CN104004224A - Rare-earth complex rubber anti-aging agent, and preparation method and application thereof - Google Patents

Rare-earth complex rubber anti-aging agent, and preparation method and application thereof Download PDF

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CN104004224A
CN104004224A CN201410217360.7A CN201410217360A CN104004224A CN 104004224 A CN104004224 A CN 104004224A CN 201410217360 A CN201410217360 A CN 201410217360A CN 104004224 A CN104004224 A CN 104004224A
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rubber
rare earth
rare
preparation
lanthanum
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CN104004224B (en
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贾志欣
郑德�
周健
陈俊
贾德民
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South China University of Technology SCUT
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South China University of Technology SCUT
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Abstract

The invention discloses a rare-earth complex rubber anti-aging agent, and a preparation method and application thereof. The preparation method of the rare-earth complex comprises the following steps: dissolving sodium sulfanilate in water to prepare a solution having a concentration of 5-60%; adding rare-earth salts of which the mole number is equivalent to 10-100% of the mole number of the sodium sulfanilate, and then performing stirring reaction at 40-95 DEG C for 2-24 hours; and filtering the obtained product, washing, and drying to obtain a powdered target product lanthanum sulfanilate. The rare-earth complex rubber anti-aging agent is applied in rubber preparation. According to the invention, the preparation method of the rare-earth complex rubber anti-aging agent is simple and easy to implement; and the rare-earth complex rubber anti-aging agent can obviously decelerate aging of rubber, can be singly used or compounded with other anti-aging agents for use, and has the advantages of causing no pollution to a rubber product, prolonging the scorching time of a rubber material, lowering the viscosity of the rubber material and the like.

Description

A kind of rare earth compounding rubber antioxidant and preparation method thereof and application
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 thereof and application.
Background technology
Rare earth element has the characteristic such as unique 4f electronic structure and thick atom magnetic moment, strong spin coupling, easily form rare earth compounding with the organic compound part containing elements such as O, N, S, ligancy can change between 6～12, and its crystalline structure is also varied.Rare earth element and title complex thereof are to be all widely used in traditional field or at high-technology field.Rubber is the important component part of macromolecular material, has the performances such as the irreplaceable special snappiness of other material, and the application of research rare earth in rubber is a heat subject in macromolecular material research.
In recent years, rare earth compounding is applied to macromolecular material auxiliary agent and demonstrates the incomparable advantage of other materials, and its development and application is more and more subject to people's attention.Rare earth compounding is applied to additives for plastics, has developed the kinds such as rare-earth stabilizer, rare earth interface modifier, rare earth nucleator and has realized industrialization, plays an increasingly important role in plastic working and field of plastic products.The research of rare earth rubber ingredients is also very active, relates to the many-sides such as rare earth promotor, rare earth anti-aging agent, rare earth interface modifier and rare earth functional modifier, but unrealized commercial application so far.The excellent properties showing from rare earth rubber ingredients, they are functional materialss that a class has application prospect, its importance by along with research and development deeply and its apply and day by day show.
Rubber antioxidant is the important kind of rubber ingredients.The developing direction of current rubber antioxidant is environmental friendliness, efficient, multi-functional, low migration, low volatilization etc.Rare earth compounding is used as to rubber antioxidant and is conducive to improve the anti-aging efficiency of anti-aging agent to hot oxygen, ozone, UV-light and dynamic aging, can also improve mechanical property and the processing characteristics of vulcanized rubber, reduce migration, volatilization and the environmental pollution of anti-aging agent, meet the developing direction of current anti-aging agent.
Summary of the invention
The present invention be directed to how to improve existing rubber antioxidant anti-aging efficiency, how to realize anti-aging agent several functions, how to reduce the problem such as migration and volatilization of existing anti-aging agent, a kind of rare earth compounding rubber antioxidant and preparation method thereof and application are provided.With the comparison of General Purpose Rubber anti-aging agent, the feature of this rare earth anti-aging agent is to have higher anti-aging efficiency, can improve the mechanical property of vulcanized rubber, improves the processing characteristics of rubber unvulcanizate, and has the characteristics such as lower migration, volatilization and pollution.
A kind of rare earth compounding rubber antioxidant, described rare earth compounding is prepared by lanthanum (La) and organic ligand Sodium sulfanilate, and its molecular structural formula is:
A preparation method for rare earth compounding rubber antioxidant, comprises the following steps:
Sodium sulfanilate is added to the water to be made into mass percentage concentration be 5%～60% solution, add mole number to be equivalent to the rare-earth salts of Sodium sulfanilate mole number 10%～100%, then at 40～95 DEG C of stirring reaction 2～24h, the product obtaining is filtered, washing, dry, obtain Powdered target product Sulphanilic Acid lanthanum, i.e. rare earth compounding rubber antioxidant.
In aforesaid method, described rare-earth salts comprises Lanthanum trichloride, lanthanum nitrate, the one in lanthanum sulfat 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.In the time of this rare earth compounding and the composite use of conventional anti-aging agent, the ageing-resistant performance of cross-linked rubber is better than adding separately conventional anti-aging agent.
In above-mentioned application, described rubber is natural rubber or various synthetic rubber.
Compared with prior art, tool of the present invention has the following advantages:
1) synthetic method of this rare earth compounding is simple, is suitable for applying.
2) in this rare earth compounding, contain primary amino, can make rubber there is good oxidation protection performance.Simultaneously due to the distinctive 4f electronic structure of rare earth element, easily with ageing of rubber process in free-radical generating coordination, thereby termination free radical reaction further improves the ageing-resistant performance of rubber.Therefore, this rare earth compounding rubber antioxidant has excellent ageing-resistant performance.
3) when this rare earth compounding and the composite use of conventional anti-aging agent, certain mass than under, the ageing-resistant performance of cross-linked rubber is better than adding separately conventional anti-aging agent.
4) this rare earth compounding uses separately or during with the composite use of conventional anti-aging agent, can extend time of scorch, is conducive to processing safety, thereby reduces the processing fluidity that compound viscosity is conducive to sizing material simultaneously, can also improve the mechanical property of cross-linked rubber.
5) relative molecular mass of this rare earth compounding is larger than the relative molecular mass of conventional rubber antioxidant, is conducive to reduce its mobility and volatility in rubber.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of embodiment 1 products obtained therefrom, and wherein a curve is Sulphanilic Acid lanthanum, and b curve is Sodium sulfanilate.
Embodiment
By the following examples the present invention is specifically described.The present embodiment is only used to further illustrate the present invention, and can not be interpreted as the restriction to invention protection domain.Person skilled in art can content according to the present invention make suitable improvement and adjustment.
Embodiment 1
200 grams of Sodium sulfanilates are dissolved in 300ml water, bathe and stir 0.5h at 80 DEG C of Water Unders, add again mole number to be equivalent to the lanthanum chloride solution 260g of Sodium sulfanilate mole number 50%, continue to stir 8h at 80 DEG C, products therefrom is filtered, washs, is drying to obtain target product Sulphanilic Acid lanthanum.
Ultimate analysis: in product C, H, N, S content be respectively 28.12%, 2.81%, 5.55% and 12.52% this show that the chemical formula of this rare earth compounding is C 12h 12s 2o 8n 2la2H 2o.Infrared spectra still keeps its characteristic peak at 3380cm-1 and 3480cm-1 place as shown in Figure 1, just due to the strong electronegativity of lanthanum ion, causes each group absorption intensity in a slight decrease.The cationic feature peak position of sulfonic acid in figure, due to the effect of lanthanum ion, the two keys of sulphur-oxygen participate in electron resonance delocalization, and electronic cloud is on average disperseed, and has also just caused the cationic characteristic peak of sulfonic acid that blue shift has occurred., from infrared spectrum, also can find out meanwhile, in two kinds of title complexs, all contain crystal water.
The basic recipe following (unit: weight part) of styrene-butadiene rubber(SBR)/white carbon black composite material of preparing as rubber antioxidant with rare earth compounding Sulphanilic Acid lanthanum: styrene-butadiene rubber(SBR) (SBR) 100; White carbon black (SiO 2) 20; Zinc oxide (ZnO) 5;
Stearic acid (SA) 2; Accelerant CZ 2.0; Sulphur (S) 1.5; Anti-aging agent variable (do not add anti-aging agent and add respectively 4010NA2.0, MB2.0, RD2.0 and Sulphanilic Acid lanthanum 2.0);
Mixing and sulfuration process: first by styrene-butadiene rubber(SBR) thin-pass 5 times (roll spacing 0.5mm) in mill.Compounding process adds white carbon black and other additives successively routinely, finally adds sulphur.On 25 tons of hydraulic flat vulcanizing agents in 160～170 DEG C
Vulcanized rubber under condition, sulfurizing time T 90measured by vulkameter.
Table 1 is styrene-butadiene rubber(SBR)/white carbon black (SBR/SiO 2) the vulcanization characteristics parameter of matrix material.Can find out, contain the sulfurizing time T of the sizing material of Sulphanilic Acid lanthanum 90with time of scorch T 10other anti-aging agent will be grown relatively, can ensure the security of processing.Simultaneously containing the minimum torque (ML) of the sizing material of Sulphanilic Acid lanthanum lower than the sizing material containing other anti-aging agent, show that the cross-linked rubber processing fluidity that adds this anti-aging agent is better than adding other anti-aging agent.On the other hand, the torque capacity (MH) of sizing material of adding Sulphanilic Acid lanthanum is close with the sizing material of interpolation anti-aging agent RD, and its cross-linking density is higher.
Table 1SBR/SiO 2the vulcanization characteristics parameter of matrix material
Table 2 is the SBR/SiO that adopt Sulphanilic Acid lanthanum to make 2the mechanical property of matrix material.Can be found out by table, containing the tensile strength of the rubber composite of Sulphanilic Acid lanthanum and elongation rate of tensile failure all higher than the cross-linked rubber that adds conventional antioxidant 4010NA, RD and MB.
Table 2SBR/SiO 2mechanical property before matrix material is aging
Table 3 and table 4 are the cross-linked rubber that adds different anti-aging agent to be put into the respectively mechanical property contrast after aging 2,4 and 6 days of thermo-oxidative ageing case of 100 DEG C.As seen from the table, add the cross-linked rubber of anti-aging agent Sulphanilic Acid lanthanum will obviously be better than 4010NA and MB to the protective capacities of thermo-oxidative ageing, approach with the anti-aging agent RD with heat-flash oxygen protective capacities, this shows that Sulphanilic Acid lanthanum has outstanding hot oxygen protective capacities to cross-linked rubber.
The tensile strength contrast of the aging different number of days postcure of table 3 glue
The elongation at break contrast of the aging different number of days postcure of table 4 glue
Embodiment 2
With the basic recipe of rare earth compounding Sulphanilic Acid lanthanum and the composite styrene-butadiene rubber(SBR)/white carbon black composite material prepared as rubber antioxidant of 4010NA, as table 5, mixing and sulfuration process are with embodiment 1.
Table 5SBR/SiO 2composite-material formula (unit: weight part)
Table 6 shows, in the time that 4010NA/ Sulphanilic Acid lanthanum is 1.9/0.1 (4010NA-1) or 1.8/0.2 (4010NA-2), and the time of scorch T of sizing material 10extend than the sizing material (4010NA-0) that all adds 4010NA, and sulfurizing time T 90shorten than the sizing material that all adds 4010NA, show that two kinds of composite uses of anti-aging agent produce synergy to sulfuration, not only can increase time of scorch and improve sizing material processing safety, can also shorten sulfurizing time and promote vulcanization rate.Simultaneously the MH under these two kinds of proportionings promotes to some extent, shows that the cross-linked network of sizing material is more perfect when composite; And ML decreases, show that compound viscosity reduces, and is more conducive to processing.
The vulcanization characteristics parameter of table 6SBR/ Sulphanilic Acid lanthanum/4010NA cross-linked rubber
As can be seen from Table 7, compared with 4010NA-0, in 4010NA-2, tensile strength does not decline, the tensile strength of other samples has decline in various degree.Mechanical property from aging, more excellent when the mass ratio that only adds antioxidant 4010NA and 4010NA/ Sulphanilic Acid lanthanum is 1.8:0.2.
The aging front mechanical property of table 7 Sulphanilic Acid lanthanum/4010NA/SBR cross-linked rubber
Table 8,9 is cross-linked rubber difference tensile strength and elongation at break after aging 2,4 and 6 days in 100 DEG C of air.Can find out, in the time of Sulphanilic Acid lanthanum and the composite use of 4010NA, both produce synergy, its thermo oxidative aging ability is all eager to excel than independent interpolation antioxidant 4010NA, wherein especially with hot oxygen conservation rate the best of 4010NA-4, after aging six days, also there is the tensile strength of 9.03Mpa and 81.3% conservation rate, there is 463% elongation rate of tensile failure simultaneously.This can produce synergy while proving two kinds of composite uses of anti-aging agent, thereby improves the hot oxygen protective capacities of butylbenzene cross-linked rubber.
Tensile strength (MPa) after table 8SBR/ Sulphanilic Acid lanthanum/4010NA cross-linked rubber thermo-oxidative ageing
Elongation rate of tensile failure (%) after table 9 Sulphanilic Acid lanthanum/4010NA/SBR cross-linked rubber thermo-oxidative ageing
Embodiment 3
Composite as rubber antioxidant with rare earth compounding Sulphanilic Acid lanthanum and antioxidant MB, the basic recipe of the styrene-butadiene rubber(SBR)/white carbon black composite material of preparation is as table 10:
Table 10SBR/SiO 2composite-material formula (unit: weight part)
Mixing and sulfuration process are with embodiment 1.
Table 11 is the vulcanization characteristics parameter to SBR/ Sulphanilic Acid lanthanum/MB cross-linked rubber.Can find out, along with the increase of Sulphanilic Acid lanthanum consumption, time of scorch T 10with sulfurizing time T 90increase gradually, show the time of scorch that can extend sizing material that adds of Sulphanilic Acid lanthanum, thereby ensure the processing safety of sizing material.Simultaneously Sulphanilic Acid lanthanum add the minimum torque ML that can reduce sizing material, improve the processing characteristics of sizing material.
The vulcanization characteristics parameter of table 11SBR/ Sulphanilic Acid lanthanum/MB cross-linked rubber
Table 12,13 be cross-linked rubber at 100 DEG C of thermo-oxidative ageings the stretching strength retentivity after 2,4 and 6 days and elongation rate of tensile failure conservation rate.Result shows, adding of Sulphanilic Acid lanthanum can produce synergy with MB, improves the hot oxygen protective capacities of sizing material.For example, in the time that MB/ Sodium sulfanilate is 1.9/0.1, at 100 DEG C of thermo-oxidative ageings, the stretching strength retentivity after 4 days and elongation rate of tensile failure conservation rate are respectively 96.16% and 75.96% to cross-linked rubber, and the cross-linked rubber that only adds antioxidant MB is at 100 DEG C of thermo-oxidative ageings, the stretching strength retentivity after 4 days and elongation rate of tensile failure conservation rate are only 77.38% and 65.68%.
Stretching strength retentivity (%) after 100 DEG C of thermo-oxidative ageings of table 12SBR/ Sulphanilic Acid lanthanum/MB cross-linked rubber
Elongation rate of tensile failure conservation rate (%) after table 13SBR/ Sulphanilic Acid lanthanum/MB cross-linked rubber thermo-oxidative ageing
The above embodiment of the present invention is only for example of the present invention is clearly described, 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 giving exhaustive to all embodiments.All any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in the protection domain of the claims in the present invention.

Claims (5)

1. a rare earth compounding rubber antioxidant, is characterized in that, described rare earth compounding is prepared by lanthanum (La) and organic ligand Sodium sulfanilate, and its molecular structural formula is:
2. the preparation method of rare earth compounding rubber antioxidant described in claim 1, is characterized in that, comprises the following steps:
Sodium sulfanilate is added to the water to be made into mass percentage concentration be 5%～60% solution, add mole number to be equivalent to the rare-earth salts of Sodium sulfanilate mole number 10%～100%, then at 40～95 DEG C of stirring reaction 2～24h, the product obtaining is filtered, washing, dry, obtain Powdered target product Sulphanilic Acid lanthanum, i.e. rare earth compounding rubber antioxidant.
3. the preparation method of rare earth compounding rubber antioxidant as claimed in claim 2, is characterized in that, described rare-earth salts comprises Lanthanum trichloride, lanthanum nitrate, the one in lanthanum sulfat or lanthanum fluoride.
4. the application of rare earth compounding rubber antioxidant in rubber preparation described in claim 1.
5. the application of rare earth compounding rubber antioxidant as claimed in claim 4, is characterized in that, described rubber is natural rubber or various synthetic rubber.
CN201410217360.7A 2014-05-21 2014-05-21 A kind of rare earth compounding rubber antioxidant and preparation method and application Expired - Fee Related CN104004224B (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
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
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
CN105504413A (en) * 2015-12-31 2016-04-20 崇夕山 Rubber gasket for high-performance motorcycle engine
CN105504604A (en) * 2015-12-31 2016-04-20 崇夕山 Tear-resistant rubber gasket for motorcycle engine
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

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Cited By (9)

* Cited by examiner, † Cited by third party
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
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
CN105504413A (en) * 2015-12-31 2016-04-20 崇夕山 Rubber gasket for high-performance motorcycle engine
CN105504604A (en) * 2015-12-31 2016-04-20 崇夕山 Tear-resistant rubber gasket for motorcycle engine
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

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