CN102850582A - Applications of lysine in aspects of vulcanization, reinforcement and aging resistance of rubber - Google Patents
Applications of lysine in aspects of vulcanization, reinforcement and aging resistance of rubber Download PDFInfo
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- CN102850582A CN102850582A CN2012103591502A CN201210359150A CN102850582A CN 102850582 A CN102850582 A CN 102850582A CN 2012103591502 A CN2012103591502 A CN 2012103591502A CN 201210359150 A CN201210359150 A CN 201210359150A CN 102850582 A CN102850582 A CN 102850582A
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Abstract
The invention discloses applications of lysine in aspects of vulcanization, reinforcement and aging resistance of rubber. A first usage method of the lysine includes adding the lysine during primary processing of the rubber, wherein the added quantity of the lysine is 0.01%-1% of the total weight of the rubber; and a second usage method of the lysine includes adding the lysine during the production of rubber products, wherein the added quantity of the lysine is 0.01%-1% of the total weight of the rubber. According to the applications of the lysine in the aspects of vulcanization, reinforcement and aging resistance of the rubber, vulcanization rates of rubber vulcanization processes can be increased, and simultaneously, tensile strength and aging resistant performances of the rubber products are improved.
Description
Technical field
The present invention relates to the application of Methionin, be specifically related to the new purposes that Methionin improves the tensile strength of vulcanization of rubber speed, Reinforced Rubber cross-linked rubber and improves the rubber ageing resistance, belong to the rubber production technical field.
Background technology
Rubber is divided into two kinds of natural rubber and synthetic rubber.Natural rubber of the present invention be the fresh latex that produces of Brazilian para ruber through solidify, slaking, crumple, granulation, drying and make.
The fresh latex that Brazil para ruber produces is commonly referred to as natural fresh latex.The composition of natural fresh latex is very complicated, except rubber hydrocarbon, also contains tens kinds of other materials, i.e. nonrubber material, these materials account for latex heavy 5%.Although the shared latex deal of these nonrubber materials is few, latex and the character that makes rubber there is in various degree impact.Usually these nonrubber materials are divided into following several large class:
(1) protein.The protein content of fresh latex accounts for the heavy 1%-2% of latex, and 20% surface that is distributed in rubber particles is wherein arranged approximately, is the important composition material of micelle protective layer, and about 20% is present in the liquid of latex bottom part, and rest part then is dissolved in the whey.In the glue production process, a part of protein flows away with whey in the latex, and remaining then still stays in the rubber.Protein still has larger impact to the performance of rubber except to latex stable influential.On the one hand, the degradation production of protein can promote the sulfuration of rubber, improves the fixed stretching strength of rubber, delays the aging of rubber, makes rubber item durable.On the other hand, it has again stronger water-absorbent, can increase the water-absorbent of rubber item and conducting electricity property, makes easily rubber item mouldy and be unfavorable for making the electrical material of insulativity.
(2) lipoid.Lipoid in the fresh latex mainly are fat, wax class, stay alcohol, stay alcohol ester and phosphide.These lipoid are all water insoluble, mainly are distributed in the rubber phase, are present on a small quantity in latex bottom and the corpora flava.The content of lipoid in latex is about 0.9%, and major part is phosphide (about 70%).The surface activity of latex phosphide is very high, and on the rubber particles surface, it and protein bound form the very thin hybrid films of one deck together, and it is exactly this reason that fresh latex can keep the stability of colloid.Ammonia is preserved the raising of latex mechanical stability in storage process, is owing to lipid acid and ammonia react in the lipoid in the latex have generated ammonium soaps, forms the result of protective membrane on the micelle surface.
(3) the molten thing of acetone.The material that can be dissolved in acetone in the latex is referred to as the molten thing of acetone.Nearly all be dissolved in acetone in the above-mentioned lipoid except phosphide, belong to the molten thing of acetone, the content in fresh latex is about 1%～2%.Contain lipid acid more than 50% in the molten thing of acetone, when rubber plastic steelmaking, play ramollescence, make rubber obtain easily plasticity-, the molten thing of acetone has age inhibiting effect to rubber simultaneously.
(4) water solubles.The about 1%-2% of the content of the water solubles in latex mainly is distributed in the whey.Carbohydrate decomposes the generation voltaile fatty acid easily under the effect of bacterium, mainly be that acetic acid also has a small amount of formic acid and propionic acid.The content of volatile fatty acids raises, and the stability of latex will reduce, even natural coagulation.
(5) inorganic salt.The content of inorganic salt about 0.3%～0.7% in the fresh latex.Mineral ion in the fresh latex, major part are distributed in the whey, and a small amount of copper, potassium ion may also have iron ion to link to each other with rubber particles, and a large amount of magnesium ions then is present in the bottom of latex.
In addition, also exist various bacteria and enzyme in the latex.
In the slaking of the solidifying of natural fresh latex, grumeleuse, crumple, in the process such as granulation, nonrubber composition major part in the latex is drained with whey, be retained in the dried glue and only have small portion, but this small portion nonrubber composition is very big on the impact of rubber performance, if remove the nonrubber composition in the natural rubber, its performance then declines to a great extent.Because the difference of adhesive-preparing technology, there are very big-difference in the kind and the content that are retained at last the nonrubber composition in the dried glue, cause the inconsistent of natural rubber performance.
Synthetic rubber then is to get through the synthetic of monomer and refining, polymerization process and rubber aftertreatment.Synthetic rubber does not contain the nonrubber composition that natural rubber has, and its over-all properties is obviously not as natural rubber.
Aging is a kind of comparatively general phenomenon that exists in the macromolecular material such as rubber, and it can make the performance degradation of rubber, affect use value and the work-ing life of rubber item, and the preventing rubber system is delay rubber aging, the work-ing life of prolongation goods.The preventing rubber system mainly is anti-aging agent, and the anti-aging agent type can be divided into chemical antiager and physical antioxidant by action principle; Target by protection is divided into oxidation inhibitor, protects ozonidate, photomask agent, metal passivator etc., also can classify by chemical structure.In order to improve the character of rubber, the researchist is unremittingly studying always.
Methionin is unique amino acid that the side chain primary amino is arranged in the protein, is the fundamental unit that consists of protein, is one of 21 seed amino acids that form human body protein, is mammiferous indispensable amino acid and ketogenic amino acid.It can promote the human development, strengthen immunologic function, and is improved the effect of central nervous tissue function.It forms collagen protein together with other nutrition.In addition, Methionin also helps health to the absorption of calcium.
Methionin is white in color or the free-pouring crystalline powder of near-white.Odorless almost.263-264 ℃ of fusing also decomposed.Usually more stable, easily lump under the high-temperature, slightly painted.Stable when relative humidity 60% is following, then generate dihydrate more than 60%.Then painted with vitamins C and vitamin K3 coexistence.Heating is then decomposed under alkaline condition and direct and the reducing sugar existence.Soluble in water, it is neutral to subacidity that the aqueous solution is, and with heating such as phosphoric acid, hydrochloric acid, sodium hydroxide, ion exchange resin, plays racemization.
Above-mentioned discussion content purpose is to introduce to the public all respects of technology that may be relevant with all respects of the present invention that below will be described and/or advocate, believe that this discussion content helps to provide background information for the public, to be conducive to understanding better all respects of the present invention, therefore, should be appreciated that it is to read these discussions with this angle, rather than admit prior art.
Summary of the invention
The object of the present invention is to provide the application of Methionin aspect the vulcanization of rubber, reinforcement and anti-aging, Methionin is as a kind of novel thiofide and/or strengthening agent and/or anti-aging agent, can improve the vulcanization rate of Vulcanization Process of Rubber, improve simultaneously tensile strength and the ageing resistance of rubber item.
Purpose of the present invention is achieved through the following technical solutions:
Methionin is as a kind of novel thiofide and/or strengthening agent and/or anti-aging agent.
Rubber preliminary working method is added Methionin in rubber preliminary working process, the adding weight of Methionin accounts for 0.01%-1% of rubber weight.
The rubber item production method is added Methionin in the rubber item production process, the add-on of Methionin accounts for 0.01%-1% of rubber.
Described rubber is natural rubber or synthetic rubber or mixed rubber.
Described Methionin is biochemical SILVER REAGENT or pharmaceutical grade or food grade or technical grade.
The invention has the beneficial effects as follows: along with the adding of Methionin, the vulcanization rate of rubber is obviously accelerated, and the tensile strength of while rubber item significantly improves with ageing resistance obviously to be improved.
Beneficial effect of the present invention can embody by following experiment:
Prescription: 100 parts of natural rubbers, 0.20 part of Methionin, 3.50 parts of Sulfurs, 0.50 part of stearic acid, 6.00 parts in zinc oxide, accelerant MBT (benzothiazolyl mercaptan, 2-Mercaptobenzothiazole) 0.50 part (by weight).Described natural rubber is that nitrogen content is the 0.012%(massfraction), foreign matter content is the 0.004%(massfraction) high-purity natural rubber, described Methionin is the biochemical reagents levels.
High-purity natural rubber is that 45 ℃-55 ℃ mill is plasticated in temperature, discharging when [ML(1+4) 100 ℃] that mooney viscosity reaches 60.Rubber through over-mastication carries out mixing at mixing roll, by above-mentioned vulcanization system and be sequentially added into vulcanization accelerator and Methionin, anti-aging agent, zinc oxide, stearic acid, Sulfur, mix rear discharging until these Synergist S-421 95s, during the roller temperature control of mixing roll at 45 ℃-55 ℃.
The rubber unvulcanizate of gained is used without the rotor vulkameter and is carried out the vulcanization characteristics test at 140 ℃, obtains its initial curing time (t
S1) be 1.25 minutes, sulfurizing time (t
90) be 16.72 minutes, its vulcanization rate is 6.46 as calculated.Rubber unvulcanizate vulcanizes at 100 tons 140 ℃ vulcanizing press, the test piece of preparation cross-linked rubber, and curing time was pressed the definite sulfurizing time of vulkameter 16.72 minutes.The test piece of preparation is carried out tension test through being cut into dumbbell-shaped test piece at electronic tensile machine, and the part of these dumbbell-shaped test pieces of while wore out 24 hours at 100 ℃ hot air aging case, then carried out tensile strength test at electronic tensile machine.Stretch test result is before aging: tensile strength 14.25MPa, tensile yield 984%; Aging back draft test-results is: tensile strength 4.40MPa, tensile yield 603%.Aging coefficient is 0.189 as calculated.
Controlled trial is not except adding the Methionin, and all test conditionss are all identical, the initial curing time (t of control sample
S1) be 3.68 minutes, sulfurizing time (t
90) be 35.42 minutes, its vulcanization rate is 3.15 as calculated; The aging front stretch test result of control sample is: tensile strength 11.4MPa, tensile yield 1083%, aging back draft test-results is: tensile strength 0.94MPa, tensile yield 470%.Aging coefficient is 0.036 as calculated.
By above-mentioned control experiment as can be known, after adding Methionin in the high-purity natural rubber, its vulcanization rate comparison has improved 105.1% in the same old way, and tensile strength has improved 25.0%, the aging coefficient of cross-linked rubber has improved 425% than control sample, and the ageing resistance of rubber item is obviously improved.
Embodiment
In order to make those skilled in the art understand better technical scheme of the present invention, the present invention is described in further detail below in conjunction with specific embodiment, need to prove that in the situation of not conflicting, the application's embodiment and the feature among the embodiment can make up mutually.
Embodiment 1
The rubber item production method, in 1 kilogram natural rubber, with other Synergist S-421 95s such as filler (such as carbon black or White Carbon black), stearic acid, zinc oxide, vulcanization accelerator, anti-aging agent, Sulfurs, the Methionin that adds 0.2 gram in mixing process is mixingly evenly made rubber item by sulfuration.
Operation steps: natural rubber is that 45 ℃-55 ℃ mill is plasticated in temperature, reaches 60[ML(1+4 at its mooney viscosity) 100 ℃] time discharging.Rubber through over-mastication carries out mixing at mixing roll, and be sequentially added into vulcanization accelerator and Methionin, anti-aging agent, zinc oxide, stearic acid, various filler, after after a while mixing, add Sulfur, mix rear discharging until these Synergist S-421 95s, during the roller temperature control of mixing roll at 45 ℃-55 ℃.Through mixing rubber roll again, extrusion, moulding, vulcanize (the optimum curing time can be determined with vulkameter first) at 140 ℃ vulcanizers and make rubber item.
Embodiment 2
The rubber item production method, in 1 kilogram synthetic rubber, with other Synergist S-421 95s such as filler (such as carbon black or White Carbon black), stearic acid, zinc oxide, vulcanization accelerator, anti-aging agent, Sulfurs, the Methionin that adds 0.5 gram in mixing process is mixingly evenly made rubber item by sulfuration.
Elastomeric kind is more, and every kind of elastomeric operational condition is the same not to the utmost, and following operation steps take polyisoprene rubber is as example.
Operation steps: the mooney viscosity of polyisoprene rubber is lower than 60[M(1+4) 100 ℃] time do not need to plasticate, the polyisoprene rubber that need to plasticate is thin-pass 1-2 time in the mill of 50 ℃ of-60 ℃ of pony roll distances in the roller temperature first, behind film bag roller, tune up a little roll spacing and continue to plasticate about 2 minutes, make rubber form continuous gloss film at roller surface and get final product.Rubber through over-mastication carries out mixing at mixing roll, and be sequentially added into vulcanization accelerator and Methionin, anti-aging agent, zinc oxide, stearic acid, various filler, after after a while mixing, add Sulfur, mix rear discharging until these Synergist S-421 95s, during the roller temperature control of mixing roll at 40 ℃-50 ℃.Through mixing rubber roll again, extrusion, moulding, vulcanize (the optimum curing time can be determined with vulkameter first) at 140 ℃ vulcanizers and make rubber item.
Embodiment 3
The rubber item production method in the mixed rubber that the synthetic rubber of 1 kilogram natural rubber and 1 kilogram forms, with other Synergist S-421 95, adds the Methionins of 2 grams in mixing process, mixingly evenly make rubber item by sulfuration.
In the mixed rubber that is comprised of natural rubber and synthetic rubber, most synthetic rubber can both have good consistency with natural rubber, and combined effect is very good.And elastomeric kind is more, and every kind of synthetic rubber is the same not to the utmost with the operational condition of the mixed rubber that natural rubber forms, and the operation steps of following mixed rubber take polyisoprene rubber and natural rubber composition is as example.
Operation steps: two kinds of rubber are plasticated respectively park first, then make the broken-(down)rubber bag roller of natural rubber at mixing roll, the polyisoprene rubber broken-(down)rubber of adding 15% is mixed mutually, relax roll spacing until the remaining polyisoprene rubber broken-(down)rubber of even rear adding and refer and synthesize, until the intrinsic white of polyisoprene rubber disappears.Be sequentially added into vulcanization accelerator and Methionin, anti-aging agent, zinc oxide, stearic acid, various filler, after after a while mixing, add Sulfur, mix rear discharging until these Synergist S-421 95s, during the roller temperature control of mixing roll at 40 ℃-50 ℃.Through mixing rubber roll again, extrusion, moulding, vulcanize (the optimum curing time can be determined with vulkameter first) at 140 ℃ vulcanizers and make rubber item.
Embodiment 4
Rubber preliminary working method, 1 kilogram of natural rubber through preliminarily dried adds 1 Methionin that restrains at postprocessor, and the natural rubber of process aftertreatment is made caouttchouc through weighing, pressure bag.
Embodiment 5
Rubber preliminary working method, 1 kilogram of synthetic rubber through preliminarily dried adds 2 Methionins that restrain at rear drying machine (or postprocessor), and then weighing, pressure bag are made the synthetic rubber rubber.
Set forth a lot of details so that fully understand the present invention in the top description, still, the present invention can also adopt other to be different from other modes described here and implement, and therefore, can not be interpreted as limiting the scope of the invention.
In a word; although the present invention has exemplified above-mentioned preferred implementation, should illustrate, although those skilled in the art can carry out various variations and remodeling; unless such variation and remodeling have departed from scope of the present invention, otherwise all should be included in protection scope of the present invention.
Claims (7)
1. the application of Methionin aspect the vulcanization of rubber, reinforcement and anti-aging is characterized in that: Methionin is as a kind of novel thiofide and/or strengthening agent and/or anti-aging agent.
2. the application of Methionin according to claim 1 aspect the vulcanization of rubber, reinforcement and anti-aging is characterized in that: add Methionin in rubber preliminary working process, the add-on of Methionin accounts for 0.01%-1% of rubber gross weight.
3. the application of Methionin according to claim 1 aspect the vulcanization of rubber, reinforcement and anti-aging is characterized in that: add Methionin in the rubber item production process, the add-on of Methionin accounts for 0.01%-1% of rubber gross weight.
4. the application of Methionin according to claim 2 aspect the vulcanization of rubber, reinforcement and anti-aging is characterized in that: behind the rubber preliminarily dried, add Methionin when aftertreatment, the rubber of process aftertreatment is made rubber raw rubber through weighing, pressure bag.
5. the application of Methionin according to claim 3 aspect the vulcanization of rubber, reinforcement and anti-aging is characterized in that: add Methionin in rubber mixing process, mixingly evenly make rubber item by sulfuration.
6. according to claim 1, the application of the described Methionin of 2,3 any one aspect the vulcanization of rubber, reinforcement and anti-aging, it is characterized in that: described Methionin is biochemical SILVER REAGENT or pharmaceutical grade or food grade or technical grade.
7. according to claim 1, the application of the described Methionin of 2,3 any one aspect the vulcanization of rubber, reinforcement and anti-aging, it is characterized in that: described rubber is natural rubber or synthetic rubber or mixed rubber.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102112538A (en) * | 2008-06-30 | 2011-06-29 | 倍耐力轮胎股份公司 | Tyre and crosslinkable elastomeric composition comprising an oxetane derivative and an amino acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102112538A (en) * | 2008-06-30 | 2011-06-29 | 倍耐力轮胎股份公司 | Tyre and crosslinkable elastomeric composition comprising an oxetane derivative and an amino acid |
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Application publication date: 20130102 |