CN107955277A - A kind of rubber and preparation method thereof - Google Patents
A kind of rubber and preparation method thereof Download PDFInfo
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- CN107955277A CN107955277A CN201610899865.5A CN201610899865A CN107955277A CN 107955277 A CN107955277 A CN 107955277A CN 201610899865 A CN201610899865 A CN 201610899865A CN 107955277 A CN107955277 A CN 107955277A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/06—Sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The present invention relates to high molecular synthetic material field, is specially a kind of rubber, which contains rubber antioxidant composition, butyl rubber, vulcanizing agent and auxiliary material；Antioxidant composition contains formula (1) and the compound shown in formula (2), and formula (3) and/or the compound shown in formula (4)；R1‑R9、R1’‑R8’、R1”‑R4" it is independently selected from the side chain of C1 C6 or the alkyl of straight chain；N is 1 10 integer.Also disclose the preparation method of rubber.Rubber antioxidant provided by the invention is applied in the preparation of butyl rubber, can play the role of collaboration between each material, is assigned the excellent resistance to thermal oxide of rubber and is prevented old performance, and has the higher feature of environmental protection.
Description
Technical field
The invention belongs to high molecular synthetic material field, a kind of specific rubber, a kind of preparation side of rubber
Method.
Background technology
Rubber, also can be inevitably in storage, transport, processing and use as one of three big synthesis high molecular materials
Generation aging.For example although butyl rubber is a kind of rubber of low-unsaturation-degree, its heat-resisting and ageing-resistant performance is much better than other
General purpose rubber, tacky, the generation aging phenomenon but it also can gradually soften with continuing for thermo-oxidative ageing.In order to further carry
The ageing-resistant performance of the high molecular materials such as high butyl rubber, slows down or delays the speed of the macromolecule material agings such as rubber, most main
The method wanted is to add antioxidant when material is processed, and is broken and crosslinked speed, extension reaction with this to reduce ageing of rubber
Induction period, so as to achieve the purpose that to improve elastomeric material ageing-resistant performance.
At present, the common antioxidant of rubber mainly has two kinds of amine and phenols.But when both antioxidants are used in butyl rubber
When in the preparation of glue product, it prevents that old effect need to be further improved.
Since the requirement to antioxidant during rubber ageing-proof is higher and higher, find a kind of efficient suitable
For butyl rubber antioxidant for butyl rubber product preparation to its anti-aging work for it is then very crucial.
The content of the invention
The purpose of the invention is to overcome disadvantages described above, there is provided a kind of to have the butyl rubber system for efficiently preventing old performance
Product, and the preparation method of the butyl rubber product.
To achieve these goals, the present invention provides a kind of rubber, wherein, which, which contains rubber, prevents always
Agent composition, butyl rubber, vulcanizing agent and auxiliary material；
Wherein, the rubber antioxidant composition contains component A, component B and component C, wherein, the component A is such as formula
(1) compound shown in, component B are the compound as shown in formula (2), and component C is for the compound as shown in formula (3) and/or such as
Compound shown in formula (4)；
Wherein, in formula (1), R1、R2、R3、R4、R5、R6、R7、R8And R9It is independently selected from the side chain or straight chain of C1-C6
Alkyl；In formula (2), n is the integer of 1-10；In formula (3), R1’、R2’、R3’、R4’、R5’、R6’、R7' and R8' each independent
The alkyl of side chain or straight chain selected from C1-C6；In formula (4), R1”、R2”、R3" and R4" it is independently selected from the side chain of C1-C6
Or the alkyl of straight chain.
Second aspect, present invention also offers the preparation method of as above rubber, this method includes：By butyl rubber,
Vulcanizing agent, auxiliary material and the rubber antioxidant composition are mixed and vulcanized.
By regarding the composition provided by the invention for containing component A, component B and component C as rubber antioxidant composition
It is applied in the preparation of butyl rubber product, collaboration can be played the role of between each material, assigns prepared vulcanization butyl
Old performance is prevented in the excellent resistance to thermal oxide of rubber, as in the embodiment shown, using rubber antioxidant group provided by the invention
Vulcanized butyl rubber product prepared by compound can effectively improve the tensile strength change rate of butyl rubber and break elongation
Change rate, and effectively improve the anti-aging coefficient of butyl rubber.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
In a first aspect, the present invention provides a kind of rubber, wherein, which contains rubber antioxidant combination
Thing, butyl rubber, vulcanizing agent and auxiliary material；
Wherein, the rubber antioxidant composition contains component A, component B and component C, wherein, the component A is such as formula
(1) compound shown in, component B are the compound as shown in formula (2), and component C is for the compound as shown in formula (3) and/or such as
Compound shown in formula (4)；
Wherein, in formula (1), R1、R2、R3、R4、R5、R6、R7、R8And R9It is independently selected from the side chain or straight chain of C1-C6
Alkyl；In formula (2), n is the integer of 1-10；In formula (3), R1’、R2’、R3’、R4’、R5’、R6’、R7' and R8' each independent
The alkyl of side chain or straight chain selected from C1-C6；In formula (4), R1”、R2”、R3" and R4" it is independently selected from the side chain of C1-C6
Or the alkyl of straight chain.
The present inventor has found in the course of the study, using the combination of component A as above, component B and component C as
During butyl rubber antioxidant, good synergistic effect can be played between each component therein, so as to assign butyl rubber product
More excellent performance, therefore complete the present invention.
, according to the invention it is preferred to, in formula (1), R1、R2、R3、R4、R5、R6、R7、R8And R9It is independently selected from C1-C4
Side chain or straight chain alkyl；In formula (2), n 1-5；In formula (3), R1’、R2’、R3’、R4’、R5’、R6’、R7' and R8' each only
The alkyl of vertical side chain or straight chain selected from C1-C4；In formula (4), R1”、R2”、R3" and R4" it is independently selected from C1-C4's
The alkyl of side chain or straight chain.
Wherein, in the case of no any opposite explanation, what term " side chain of C1-C4 or the alkyl of straight chain " referred to is
Methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group and the tert-butyl group.
According to the present invention, R1、R2、R3、R4、R5、R6、R1’、R2’、R3’、R4’、R5’、R6’、R7’、R8’、R1”、R2”、R3" and
R4" butyl is both preferably, it is most preferably the tert-butyl group；R7、R8And R9Both preferably methyl.
Correspondingly, work as R1、R4、R3、R4、R5And R6For the tert-butyl group, and R7、R8And R9When being methyl, component A is 1,3,5-
Trimethyl -2,4,6- three (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene；In component B, n is preferably the integer of 1-5, and is preferably
The mixture of p-methyl phenol-dicyclopentadiene-tert-butylation resin shown in following formula (5), its average molecular weight are preferably
460-1420, more preferably 460-700；Work as R1’、R2’、R3’、R4’、R5’、R6’、R7' and R8' when being the tert-butyl group, the formula
(3) compound shown in is four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters；Work as R1”、R2”、R3" and
R4" when being the tert-butyl group, the compound shown in the formula (4) is double (2,4- di-tert-butyl-phenyl) pentaerythrite diphosphorous acids
Ester.
According to the present invention, as long as carrying out each component as above with the use of the goal of the invention that can realize the present invention,
And for the content of each component in the rubber antioxidant composition, the not excessive limitation of the present invention, they can compared with
It is changed in wide scope.But in situations where it is preferred, relative to the component A of 100 parts by weight, the component B's contains
Measure as 4-800 parts by weight, be preferably 50-800 parts by weight, more preferably 50-300 parts by weight, the content of the component C is 15-
1100 parts by weight, are preferably 50-640 parts by weight, more preferably 90-400 parts by weight.
Herein it should be noted that the present invention rubber antioxidant composition in, when containing component C be selected from be two kinds
During compound, term " content of component C " refers to the total content of two kinds of compounds, when containing component C be selected from be one kindization
During compound, term " content of component C " refers to a kind of content of its compound being selected from.
A kind of embodiment according to the present invention, the component C are that double (2,4- di-tert-butyl-phenyl) pentaerythrites two are sub-
Phosphate, that is, the antioxidant composition contains 1,3,5- trimethyls -2,4, (3, the 5- di-t-butyl -4- hydroxyl benzyls of 6- tri-
Base) benzene, p-methyl phenol-dicyclopentadiene-tert-butylation resin and double two phosphorous of (2,4- di-tert-butyl-phenyls) pentaerythrite
Acid esters.
A kind of preferred embodiment according to the present invention, the component C are four [β-(3,5- di-t-butyl -4- hydroxy benzenes
Base) propionic acid] pentaerythritol ester, that is, the antioxidant composition contains 1,3,5- trimethyls -2,4, (3, the 5- bis- tertiary fourths of 6- tri-
Base -4- hydroxybenzyls) benzene, p-methyl phenol-dicyclopentadiene-tert-butylation resin and four [β-(3,5- di-t-butyl -4- hydroxyls
Base phenyl) propionic acid] pentaerythritol ester.
Another preferred embodiment according to the present invention, the component C are four [β-(3,5- di-t-butyl -4- hydroxy benzenes
Base) propionic acid] pentaerythritol ester and double (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites, that is, the antioxidant group
Compound contains 1,3,5- trimethyls -2,4,6- three (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene, p-methyl phenol-bicyclic penta 2
Alkene-tert-butylation resin, four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters and double (bis- tertiary fourths of 2,4-
Base phenyl) pentaerythritol diphosphites.
Wherein, although in the case that the rubber antioxidant composition of the present invention contains as above 4 kinds of compounds, each group divides it
Between synergistic effect can be further enhanced, but it was found by the inventors of the present invention that as four [β-(3,5- di-t-butyl -4-
Hydroxy phenyl) propionic acid] weight ratio of pentaerythritol ester and double (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites is 1:
0.25-10, more preferably 1:In the case of 1-10, the synergistic effect can be lifted further.
Rubber according to the present invention, the preparation method of the rubber antioxidant composition are preferably：By component A, group
B and component C is divided to be mixed.
According to the present invention, the not excessive limitation of the mixing condition present invention of the present invention for the above components, as long as
Each component is sufficiently mixed.For example, the temperature of the mixing can be 30-70 DEG C, speed of agitator can be 100-
2000rpm, time can be 10-30min.
Wherein, the dosage of each component is referred to description as above, and it is no longer repeated herein.
The amount of rubber antioxidant composition of the present invention to containing in the butyl rubber product is not particularly limited,
As long as it can assign the prepared age inhibiting performance of rubber.Preferably, relative to the butyl rubber of 100 parts by weight
Collagen material, the content of the antioxidant composition is 1-5 parts by weight, more preferably 1-3 parts by weight.
According to the present invention, it was found by the inventors of the present invention that rubber antioxidant composition as described above is especially suitable for fourth
Base rubber, it can effectively improve the tensile strength change rate of butyl rubber and break elongation change, and effectively improve
The anti-aging coefficient of butyl rubber.Wherein, term " butyl rubber " is one kind of synthetic rubber, by isobutene and a small amount of isoamyl two
Alkene synthesizes.
Wherein, the butyl rubber can be conventional butyl rubbers (non-halogenated butyl rubber), or halobutyl
Rubber, such as can be chlorinated scoline and/or brombutyl, it is preferably brombutyl.
In addition, the present invention also has no particular limits the species and content of vulcanizing agent and auxiliary material, can be according to this area
Conventional selection carries out, for example, relative to the butyl rubber of 100 parts by weight, the dosage of the vulcanizing agent can be 1-5 weight
Part, it is preferably 1-2.5 parts by weight.
Wherein, the present invention can be the selection of this area routine to the vulcanizing agent selected from being not particularly limited.
Preferably, the one kind or more of the vulcanizing agent in insoluble sulfur, two thio morpholines and four two thio morpholines of vulcanization
Kind.
Rubber according to the present invention, the auxiliary material can be used to prepare the auxiliary of rubber for this area routine
Material, for example, can be carbon black, activator and accelerating agent.Preferably, relative to the butyl rubber of 100 parts by weight, the carbon black
Dosage can be 10-70 parts by weight, be preferably 30-50 parts by weight；The dosage of the activator can be 2-10 parts by weight, preferably
For 2-8 parts by weight；The dosage of the accelerating agent can be 0.2-2 parts by weight, be preferably 0.5-1 parts by weight.
Wherein, the carbon black, activator and accelerating agent can be various carbon blacks, activator and rush commonly used in the art
Into agent, for example, the carbon black can be the one or more in carbon black N550, carbon black N774 and carbon black N330；The activator
Can be zinc oxide and/or stearic acid；The accelerating agent can be guanidine type accelerating agent, thiazole type accelerator, sulfenamide type rush
One kind or more into agent, thiuram type accelerating agent, dithiocar-bamate type accelerating agent and D2EHDTPA salt form accelerating agent
Kind；Preferably, the accelerating agent is two thio tetra methylthiurams (TMTD).
Second aspect, the present invention separately provide the preparation method of rubber as described above, and this method includes：Will as above
Butyl rubber, vulcanizing agent as described above, auxiliary material as described above and the rubber antioxidant composition as described above
It is kneaded and vulcanizes.
According to the present invention, the method for the mixing and vulcanization can also be the method for this area routine, it is of the invention herein not
Repeat again.
The present invention will be described in detail by way of examples below.In following embodiments,
According to GB/T528-2009《Vulcanize the measure of rubber or thermoplastic elastomer tensile stress-strain performance》Middle regulation, choosing
The obtained rubber D1-D4 of the rubber Y1-Y10 and comparative example that are obtained in embodiment is cut into I type dumbbell shapeds with I type dumbbell shaped cut-off knives
Standard specimen, in 23 DEG C ± 2 DEG C and the translational speed of puller system (Beijing You Shen Electron equipment Co., Ltd, T2000E) clamper
Under conditions of 500mm/min ± 50mm/min, tensile strength and elongation rate of tensile failure before aging are tested.
According to GB/T528-2009《Vulcanize the measure of rubber or thermoplastic elastomer tensile stress-strain performance》In regulation,
Select I type dumbbell shaped cut-off knives that the obtained rubber D1-D4 of the rubber Y1-Y10 and comparative example that are obtained in embodiment is cut into Ι type dumbbells
Shape standard specimen, then according to GB/T3512-2014《Vulcanize rubber or the accelerated ageing of thermoplastic elastomer hot-air and resistance to heat examination
Test》In regulation, under conditions of selecting 145 DEG C, in free state standard specimen is suspended on hot air aging case, and (Chongqing is intelligent
Up to laboratory apparatus factory, LR-1) in, when thermo-oxidative ageing 72 is small after take out sample, and 23 DEG C ± 2 DEG C and relative humidity for 50% ±
When small to sample adjusting 16 under 10% laboratory environment, according still further to the regulation in GB/T528-2009, it is in laboratory temperature
Under conditions of the translational speed of 23 DEG C ± 2 DEG C and puller system clamper is 500mm/min ± 50mm/min, after measuring sample aging
Tensile strength and elongation rate of tensile failure, finally calculate the change rate and aging coefficient of tensile property.
Carry out tensile strength calculated change rate according to the following equation, break elongation change and aging coefficient.
Before tensile strength change rate=100% × (tensile strength before tensile strength-aging after aging)/aging
Tensile strength, absolute value are the smaller the better.
Break elongation change=100% × (elongation rate of tensile failure before elongation rate of tensile failure-aging after aging)/aging
Preceding elongation rate of tensile failure, absolute value are the smaller the better.
Aging coefficient=(elongation rate of tensile failure after tensile strength × aging after aging)/(tensile strength before aging ×
Elongation rate of tensile failure before aging), absolute value is the bigger the better.
Preparation example 1-9 and contrast preparation example 1-4
Illustrate the preparation of rubber antioxidant composition
Under room temperature (25 DEG C), mixed according to each component in the preparation example and contrast preparation example listed in table 1 and dosage
Uniformly, the antioxidant F1-F9 of corresponding preparation example 1-9, the antioxidant D F1-DF4 of corresponding contrast preparation example 1-4 are respectively obtained.
Table 1
Note：1,3,5- trimethyls -2,4,6- three (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene has purchased from Beijing easily chemical industry
Limit company；P-methyl phenol-dicyclopentadiene-tert-butylation resin is purchased from Nantong Xin Chang Chemical Co., Ltd.s, is an aggressiveness (n
=1) and dimer (n=2) mixture, its average molecular weight be 650；Four [β-(3,5- di-tert-butyl-hydroxy phenyls) third
Acid] pentaerythritol ester is purchased from Tianjin City Chenguang Chemical Co., Ltd；Double (2,4- di-tert-butyl-phenyls) pentaerythrite diphosphorous acids
Ester is purchased from Beijing Jiyi Chemicals Co., Ltd.；2,6- di-tert-butyl-4-methy phenols are limited purchased from Taiwan Ou Shiman rubber chemicals
Company；N- isopropyl-N'- phenyl-pphenylenediamines are purchased from Guangzhou Fu Yu Chemical Co., Ltd.s.
Embodiment 1-9
The preparation and test of rubber
By the non-halogenated butyl rubber of 100 parts by weight (Sinopec Beijing Yanshan Mountain branch company product, IIR1751), 50 weights
Measure part carbon black N330 (Shanghai Capote, N330), 1 parts by weight stearic acid (Shanghai Bei Te Chemical Co., Ltd.s), 3 parts by weight of rubber
(Zibo sea is along zinc for antioxidant (the antioxidant F1-F9 in preparation example 1-9 is separately added into embodiment 1-9), 3 part by weight of zinc oxide
Industry Co., Ltd), 1.75 parts by weight insoluble sulfurs (U.S. Yi Siman) and 1 parts by weight Vulcanization accelerator TMTD (change chemical industry in Tianjin one
Co., Ltd) it is added in open mill (Shanghai rubber machinery plant, XK-160A), mixed 18 minutes under 45 DEG C, 500rpm, will
The film of thickness about 2.2mm is made in sizing material.Parked after rubber compounding 24 it is small when after, in vulcanizing press (Huzhou under the conditions of 150 DEG C
Hong Qiao rubber manufacturing machineries Co., Ltd, XLX-D600 × 600 × 3) in vulcanization 25 minutes, then test piece is removed from the molds and is put into
Cool down 15 minutes in water, then dry water mark, parked at 23 DEG C ± 2 DEG C of laboratory temperature 16 it is small when, respectively obtain thickness
For the butyl rubber product Y1-Y9 of 2 millimeters of the antioxidants using preparation example 1-9.
The tensile strength change rate before and after the thermo-oxidative ageing of butyl rubber product Y1-Y9 is measured respectively, breaks variable elongation
Rate and aging coefficient, the results are shown in Table 2.
Embodiment 10
Method according to embodiment 1 (using the rubber antioxidant F1 in embodiment 1) carries out the preparation of butyl rubber product
And performance test, difference are, 100 parts by weight brombutyls (Sinopec Beijing Yanshan Mountain is used in the present embodiment
Branch company's product, BIIR2046) instead of the butyl rubber in embodiment 1, butyl rubber product Y10 is made, measures butyl rubber
Tensile strength change rate before and after the thermo-oxidative ageing of product Y10, break elongation change and aging coefficient, the results are shown in Table 2.
Comparative example 1-4
The butyl rubber product using the rubber antioxidant in contrast preparation example 1-4 is prepared according to the method in embodiment 1
D1-D4, other components and dosage and preparation condition are constant, and what difference was only that 3 parts by weight of rubber antioxidants use is respectively
Contrast the antioxidant D F1-DF4 in preparation example 1-4.
Measure the tensile strength change rate before and after the thermo-oxidative ageing of rubber D1-D4 respectively, break elongation change and
Aging coefficient, the results are shown in Table 2.
Table 2
| Numbering | Tensile strength change rate/% | Break elongation change/% | Aging coefficient |
| Embodiment 1 (Y1) | -27 | -20 | 0.58 |
| Embodiment 2 (Y2) | -30 | -20 | 0.56 |
| Embodiment 3 (Y3) | -30 | -22 | 0.55 |
| Embodiment 4 (Y4) | -34 | -24 | 0.50 |
| Embodiment 5 (Y5) | -33 | -24 | 0.51 |
| Embodiment 6 (Y6) | -36 | -26 | 0.47 |
| Embodiment 7 (Y7) | -33 | -22 | 0.52 |
| Embodiment 8 (Y8) | -34 | -20 | 0.53 |
| Embodiment 9 (Y9) | -37 | -24 | 0.48 |
| Embodiment 10 (Y10) | -24 | -18 | 0.63 |
| Comparative example 1 (D1) | -44 | -33 | 0.38 |
| Comparative example 2 (D2) | -46 | -33 | 0.36 |
| Comparative example 3 (D3) | -68 | -44 | 0.18 |
| Comparative example 4 (D4) | -33 | -21 | 0.53 |
Applied it can be seen from upper table 2 compared to comparative example 1-4, rubber antioxidant composition provided by the invention
With excellent heatproof air aging performance when in the preparation of butyl rubber product.Also, by the embodiment of the present invention 1-3 and reality
Apply a 4-9 to compare, it can be seen that in the case of preferable component proportion, antioxidant composition of the invention is applied to butyl
The performance of butyl rubber product can be lifted further obtained in the preparation of rubber, by embodiment 1 and embodiment
10 comparison can be seen that can further be changed using the performance of the rubber prepared by brombutyl
It is kind.
In addition, each component that rubber antioxidant composition is prepared in the present invention is nontoxic or less toxic component, and in rubber
It is kneaded or will not generates noxious material during vulcanizing, therefore, belongs to environmentally-frierubber rubber anti-ageing agent.Although contrast preparation example
The anti-old performance of 4 rubber antioxidant can also meet the requirements, but its antioxidant used can produce environment certain pollution,
Belong to the rubber antioxidant of non-environmental protection type.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of rubber, it is characterised in that the rubber contains rubber antioxidant composition, butyl rubber, vulcanizing agent
And auxiliary material；
Wherein, the rubber antioxidant composition contains component A, component B and component C, wherein, the component A is such as formula (1) institute
The compound shown, component B are the compound as shown in formula (2), and component C is for the compound as shown in formula (3) and/or such as formula (4)
Shown compound；
Wherein, in formula (1), R1、R2、R3、R4、R5、R6、R7、R8And R9It is independently selected from the side chain of C1-C6 or the hydrocarbon of straight chain
Base；In formula (2), n is the integer of 1-10；In formula (3), R1’、R2’、R3’、R4’、R5’、R6’、R7' and R8' be independently selected from
The side chain of C1-C6 or the alkyl of straight chain；In formula (4), R1”、R2”、R3" and R4" it is independently selected from the side chain or straight of C1-C6
The alkyl of chain.
2. rubber according to claim 1, wherein, in formula (1), R1、R2、R3、R4、R5、R6、R7、R8And R9Each solely
The alkyl of vertical side chain or straight chain selected from C1-C4；In formula (2), n is the integer of 1-5；In formula (3), R1’、R2’、R3’、R4’、
R5’、R6’、R7' and R8' it is independently selected from the side chain of C1-C4 or the alkyl of straight chain；In formula (4), R1”、R2”、R3" and R4" each
From the independent side chain selected from C1-C4 or the alkyl of straight chain.
3. rubber according to claim 2, wherein, R1、R2、R3、R4、R5、R6、R1’、R2’、R3’、R4’、R5’、R6’、
R7’、R8’、R1”、R2”、R3" and R4" it is butyl；R7、R8And R9It is methyl.
4. according to the rubber described in any one in claim 1-3, wherein, in the rubber antioxidant composition, phase
For the component A of 100 parts by weight, the content of component B is 4-800 parts by weight, and the content of the component C is 15-1100 parts by weight；
Preferably, it is 50-800 parts by weight relative to the content of the component A, the component B of 100 parts by weight, the component C's contains
Measure as 50-640 parts by weight.
5. according to the rubber described in any one in claim 1-4, wherein, in the rubber antioxidant composition, institute
It is the compound as shown in formula (3) and the compound as shown in formula (4) to state component C；
Wherein, the weight ratio of the compound as shown in formula (3) and the compound as shown in formula (4) is 1:0.25-10, is preferably 1:
1-10。
6. according to the rubber described in any one in claim 1-5, wherein, the preparation of the rubber antioxidant composition
Method includes：Component A, component B and component C are mixed.
7. rubber according to claim 6, wherein, the condition of the mixing includes：Temperature is 30-70 DEG C, stirring
Rotating speed is 100-2000rpm, time 10-30min.
8. rubber according to claim 1, wherein, the butyl rubber is non-halogenated butyl rubber and/or halogenation
Butyl rubber.
9. rubber according to claim 8, wherein, the halogenated butyl rubber is chlorinated scoline and/or bromine
Change butyl rubber.
10. the preparation method of the rubber in claim 1-9 described in any one, this method include：By butyl rubber, sulphur
Agent, auxiliary material and rubber antioxidant composition are kneaded and vulcanize.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967223A (en) * | 2010-09-28 | 2011-02-09 | 江苏飞亚化学工业有限责任公司 | Synthesis method of paracresol-dicyclopentadiene isobutylation resin antioxidant |
| CN102993580A (en) * | 2012-11-30 | 2013-03-27 | 西安致泰橡塑工业有限公司 | High-strength rubber for mine inner tube |
| CN103319315A (en) * | 2013-06-17 | 2013-09-25 | 湖北工业大学 | Method for producing aggregate-type hindered phenol antioxidant |
| CN103420807A (en) * | 2012-05-22 | 2013-12-04 | 中国石油化工股份有限公司 | Preparation method for polymerization-type asymmetric hindered phenol anti-oxidant resins |
| CN104693519A (en) * | 2015-03-25 | 2015-06-10 | 江苏飞亚化学工业有限责任公司 | Preparation method for butadiene rubber composite |
| CN105255026A (en) * | 2015-10-21 | 2016-01-20 | 北京化工大学 | Reactively compatibilized butyl rubber/polyamide TPV (thermoplastic vulcanzate) and preparation method thereof |
| CN105367922A (en) * | 2015-12-24 | 2016-03-02 | 河南乐山电缆有限公司 | Environment-friendly and energy-saving natural cross-linked rubber material and production method thereof |
| CN106566095A (en) * | 2016-10-28 | 2017-04-19 | 无锡市永兴金属软管有限公司 | Butyl rubber for steam hose |
-
2016
- 2016-10-14 CN CN201610899865.5A patent/CN107955277B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101967223A (en) * | 2010-09-28 | 2011-02-09 | 江苏飞亚化学工业有限责任公司 | Synthesis method of paracresol-dicyclopentadiene isobutylation resin antioxidant |
| CN103420807A (en) * | 2012-05-22 | 2013-12-04 | 中国石油化工股份有限公司 | Preparation method for polymerization-type asymmetric hindered phenol anti-oxidant resins |
| CN102993580A (en) * | 2012-11-30 | 2013-03-27 | 西安致泰橡塑工业有限公司 | High-strength rubber for mine inner tube |
| CN103319315A (en) * | 2013-06-17 | 2013-09-25 | 湖北工业大学 | Method for producing aggregate-type hindered phenol antioxidant |
| CN104693519A (en) * | 2015-03-25 | 2015-06-10 | 江苏飞亚化学工业有限责任公司 | Preparation method for butadiene rubber composite |
| CN105255026A (en) * | 2015-10-21 | 2016-01-20 | 北京化工大学 | Reactively compatibilized butyl rubber/polyamide TPV (thermoplastic vulcanzate) and preparation method thereof |
| CN105367922A (en) * | 2015-12-24 | 2016-03-02 | 河南乐山电缆有限公司 | Environment-friendly and energy-saving natural cross-linked rubber material and production method thereof |
| CN106566095A (en) * | 2016-10-28 | 2017-04-19 | 无锡市永兴金属软管有限公司 | Butyl rubber for steam hose |
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