbium Quito part vulcanization accelerator and preparation method thereof
CN103819728B (en) The preparation method of a kind of europium Quito part thiofide
CN103834060B (en) A kind of gadolinium Quito part thiofide and preparation method thereof
CN103819729B (en) The preparation method of a kind of europium Quito part vulcanization accelerator
CN103819725B (en) The preparation method of a kind of samarium Quito part vulcanization accelerator
CN103819730B (en) The preparation method of a kind of erbium Quito part thiofide
CN103819715B (en) A kind of lanthanum Quito part vulcanization accelerator and preparation method thereof
CN103819723B (en) A kind of cerium Quito part vulcanization accelerator and preparation method thereof
CN103819718B (en) The preparation method of a kind of samarium Quito part thiofide
CN103819724B (en) A kind of erbium Quito part vulcanization accelerator and preparation method thereof
CN103819727B (en) A kind of holmium Quito part thiofide and preparation method thereof
CN103819714B (en) The preparation method of a kind of praseodymium Quito part thiofide
CN103819721B (en) A kind of praseodymium Quito part vulcanization accelerator and preparation method thereof
CN103819722B (en) The preparation method of a kind of cerium Quito part thiofide
CN103819719B (en) A kind of neodymium Quito part vulcanization accelerator and preparation method thereof
CN103819717B (en) A kind of holmium Quito part vulcanization accelerator and preparation method thereof
CN104725432B (en) A kind of diethyldithiocar bamic acid base rare-earth transition metal bimetal complexes vulcanization accelerator
CN104725433B (en) A kind of diethyldithiocar bamic acid bimetallic complex vulcanization accelerator

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant