CN104004224B - A kind of rare earth compounding rubber antioxidant and preparation method and application - Google Patents
A kind of rare earth compounding rubber antioxidant and preparation method and application Download PDFInfo
- Publication number
- CN104004224B CN104004224B CN201410217360.7A CN201410217360A CN104004224B CN 104004224 B CN104004224 B CN 104004224B CN 201410217360 A CN201410217360 A CN 201410217360A CN 104004224 B CN104004224 B CN 104004224B
- Authority
- CN
- China
- Prior art keywords
- rare earth
- rubber
- earth compounding
- preparation
- antioxidant
- 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.)
- Expired - Fee Related
Links
Abstract
The invention discloses a kind of rare earth compounding rubber antioxidant and preparation method and application.The preparation method of this rare earth compounding is to be made into, by soluble in water for sodium sulfanilate, the solution that concentration is 5%～60%, add molal quantity and be equivalent to the rare-earth salts of sodium sulfanilate molal quantity 10%～100%, then 40～95 DEG C of stirring reactions 2～24h, by the product filtration obtained, washing, the target product p-aminobenzene sulfonic acid lanthanum of drying to obtain powder.The application in prepared by rubber of the rare earth compounding rubber antioxidant.The preparation method of the rare earth compounding rubber antioxidant of the present invention is simple, it can significantly slow ageing of rubber, can be used alone or use compounding with other age resistor, have simultaneously and rubber is not produced pollution, prolongation sizing material time of scorch and reduces the advantages such as sizing material viscosity.
Description
Technical field
The present invention relates to a kind of rubber antioxidant and preparation thereof and application, be specifically related to a kind of rare earth compounding rubber antioxidant and preparation method and application.
Background technology
Rare earth element has the characteristics such as 4f electronic structure and thick atom magnetic moment, the strong spin coupling of uniqueness, easily forms rare earth compounding with the organic compound part containing elements such as O, N, S, and ligancy can change between 6～12, and its crystal structure is the most varied.Rare earth element and coordination compound thereof are either still widely used at high-technology field in traditional field.Rubber is the important component part of macromolecular material, has the performances such as the irreplaceable special high resiliency of other material, and research rare earth application in rubber is a heat subject in macromolecular material research.
In recent years, rare earth compounding is applied to the advantage that macromolecular material auxiliary agent demonstrates that other materials is incomparable, and its development and application is increasingly paid attention to by people.Rare earth compounding is applied to plastic additive, has developed the kinds such as rare-earth stabilizer, rare earth interface modifier, rare earth nucleator and has realized industrialization, having played an increasingly important role in plastic processing and field of plastic products.The research of rare-earth rubber auxiliary agent is the most active, relates to the many-sides such as rare earth accelerator, rare earth age resistor, rare earth interface modifier and rare earth functional modifier, but the most unrealized commercial application.From the point of view of the excellent properties that rare-earth rubber auxiliary agent shows, they are the functional materials that a class has application prospect, and its importance will show day by day along with the deep of research and development and its popularization and application.
Rubber antioxidant is the important kind of rubber chemicals.The developing direction of current rubber antioxidant is environmental friendliness, migration efficient, multi-functional, low, low volatilization etc..Rare earth compounding is used as rubber antioxidant be conducive to improving the age resistor anti-aging efficiency to hot oxygen, ozone, ultraviolet light and dynamic aging, mechanical property and the processing characteristics of vulcanite can also be improved, reduce the migration of age resistor, volatilization and environmental pollution, meet the developing direction of current age resistor.
Summary of the invention
The present invention be directed to how to improve the anti-aging efficiency of existing rubber antioxidant, how to realize the problems such as the several functions of age resistor, the migration how reducing existing age resistor and volatilization, it is provided that a kind of rare earth compounding rubber antioxidant and preparation method and application.Comparing with General Purpose Rubber age resistor, the feature of this rare earth age resistor is to have higher anti-aging efficiency, can improve the mechanical property of vulcanite, improves the processing characteristics of elastomeric compound, and has relatively low migration, volatilizees and the characteristic such as pollution.
A kind of rare earth compounding rubber antioxidant, described rare earth compounding is prepared with organic ligand sodium sulfanilate by lanthanum (La), and its molecular structural formula is:
The preparation method of a kind of rare earth compounding rubber antioxidant, comprises the following steps:
Sodium sulfanilate is added to the water and is made into the solution that mass percentage concentration is 5%～60%, add molal quantity and be equivalent to the rare-earth salts of sodium sulfanilate molal quantity 10%～100%, then 40～95 DEG C of stirring reactions 2～24h, the product obtained is filtered, washing, it is dried, obtains powder target product p-aminobenzene sulfonic acid lanthanum, i.e. rare earth compounding rubber antioxidant.
In said method, described rare-earth salts includes the one in lanthanum chloride, Lanthanum (III) nitrate, lanthanum sulfate or lanthanum fluoride.
Above-mentioned rare earth compounding rubber antioxidant is applied in rubber preparation, and this rare earth compounding adds in rubber compounding can produce significant anti-aging effect to rubber.When the use compounding with conventional age resistor of this rare earth compounding, the ageing-resistant performance of vulcanizate is better than individually adding conventional age resistor.
In above-mentioned application, described rubber is natural rubber or various synthetic rubber.
Compared with prior art, present invention have the advantage that
1) synthetic method of this rare earth compounding is simple, is suitable to popularization and application.
2) containing primary amino radical in this rare earth compounding, rubber can be made to have good oxidation protection performance.Simultaneously because rare earth element distinctive 4f electronic structure, the free radical easily and during ageing of rubber produces coordination, thus stops radical reaction, improves the ageing-resistant performance of rubber further.Therefore, this rare earth compounding rubber antioxidant has the ageing-resistant performance of excellence.
3), during the use compounding with conventional age resistor of this rare earth compounding, under certain mass ratio, the ageing-resistant performance of vulcanizate is better than individually adding conventional age resistor.
4) this rare earth compounding is used alone or compounding with conventional age resistor when using, and can extend time of scorch, beneficially process safety, reduces compound viscosity thus the processing fluidity of beneficially sizing material, moreover it is possible to improve the mechanical property of vulcanizate simultaneously.
5) relative molecular mass of this rare earth compounding is bigger than the relative molecular mass of conventional rubber antioxidant, advantageously reduces its mobility in rubber and volatility.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of embodiment 1 products obtained therefrom, and wherein a curve is p-aminobenzene sulfonic acid lanthanum, and b curve is sodium sulfanilate.
Detailed description of the invention
By the following examples the present invention is specifically described.The present embodiment is served only for being further described the present invention, it is impossible to be interpreted as the restriction to invention protection domain.Person skilled in art can make according to present disclosure and be suitably modified and adjust.
Embodiment 1
200 grams of sodium sulfanilates are dissolved in 300ml water, stirring in water bath 0.5h under the conditions of 80 DEG C, add molal quantity and be equivalent to the lanthanum chloride solution 260g of sodium sulfanilate molal quantity 50%, continue to stir 8h at 80 DEG C, by products therefrom filtration, washing, drying to obtain target product p-aminobenzene sulfonic acid lanthanum.
Elementary analysis: in product C, H, N, S content respectively 28.12%, 2.81%, 5.55% and 12.52% this show that the chemical formula of this rare earth compounding is C12H12S2O8N2La·2H2O.Infrared spectrum remains in that its characteristic peak as shown in Figure 1 at 3380cm-1 and 3480cm-1, only because the electronegativity that lanthanum ion is strong, causes each group absorptions intensity in a slight decrease.The feature peak position of Sulfonic acid cation in figure, due to the effect of lanthanum ion, sulfur-oxygen double bond participates in electron resonance delocalization, and electron cloud is averaged dispersion, and the characteristic peak also having led to Sulfonic acid cation there occurs blue shift.Meanwhile, it can also be seen that two kinds of coordination compounds all contain water of crystallization from infrared spectrum.
The basic recipe of the butadiene-styrene rubber/white carbon black composite material prepared as rubber antioxidant with rare earth compounding p-aminobenzene sulfonic acid lanthanum is following (unit: weight portion): butadiene-styrene rubber (SBR) 100；White carbon (SiO2)20；Zinc oxide (ZnO) 5；
Stearic acid (SA) 2；Accelerant CZ 2.0；Sulfur (S) 1.5；Age resistor variable (is not added with age resistor and is separately added into 4010NA2.0, MB2.0, RD2.0 and p-aminobenzene sulfonic acid lanthanum 2.0)；
Mixing and sulfuration process: first by the thinnest for butadiene-styrene rubber logical 5 times (roll spacing 0.5mm).Compounding process is sequentially added into white carbon and other additives routinely, is eventually adding sulfur.In 160～170 DEG C on 25 tons of hydraulic flat vulcanizing agents
Under the conditions of vulcanized rubber, sulfurizing time T90Measured by vulcameter.
Table 1 is butadiene-styrene rubber/white carbon (SBR/SiO2) the vulcanization characteristics parameter of composite.It can be seen that the sulfurizing time T of the sizing material containing p-aminobenzene sulfonic acid lanthanum90With time of scorch T10Other age resistor relatively to be grown, it is possible to ensures the safety of processing.The minimum torque (ML) of the sizing material containing p-aminobenzene sulfonic acid lanthanum is less than the sizing material containing other age resistor simultaneously, shows that the vulcanizate processing fluidity adding this age resistor is better than adding other age resistor.On the other hand, the torque capacity (MH) of the sizing material adding p-aminobenzene sulfonic acid lanthanum is close with the sizing material adding anti-aging agent RD, and its crosslink density is higher.
Table 1SBR/SiO2The vulcanization characteristics parameter of composite
Table 2 is the SBR/SiO using p-aminobenzene sulfonic acid lanthanum to prepare2The mechanical property of composite.By table it can be seen that the hot strength of rubber composite and elongation rate of tensile failure containing p-aminobenzene sulfonic acid lanthanum are above adding the vulcanizate of conventional antioxidant 4010NA, RD and MB.
Table 2SBR/SiO2Mechanical property before composite is aging
Table 3 and table 4 are the vulcanizate adding different age resistor to be put in the thermo-oxidative ageing case of 100 DEG C mechanical property after aging 2,4 and 6 days respectively contrast.As seen from the table, the vulcanizate of addition age resistor p-aminobenzene sulfonic acid lanthanum protective capacities 4010NA and MB to be substantially better than to thermo-oxidative ageing, close with the anti-aging agent RD with heat-flash oxygen protective capacities, this shows that p-aminobenzene sulfonic acid lanthanum has prominent hot oxygen protective capacities to vulcanizate.
The hot strength contrast of table 3 aging different number of days after cure glue
The elongation at break contrast of table 4 aging different number of days after cure glue
Embodiment 2
With basic recipe such as the table 5 of the compounding butadiene-styrene rubber/white carbon black composite material prepared as rubber antioxidant of rare earth compounding p-aminobenzene sulfonic acid lanthanum and 4010NA, mixing and sulfuration process is with embodiment 1.
Table 5SBR/SiO2Composite-material formula (unit: weight portion)
Table 6 shows, when 4010NA/ p-aminobenzene sulfonic acid lanthanum is 1.9/0.1 (4010NA-1) or during 1.8/0.2 (4010NA-2), and the time of scorch T of sizing material10Extend than the sizing material (4010NA-0) all adding 4010NA, and sulfurizing time T90Then the sizing material than all addition 4010NA shortens, and shows that two kinds of age resistor are compounding and uses sulfuration generation synergism, can not only increase time of scorch and improve sizing material process safety, moreover it is possible to shorten sulfurizing time and promote curingprocess rate.MH under both proportionings has promoted simultaneously, and when showing compounding, the cross-linked network of sizing material is more perfect；And ML decreases, show that compound viscosity reduces, be more conducive to processing.
The vulcanization characteristics parameter of table 6SBR/ p-aminobenzene sulfonic acid lanthanum/4010NA vulcanizate
As can be seen from Table 7, compared with 4010NA-0, in addition in 4010NA-2, hot strength does not decline, the hot strength of other samples has decline in various degree.From the point of view of mechanical property before aging, only the mass ratio of interpolation antioxidant 4010NA and 4010NA/ p-aminobenzene sulfonic acid lanthanum is more excellent when being 1.8:0.2.
Table 7 p-aminobenzene sulfonic acid lanthanum/aging front mechanical property of 4010NA/SBR vulcanizate
Table 8,9 is the hot strength after vulcanizate is distinguished aging 2,4 and 6 days in 100 DEG C of air and elongation at break.Can be seen that, when the use compounding with 4010NA of p-aminobenzene sulfonic acid lanthanum, both produce synergism, its thermo oxidative aging ability is all added antioxidant 4010NA than individually and is eager to excel, the most especially hot oxygen conservation rate with 4010NA-4 is optimal, also there is after aging six days the hot strength of 9.03Mpa and the conservation rate of 81.3%, there is the elongation rate of tensile failure of 463% simultaneously.This proves that two kinds of age resistor are compounding and can produce synergism when using, thus improves the hot oxygen protective capacities of butylbenzene vulcanizate.
Hot strength (MPa) after table 8SBR/ p-aminobenzene sulfonic acid lanthanum/4010NA vulcanizate thermo-oxidative ageing
Elongation rate of tensile failure (%) after table 9 p-aminobenzene sulfonic acid lanthanum/4010NA/SBR vulcanizate thermo-oxidative ageing
Embodiment 3
Compounding as rubber antioxidant with rare earth compounding p-aminobenzene sulfonic acid lanthanum and antioxidant MB, the basic recipe of the butadiene-styrene rubber/white carbon black composite material of preparation such as table 10:
Table 10SBR/SiO2Composite-material formula (unit: weight portion)
Mixing with sulfuration process with embodiment 1.
Table 11 is the vulcanization characteristics parameter to SBR/ p-aminobenzene sulfonic acid lanthanum/MB vulcanizate.It can be seen that along with the increase of p-aminobenzene sulfonic acid lanthanum consumption, time of scorch T10With sulfurizing time T90It is gradually increased, shows that the addition of p-aminobenzene sulfonic acid lanthanum can extend the time of scorch of sizing material, thus ensure the process safety of sizing material.The addition of p-aminobenzene sulfonic acid lanthanum simultaneously can reduce the minimum torque ML of sizing material, improves the processing characteristics of sizing material.
The vulcanization characteristics parameter of table 11SBR/ p-aminobenzene sulfonic acid lanthanum/MB vulcanizate
Stretching strength retentivity that table 12,13 is vulcanizate after 100 DEG C of thermo-oxidative ageings 2,4 and 6 days and elongation rate of tensile failure conservation rate.Result shows, the addition of p-aminobenzene sulfonic acid lanthanum can produce synergism with MB, improves the hot oxygen protective capacities of sizing material.Such as, when MB/ sodium sulfanilate is 1.9/0.1, vulcanizate stretching strength retentivity after 100 DEG C of thermo-oxidative ageings 4 days and elongation rate of tensile failure conservation rate are respectively 96.16% and 75.96%, and only add the vulcanizate of the antioxidant MB stretching strength retentivity after 100 DEG C of thermo-oxidative ageings 4 days and elongation rate of tensile failure conservation rate is only 77.38% and 65.68%.
Stretching strength retentivity (%) after table 12SBR/ p-aminobenzene sulfonic acid lanthanum/MB vulcanizate 100 DEG C thermo-oxidative ageing
Elongation rate of tensile failure conservation rate (%) after table 13SBR/ p-aminobenzene sulfonic acid lanthanum/MB vulcanizate thermo-oxidative ageing
The above embodiment of the present invention is only for clearly demonstrating example of the present invention, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here without also cannot all of embodiment be given exhaustive.All any amendment, equivalent and improvement etc. made within the spirit and principles in the present invention, within should be included in the protection domain of the claims in the present invention.
Claims (4)
1. the preparation method of a rare earth compounding rubber antioxidant, it is characterised in that comprise the following steps:
Sodium sulfanilate is added to the water and is made into the solution that mass percentage concentration is 5%～60%, add molal quantity and be equivalent to the rare-earth salts of sodium sulfanilate molal quantity 10%～100%, then 40～95 DEG C of stirring reactions 2～24h, the product obtained is filtered, washing, it is dried, obtains powder target product p-aminobenzene sulfonic acid lanthanum, i.e. rare earth compounding rubber antioxidant.
2. the preparation method of rare earth compounding rubber antioxidant as claimed in claim 1, it is characterised in that described rare-earth salts includes the one in lanthanum chloride, Lanthanum (III) nitrate, lanthanum sulfate or lanthanum fluoride.
3. the rare earth compounding rubber antioxidant that preparation method described in claim 2 prepares application in prepared by rubber.
4. the application of rare earth compounding rubber antioxidant as claimed in claim 3, it is characterised in that described rubber is natural rubber or various synthetic rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410217360.7A CN104004224B (en) | 2014-05-21 | 2014-05-21 | A kind of rare earth compounding rubber antioxidant and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410217360.7A CN104004224B (en) | 2014-05-21 | 2014-05-21 | A kind of rare earth compounding rubber antioxidant and preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104004224A CN104004224A (en) | 2014-08-27 |
| CN104004224B true CN104004224B (en) | 2016-08-17 |
Family
ID=51365144
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410217360.7A Expired - Fee Related CN104004224B (en) | 2014-05-21 | 2014-05-21 | A kind of rare earth compounding rubber antioxidant and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104004224B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105111546A (en) * | 2015-08-17 | 2015-12-02 | 繁昌县菲德通讯材料设计有限公司 | Special high-strength low-temperature-resistant cable used for oil platform |
| CN105504604A (en) * | 2015-12-31 | 2016-04-20 | 崇夕山 | Tear-resistant rubber gasket for motorcycle engine |
| CN105504413A (en) * | 2015-12-31 | 2016-04-20 | 崇夕山 | Rubber gasket for high-performance motorcycle engine |
| CN105419034A (en) * | 2015-12-31 | 2016-03-23 | 崇夕山 | Motorcycle engine rubber gasket with excellent heat stability |
| CN105504418A (en) * | 2015-12-31 | 2016-04-20 | 崇夕山 | Rubber material for motorcycle engine gasket |
| CN105670040A (en) * | 2016-02-25 | 2016-06-15 | 华南理工大学 | Loaded rubber anti-aging agent and preparation method and application thereof |
| CN106519294A (en) * | 2016-10-26 | 2017-03-22 | 华南理工大学 | Lanthanum sulfonate-calixarene complex antioxidant, and preparation method and application thereof |
| CN108623867A (en) * | 2018-04-23 | 2018-10-09 | 太和县彬峰绳网有限公司 | A kind of anti-aging fire retardant glue rope |
| CN109485935A (en) * | 2018-11-19 | 2019-03-19 | 永橡胶有限公司 | A kind of high life solid tyre and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781324A (en) * | 2009-12-17 | 2010-07-21 | 华南理工大学 | Rare earth complex and preparation method and application thereof |
-
2014
- 2014-05-21 CN CN201410217360.7A patent/CN104004224B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781324A (en) * | 2009-12-17 | 2010-07-21 | 华南理工大学 | Rare earth complex and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| "镧(Ⅲ)配台物的微型实验合成与晶体结构";朱立红等;《第六届全国微型化学实验专辑论文集》;20040731;第34－36页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104004224A (en) | 2014-08-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104004224B (en) | A kind of rare earth compounding rubber antioxidant and preparation method and application | |
| CN102964697B (en) | The EPT rubber cable material that a kind of Nano wollastonite powder is modified | |
| CN103923351B (en) | A kind of lignocellulose/the preparation method of polynite rubber reinforcing filler and the reinforcement of rubber | |
| CN102924761B (en) | Tread rubber of zinc oxide pre-dispersion master colloidal particle and preparation method thereof | |
| CN102838801A (en) | Semiconductor shielding cable material | |
| CN113999475B (en) | Sunlight-resistant anti-UV material and preparation method thereof | |
| CN103665682B (en) | A kind of High-elasticity low-compressive deformation rubber gasket material and preparation method thereof | |
| WO2023024661A1 (en) | Antibacterial agent, and antibacterial polysulfone composite material and preparation method therefor | |
| CN113652031A (en) | Low-compression permanent deformation low-temperature-resistant EPDM (ethylene-propylene-diene monomer) sealing strip as well as preparation method and application thereof | |
| CN103497384B (en) | A kind of ageing-resistant rubber composition containing metallic salts of unsaturated carboxylate vulcanizing agent | |
| CN106117694B (en) | A kind of attapulgite activeness and quietness resists long-term ultraviolet ageing floating material masterbatch | |
| JP2019001979A (en) | Compound for producing elastic composite material and method for producing elastic composite material | |
| CN107805345A (en) | A kind of anti-skidding high-temperature resistance plastice woven bag composition of raw materials | |
| CN103613867A (en) | Modified compounded rubber sealing gasket material and preparation method thereof | |
| CN103524842A (en) | Soft environment-friendly polyolefin cable material | |
| KR100513239B1 (en) | Silica Tread Rubber Composition with Carbon Nano Tube | |
| CN103613892A (en) | Modified compounded rubber sealing gasket material and preparation method thereof | |
| CN106117695A (en) | A kind of anti-long-term ultraviolet ageing high-density polyethylene material | |
| CN110819049A (en) | Preparation method of high-strength AEM and FKM combined sizing material | |
| CN105295249A (en) | Hydrotalcite-rare earth composite environmental protection stabilizer for PVC, and preparation method thereof | |
| CN108129693B (en) | Oil-extended insoluble sulfur and preparation method and application thereof | |
| CN103819720B (en) | The preparation method of a kind of gadolinium Quito part vulcanization accelerator | |
| CN108250567B (en) | Preparation method of high-impact-strength photo-oxidative-aging-resistant polypropylene | |
| CN109735022B (en) | Preparation method of high-weather-resistance printing base film | |
| CN105602128B (en) | A kind of gum filler and preparation method thereof |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160817 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |