CN112239568A - Anti-aging agent composition and application thereof, rubber composition, vulcanized rubber and preparation method thereof - Google Patents
Anti-aging agent composition and application thereof, rubber composition, vulcanized rubber and preparation method thereof Download PDFInfo
- Publication number
- CN112239568A CN112239568A CN201910657086.8A CN201910657086A CN112239568A CN 112239568 A CN112239568 A CN 112239568A CN 201910657086 A CN201910657086 A CN 201910657086A CN 112239568 A CN112239568 A CN 112239568A
- Authority
- CN
- China
- Prior art keywords
- weight
- parts
- rubber
- amount
- tert
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of anti-aging agents, and discloses an anti-aging agent composition and application thereof, a rubber composition, vulcanized rubber and a preparation method thereof, wherein the anti-aging agent composition contains beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid isooctyl alcohol ester, 2, 6-di-tert-butyl-p-cresol, liquid paraffin and a phosphite ester compound shown in a formula (1). Hair brushThe antioxidant composition can improve the vulcanization efficiency and obviously improve the aging resistance of rubber products when the rubber products are prepared, is not easy to generate the blooming phenomenon, and has the advantage of environmental protection.
Description
Technical Field
The invention relates to the field of anti-aging agents, and in particular relates to an anti-aging agent composition, application of the anti-aging agent composition in preparation of rubber products, a rubber composition, a method for preparing vulcanized rubber and the vulcanized rubber prepared by the method.
Background
The rubber anti-aging agent not only can resist thermal oxidation aging and ozone aging, but also has remarkable effects on resisting copper ions, light, flexion and other aging.
At present, the antioxidants used for rubber products are roughly classified into amines and hindered phenols. The amine anti-aging agent has the most prominent protective effect and is the earliest discovered anti-aging agent with the most varieties and the most extensive application.
However, amine-based antioxidants change the color of the rubber or cause pollution to the surrounding environment. At present, the amine anti-aging agent is only used in the tire industry with low requirements on toxicity and color pollution, but cannot be used in the aspects of medical rubber products, plastics, fibers and the like.
Hindered phenol antioxidants are less polluting, but their anti-aging effect is inferior to that of amine antioxidants.
CN106589982A discloses a less toxic anti-aging agent composition, which contains glycol bis beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, stearate, liquid paraffin and phosphite ester compound. The anti-aging agent composition can improve the aging resistance of rubber. However, the safety and vulcanization efficiency of the vulcanized rubber formed by the antioxidant composition of the prior art are still to be improved.
Disclosure of Invention
The invention aims to overcome the defect of low vulcanization efficiency when the rubber composition in the prior art is formed into vulcanized rubber.
In order to achieve the above object, the present invention provides an antioxidant composition comprising isooctyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2, 6-di-tert-butyl-p-cresol, liquid paraffin, and a phosphite compound represented by formula (1), wherein the isooctyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate is contained in an amount of 30 to 600 parts by weight, the 2, 6-di-tert-butyl-p-cresol is contained in an amount of 80 to 700 parts by weight, and the liquid paraffin is contained in an amount of 10 to 400 parts by weight, based on 100 parts by weight of the phosphite compound represented by formula (1),
wherein, in the formula (1), R1、R2、R3、R4、R5、R6Each independently selected from C1-C7Alkyl group of (1).
The invention also provides application of the anti-aging agent composition in preparation of rubber products.
The invention also provides a rubber composition which contains a rubber matrix, carbon black, an anti-aging agent, an activator and a vulcanizing agent, wherein the anti-aging agent is the anti-aging agent composition, and the rubber matrix is selected from at least one of natural rubber, styrene butadiene rubber and butadiene rubber.
The present invention also provides a process for preparing a vulcanized rubber, the process comprising:
(1) mixing and contacting a first rubber matrix with the components in the antioxidant composition to obtain an antioxidant mixture;
(2) carrying out first mixing on the anti-aging agent mixture, carbon black, an activating agent and a second rubber matrix to obtain a first-section rubber compound;
(3) carrying out second mixing on the first-stage rubber compound and a vulcanizing agent to obtain a second-stage rubber compound;
(4) carrying out plate vulcanization on the two-stage rubber compound,
wherein the first rubber matrix and the second rubber matrix are each independently selected from at least one of natural rubber, styrene butadiene rubber, and butadiene rubber.
The invention also provides vulcanized rubber prepared by the method for preparing vulcanized rubber.
The rubber composition formed from the antioxidant composition of the present invention has excellent vulcanization efficiency when forming a vulcanized rubber.
In addition, the anti-aging agent composition provided by the invention has the advantages of excellent anti-aging effect and environmental protection, and does not cause environmental pollution. In addition, when the anti-aging agent composition is used for preparing rubber products, the tensile strength of the rubber products can be ensured, the aging resistance of the rubber products is obviously improved, and the phenomenon of blooming is not easy to occur.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides an antioxidant composition comprising isooctyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2, 6-di-tert-butyl-p-cresol, liquid paraffin, and a phosphite compound represented by formula (1), wherein the content of isooctyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate is 30 to 600 parts by weight, the content of 2, 6-di-tert-butyl-p-cresol is 80 to 700 parts by weight, and the content of liquid paraffin is 10 to 400 parts by weight, based on 100 parts by weight of the phosphite compound represented by formula (1),
wherein, in the formula (1), R1、R2、R3、R4、R5、R6Each independently selected from C1-C7Alkyl group of (1).
Said "C" of the present invention1-C7The alkyl group of (1) includes a straight-chain alkyl group, a branched-chain alkyl group or a cyclic alkyl group, and may be, for example, a straight-chain alkyl group, a branched-chain alkyl group or a cyclic alkyl group having 1, 2, 3, 4, 5, 6, 7 total carbon atoms, and may be, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a n-hexyl group, a cyclopropyl group, a methylcyclopropyl group, an.
Preferably, in formula (1), R1、R2、R3、R4、R5、R6Each independently selected from C2-C5Straight chain alkyl of (2) and C2-C5Branched alkyl groups of (a). More preferably, in formula (1), R1、R2、R3、R4、R5、R6Each independently selected from C3-C4Straight chain alkyl of (2) and C3-C4Branched alkyl groups of (a).
More preferably, the phosphite compound represented by formula (1) is tris (2, 4-di-tert-butylphenyl) phosphite and/or tris (2, 4-dipropylphenyl) phosphite.
Particularly preferably, the phosphite compound represented by formula (1) is tris (2, 4-di-tert-butylphenyl) phosphite.
The beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) isooctyl propionate, 2, 6-di-tert-butyl-p-cresol, liquid paraffin and the phosphite ester compound shown in the formula (1) contained in the anti-aging agent composition have a synergistic effect, the anti-aging agent composition obtained by compounding has good aging resistance, and particularly when the phosphite ester compound shown in the formula (1) is tris (2, 4-di-tert-butylphenyl) phosphite, the anti-aging agent composition obtained by compounding has excellent aging resistance.
The isooctyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate has the following structure (2):
the 2, 6-di-tert-butyl-p-cresol has a structure shown as the following formula (3):
the main component of the liquid paraffin is C16-C20Of (a) is a normal alkane.
More preferably, the isooctyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate is contained in an amount of 60 to 400 parts by weight, the 2, 6-di-tert-butyl-p-cresol is contained in an amount of 120 to 600 parts by weight, and the liquid paraffin is contained in an amount of 30 to 250 parts by weight, relative to 100 parts by weight of the phosphite compound represented by the formula (1).
As mentioned above, the second aspect of the present invention provides the use of the antioxidant composition as described in the first aspect in the preparation of a rubber product.
As described above, the third aspect of the present invention provides a rubber composition containing a rubber matrix, carbon black, an antioxidant, an activator and a vulcanizing agent, wherein the antioxidant is the antioxidant composition described in the first aspect, and the rubber matrix is at least one selected from the group consisting of natural rubber, styrene-butadiene rubber and butadiene rubber.
Preferably, the cis content in the natural rubber is greater than 95 wt%.
Preferably, the styrene-butadiene rubber has a vinyl content of 50 to 70 wt%.
Preferably, the cis content in the butadiene rubber is 90 to 99 wt%.
The content of the antioxidant is preferably 10 to 100 parts by weight, more preferably 30 to 60 parts by weight, based on 100 parts by weight of the rubber base.
Preferably, the carbon black is at least one selected from carbon black N550, carbon black N774 and carbon black N330.
Preferably, the activator is selected from at least one of zinc oxide and stearic acid.
Preferably, the vulcanizing agent is selected from at least one of sulphur, dithiomorphine and dimorpholine tetrasulfide. The sulfur may be, for example, insoluble sulfur.
Preferably, the carbon black is contained in an amount of 10 to 70 parts by weight, more preferably 30 to 50 parts by weight, based on 100 parts by weight of the rubber matrix.
Preferably, the activator is contained in an amount of 2 to 10 parts by weight, more preferably 4 to 8 parts by weight, relative to 100 parts by weight of the rubber matrix.
Preferably, the vulcanizing agent is contained in an amount of 1 to 5 parts by weight, more preferably 1 to 3 parts by weight, relative to 100 parts by weight of the rubber matrix.
As previously mentioned, a fourth aspect of the present invention provides a method for preparing a vulcanized rubber, the method comprising:
(1) mixing and contacting a first rubber matrix and each component in the antioxidant composition in the first aspect to obtain an antioxidant mixture;
(2) carrying out first mixing on the anti-aging agent mixture, carbon black, an activating agent and a second rubber matrix to obtain a first-section rubber compound;
(3) carrying out second mixing on the first-stage rubber compound and a vulcanizing agent to obtain a second-stage rubber compound;
(4) carrying out plate vulcanization on the two-stage rubber compound,
wherein the first rubber matrix and the second rubber matrix are each independently selected from at least one of natural rubber, styrene butadiene rubber, and butadiene rubber.
The types of components involved in this aspect of the invention are the same as those described above in the present invention, and the present invention will not be repeated here in order to avoid redundancy.
Also, the first rubber matrix and the second rubber matrix of the present invention together constitute the rubber matrix in the aforementioned aspect of the rubber composition.
Particularly preferably, the second rubber matrix is styrene-butadiene rubber and/or butadiene rubber.
Preferably, in the step (1), the antioxidant composition is used in an amount of 40 to 70 parts by weight, preferably 45 to 65 parts by weight, relative to 100 parts by weight of the first rubber substrate.
Preferably, the amount of the carbon black is 10 to 70 parts by weight, the amount of the antioxidant mixture is 1 to 5 parts by weight, the amount of the activator is 2 to 10 parts by weight, and the amount of the vulcanizing agent is 1 to 5 parts by weight, relative to 100 parts by weight of the second rubber matrix.
More preferably, the carbon black is used in an amount of 30 to 50 parts by weight, the antioxidant mixture is used in an amount of 1 to 2.5 parts by weight, the activator is used in an amount of 4 to 8 parts by weight, and the vulcanizing agent is used in an amount of 1 to 3 parts by weight, based on 100 parts by weight of the second rubber matrix.
Preferably, in step (1), the conditions of the mixing contact include: the contact temperature is 10-80 deg.C, and the contact time is 10-60 min.
Preferably, in step (2), the conditions of the first mixing include: the mixing temperature is 50-70 deg.C, and the mixing time is 5-20 min. The first mixing may be carried out in an internal mixer, for example.
Preferably, in step (3), the conditions of the second mixing include: the mixing temperature is 35-55 deg.C, and the mixing time is 5-20 min. The second mixing may be performed, for example, in an open mill.
Preferably, in step (4), the vulcanizing conditions of the plate include: the temperature is 150 ℃ and 180 ℃, the pressure is 10-20MPa, and the time is 10-30 min.
As previously mentioned, a fifth aspect of the present invention provides a vulcanizate prepared by the method described in the fourth aspect.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available ones unless otherwise specified.
In the following examples, parts by weight, when referred to, represent 1g per part by weight.
Preparation example 1
20g of isooctyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 60g of 2, 6-di-tert-butyl-p-cresol, 20g of tris (2, 4-di-tert-butylphenyl) phosphite, 25g of liquid paraffin (purchased from Shandong Rui chemical Co., Ltd., the same below) and 250g of natural rubber (provided by Shanghai Kangshi chemical technology Co., Ltd.) having a cis content of 98 wt% were mixed at 70 ℃ for 15 minutes and mixed uniformly to obtain an antioxidant X1 mixture.
Preparation example 2
40g of isooctyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 50g of 2, 6-di-tert-butyl-p-cresol, 10g of tris (2, 4-dipropylphenyl) phosphite, 20g of liquid paraffin, and 218g of styrene-butadiene rubber (provided by Beijing Yanshan petrochemical company) with a vinyl content of 60 wt% were mixed at 30 ℃ for 35 minutes and mixed uniformly to obtain an antioxidant mixture X2.
Preparation example 3
30g of isooctyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 40g of 2, 6-di-tert-butyl-p-cresol, 30g of tris (2, 4-di-tert-butylphenyl) phosphite, 10g of liquid paraffin, 183g of butadiene rubber (available from Beijing Yanshan petrochemical company) having a cis content of 98% by weight were mixed at 50 ℃ for 20 minutes and mixed uniformly to obtain an antioxidant mixture X3.
Preparation example 4
This preparation was carried out in a similar manner to preparation 1, except that in this preparation the tris (2, 4-di-tert-butylphenyl) phosphite in preparation 1 was replaced with the tris (2, 4-dipropylphenyl) phosphite in the same amount by weight.
The antioxidant mixture X4 was obtained in this preparation example.
Comparative preparation example 1
This comparative preparation was carried out in a similar manner to preparation 1, except that the same weight of triphenoxyphos was used in place of tris (2, 4-di-tert-butylphenyl) phosphite as in preparation 1.
The comparative preparation example obtained an antioxidant mixture DX 1.
Comparative preparation example 2
This comparative preparation was carried out in a similar manner to preparation 1, except that the same weight of ethyleneglycol bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate was used instead of isooctyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate used in example 1.
The comparative preparation example obtained an antioxidant mixture DX 2.
Example 1
The rubber composition formula comprises:
the preparation method comprises the following steps:
1) adding the anti-aging agent mixture (X1), carbon black (carbon black N550), an activating agent (zinc oxide) and a second rubber matrix (natural rubber and styrene butadiene rubber) into an internal mixer, and mixing for 10 minutes at 55 ℃ to obtain a first-stage rubber compound;
2) mixing the first-stage rubber compound and a vulcanizing agent (insoluble sulfur) in an open mill for 10 minutes at 40 ℃ to obtain a second-stage rubber compound;
3) and adding the two-stage rubber compound into a 50T flat vulcanizing machine (Chengdu aviation hydraulic engineering Co., Ltd.) for flat vulcanization, and vulcanizing for 15 minutes at 165 ℃ and 15MPa to obtain vulcanized rubber S1 with the thickness of 2 mm.
Example 2
The rubber composition formula comprises:
the preparation method comprises the following steps:
1) adding the anti-aging agent mixture (X2), carbon black (carbon black N550), an activating agent (zinc oxide) and a second rubber matrix (natural rubber) into an internal mixer, and mixing for 15 minutes at 50 ℃ to obtain a first-stage rubber compound;
2) mixing the first-stage rubber compound and a vulcanizing agent (insoluble sulfur) in an open mill for 10 minutes at 40 ℃ to obtain a second-stage rubber compound;
3) and adding the two-stage rubber compound into a 50T flat vulcanizing machine (Chengdu aviation hydraulic engineering Co., Ltd.) for flat vulcanization, and vulcanizing for 15 minutes at 165 ℃ and 15MPa to obtain vulcanized rubber S2 with the thickness of 2 mm.
Example 3
The rubber composition formula comprises:
the preparation method comprises the following steps:
1) adding the anti-aging agent mixture (X3), carbon black (carbon black N550), an activating agent (zinc oxide) and a second rubber matrix (natural rubber) into an internal mixer, and mixing for 10 minutes at 60 ℃ to obtain a first-stage rubber compound;
2) mixing the first-stage rubber compound and a vulcanizing agent (insoluble sulfur) in an open mill for 10 minutes at 40 ℃ to obtain a second-stage rubber compound;
3) and adding the two-stage rubber compound into a 50T flat vulcanizing machine (Chengdu aviation hydraulic engineering Co., Ltd.) for flat vulcanization, and vulcanizing for 15 minutes at 165 ℃ and 15MPa to obtain vulcanized rubber S3 with the thickness of 2 mm.
Example 4
The rubber composition formula comprises:
the rubber composition formulation in this example was similar to the corresponding formulation in example 1, except that the same parts by weight of antioxidant blend X4 was used in place of the antioxidant blend X1 in example 1.
The preparation method comprises the following steps:
the process for the preparation of the vulcanizates in this example was exactly the same as the process for the preparation of the vulcanizates in example 1.
This example gives a vulcanized rubber S4 having a thickness of 2 mm.
Comparative example 1
The rubber composition formula comprises:
the formulation of the rubber composition in this comparative example was similar to the corresponding formulation in example 1, except that the same parts by weight of antioxidant 4010NA was used in place of the antioxidant blend X1 in example 1.
The preparation method comprises the following steps:
the process for the preparation of the vulcanizate in this comparative example is exactly the same as that of the vulcanizate in example 1.
This comparative example gives a vulcanizate DS1 having a thickness of 2 mm.
Comparative example 2
The rubber composition formula comprises:
the rubber composition formulation in this comparative example was similar to the corresponding formulation in example 1 except that the same parts by weight of antioxidant 4020 was used in place of the antioxidant blend X1 in example 1.
The preparation method comprises the following steps:
the process for the preparation of the vulcanizate in this comparative example is exactly the same as that of the vulcanizate in example 1.
This comparative example gives a vulcanizate DS2 having a thickness of 2 mm.
Comparative example 3
The rubber composition formula comprises:
the formulation of the rubber composition in this comparative example is similar to the corresponding formulation of example 1, except that the same parts by weight of the antioxidant mixture DX1 was used in this comparative example instead of the antioxidant mixture X1 in example 1.
The preparation method comprises the following steps:
the process for the preparation of the vulcanizate in this comparative example is exactly the same as that of the vulcanizate in example 1.
This comparative example gives a vulcanizate DS3 having a thickness of 2 mm.
Comparative example 4
The rubber composition formula comprises:
the formulation of the rubber composition in this comparative example is similar to the corresponding formulation of example 1, except that the same parts by weight of the antioxidant mixture DX2 was used in this comparative example instead of the antioxidant mixture X1 in example 1.
The preparation method comprises the following steps:
the process for the preparation of the vulcanizate in this comparative example is exactly the same as that of the vulcanizate in example 1.
This comparative example gives a vulcanizate DS4 having a thickness of 2 mm.
Test example
The vulcanized rubbers obtained in examples and comparative examples were tested for tensile properties, aging resistance and deformation resistance, respectively, according to the following methods.
(1) And (3) testing tensile property:
the vulcanized rubber was cut into dumbbell-shaped standard pieces by a type 1 dumbbell cutter as specified in GB/T528-92, and the tensile strength and elongation at break were measured at a test temperature of 25 ℃ and a drawing speed of 500 mm/min, and the results are shown in Table 1.
(2) And (3) aging resistance testing: according to the method specified in GB3512-83, vulcanized rubber is aged for 72 hours under thermal oxidation at 100 ℃, then the vulcanized rubber is cut into dumbbell-shaped standard sheets according to a 1-type dumbbell-shaped cutter specified in GB/T528-92, and the tensile strength and the elongation at break before and after aging are respectively tested by a tensile tester (model 401A, purchased from Nantong Zhonghao laboratory instruments Co., Ltd.) under the conditions that the test temperature is 25 ℃ and the traction speed is 500 mm/min.
The aging factor (tensile strength after aging × elongation at break) ÷ (tensile strength before aging × elongation at break) is shown in table 1.
(3) And (3) testing the deformation resistance:
the vulcanized rubber was cut into dumbbell-shaped standard pieces by a type 1 dumbbell cutter as specified in GB/T528-92, and the test pieces were stretch-broken at a test temperature of 25 ℃ and a pulling speed of 500 mm/min. Placing the sample after tensile fracture for 3min, then jointing the two fractured parts together, measuring the distance between two parallel lines after jointing, and calculating the permanent deformation value after breaking according to the following formula:
Sb＝100(Lt-L0)/L0wherein S isbPermanent set at break,%; l istTwo lines are parallel after sample anastomosisDistance between lines, mm; l is0Initial test length, mm. The results obtained are shown in table 1.
(4) Test for vulcanization Properties
Adopting a GT-M2000A rotor-free vulcanizer, a high-speed rail detection instrument, a vulcanization temperature of 160 ℃, a vibration angle of +/-0.5 degrees, a vibration frequency of 1.66Hz, an air pressure of 0.46Mpa and a sample volume of 5cm3。t10Time corresponding to a degree of vulcanization of 10%, t90The time corresponding to a degree of vulcanization of 90%. In general t10The longer the time, the better the processing safety; t is t90-t10The smaller the value, the higher the vulcanization efficiency, which indicates the time required for vulcanization.
TABLE 1
From the results, the vulcanized rubber prepared by the antioxidant provided by the invention has excellent aging resistance, good mechanical property, good vulcanization processing safety and high vulcanization efficiency, and the antioxidant provided by the invention has the advantage of environmental protection.
Further, as can be seen by comparing the effects of the examples of the present invention and comparative examples 1 to 2, the effect of the antioxidant provided by the present invention is equivalent to that of the amine type antioxidant having the best effect in the art, and further has the advantage of environmental protection compared to the amine type antioxidant.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (14)
1. An antioxidant composition comprising isooctyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, 2, 6-di-tert-butyl-p-cresol, liquid paraffin, and a phosphite compound represented by the formula (1), wherein the content of isooctyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate is 30 to 600 parts by weight, the content of 2, 6-di-tert-butyl-p-cresol is 80 to 700 parts by weight, and the content of liquid paraffin is 10 to 400 parts by weight, based on 100 parts by weight of the phosphite compound represented by the formula (1),
wherein, in the formula (1), R1、R2、R3、R4、R5、R6Each independently selected from C1-C7Alkyl group of (1).
2. The antioxidant composition according to claim 1, wherein, in formula (1), R1、R2、R3、R4、R5、R6Each independently selected from C2-C5Straight chain alkyl of (2) and C2-C5A branched alkyl group of (a);
preferably, in formula (1), R1、R2、R3、R4、R5、R6Each independently selected from C3-C4Straight chain alkyl of (2) and C3-C4Branched alkyl groups of (a).
3. The antioxidant composition according to claim 1, wherein the phosphite ester compound represented by formula (1) is at least one of tris (2, 4-di-tert-butylphenyl) phosphite and/or tris (2, 4-dipropylphenyl) phosphite;
preferably, the phosphite ester compound represented by the formula (1) is tris (2, 4-di-tert-butylphenyl) phosphite.
4. The antioxidant composition according to any one of claims 1 to 3, wherein the isooctyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate is contained in an amount of 60 to 400 parts by weight, the 2, 6-di-tert-butyl-p-cresol is contained in an amount of 120-600 parts by weight, and the liquid paraffin is contained in an amount of 30 to 250 parts by weight, based on 100 parts by weight of the phosphite compound represented by formula (1).
5. Use of the antioxidant composition according to any one of claims 1 to 4 for the preparation of rubber products.
6. A rubber composition, which contains a rubber matrix, carbon black, an anti-aging agent, an activator and a vulcanizing agent, wherein the anti-aging agent is the anti-aging agent composition according to any one of claims 1 to 4, and the rubber matrix is selected from at least one of natural rubber, styrene-butadiene rubber and butadiene rubber;
preferably, the antioxidant is contained in an amount of 10 to 100 parts by weight, preferably 30 to 60 parts by weight, based on 100 parts by weight of the rubber base.
7. The rubber composition of claim 6, wherein the cis content in the natural rubber is greater than 95 wt%;
preferably, the vinyl content in the styrene-butadiene rubber is 50 to 70 wt%;
preferably, the cis content in the butadiene rubber is 90 to 99 wt%.
8. The rubber composition according to claim 6 or 7, wherein the carbon black is selected from at least one of carbon black N550, carbon black N774 and carbon black N330;
preferably, the activator is selected from at least one of zinc oxide and stearic acid;
preferably, the vulcanizing agent is selected from at least one of sulphur, dithiomorphine and dimorpholine tetrasulfide.
9. The rubber composition according to any one of claims 6 to 8, wherein the carbon black is contained in an amount of 10 to 70 parts by weight, preferably 30 to 50 parts by weight, relative to 100 parts by weight of the rubber matrix;
preferably, the activator is contained in an amount of 2 to 10 parts by weight, preferably 4 to 8 parts by weight, relative to 100 parts by weight of the rubber matrix;
preferably, the vulcanizing agent is contained in an amount of 1 to 5 parts by weight, preferably 1 to 3 parts by weight, relative to 100 parts by weight of the rubber matrix.
10. A method of preparing a vulcanized rubber, the method comprising:
(1) mixing and contacting a first rubber matrix and each component in the antioxidant composition as defined in any one of claims 1-4 to obtain an antioxidant mixture;
(2) carrying out first mixing on the anti-aging agent mixture, carbon black, an activating agent and a second rubber matrix to obtain a first-section rubber compound;
(3) carrying out second mixing on the first-stage rubber compound and a vulcanizing agent to obtain a second-stage rubber compound;
(4) carrying out plate vulcanization on the two-stage rubber compound,
wherein the first rubber matrix and the second rubber matrix are each independently selected from at least one of natural rubber, styrene butadiene rubber, and butadiene rubber.
11. The method according to claim 10, wherein, in step (1), the antioxidant composition is used in an amount of 40 to 70 parts by weight, preferably 45 to 65 parts by weight, relative to 100 parts by weight of the first rubber substrate.
12. The method according to claim 10 or 11, wherein the carbon black is used in an amount of 10 to 70 parts by weight, the antioxidant mixture is used in an amount of 1 to 5 parts by weight, the activator is used in an amount of 2 to 10 parts by weight, and the vulcanizing agent is used in an amount of 1 to 5 parts by weight, relative to 100 parts by weight of the second rubber matrix;
preferably, the carbon black is used in an amount of 30-50 parts by weight, the antioxidant mixture is used in an amount of 1-2.5 parts by weight, the activator is used in an amount of 4-8 parts by weight, and the vulcanizing agent is used in an amount of 1-3 parts by weight, based on 100 parts by weight of the second rubber matrix.
13. The method of any one of claims 10-12, wherein in step (1), the conditions of the mixing contact comprise: the contact temperature is 10-80 ℃, and the contact time is 10-60 min;
preferably, in step (2), the conditions of the first mixing include: the mixing temperature is 50-70 ℃, and the mixing time is 5-20 min;
preferably, in step (3), the conditions of the second mixing include: the mixing temperature is 35-55 ℃, and the mixing time is 5-20 min;
preferably, in step (4), the vulcanizing conditions of the plate include: the temperature is 150 ℃ and 180 ℃, the pressure is 10-20MPa, and the time is 10-30 min.
14. A vulcanized rubber produced by the process of any one of claims 10-13.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910657086.8A CN112239568A (en) | 2019-07-19 | 2019-07-19 | Anti-aging agent composition and application thereof, rubber composition, vulcanized rubber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910657086.8A CN112239568A (en) | 2019-07-19 | 2019-07-19 | Anti-aging agent composition and application thereof, rubber composition, vulcanized rubber and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112239568A true CN112239568A (en) | 2021-01-19 |
Family
ID=74167863
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910657086.8A Pending CN112239568A (en) | 2019-07-19 | 2019-07-19 | Anti-aging agent composition and application thereof, rubber composition, vulcanized rubber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112239568A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116675906A (en) * | 2023-07-12 | 2023-09-01 | 江苏驰硕新材料科技有限公司 | Antioxidant for rubber and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467798A (en) * | 2012-06-06 | 2013-12-25 | 中国石油化工股份有限公司 | Elastomer composition and oil-extended rubber |
| CN103709439A (en) * | 2012-09-29 | 2014-04-09 | 中国石油化工股份有限公司 | Antioxidant composition and its preparation method, styrene-based thermoplastic elastomer and its preparation method |
| CN106589982A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Rubber antioxidant composition, rubber master batch as well as preparation method thereof and rubber and preparation method thereof |
-
2019
- 2019-07-19 CN CN201910657086.8A patent/CN112239568A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467798A (en) * | 2012-06-06 | 2013-12-25 | 中国石油化工股份有限公司 | Elastomer composition and oil-extended rubber |
| CN103709439A (en) * | 2012-09-29 | 2014-04-09 | 中国石油化工股份有限公司 | Antioxidant composition and its preparation method, styrene-based thermoplastic elastomer and its preparation method |
| CN106589982A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Rubber antioxidant composition, rubber master batch as well as preparation method thereof and rubber and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116675906A (en) * | 2023-07-12 | 2023-09-01 | 江苏驰硕新材料科技有限公司 | Antioxidant for rubber and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1967387B1 (en) | Rubber composition and tire sidewall with such a composition comprising emulsion styrene/butadiene rubber, cis1,4-polyisoprene rubber and cis 1,4-polybutadiene rubber | |
| CN109384965B (en) | Rubber composition for tire side wall of tire, vulcanized rubber, and preparation method and application thereof | |
| CN112300440B (en) | Antioxidant composition, antioxidant masterbatch and rubber composition | |
| CN109400979B (en) | Rubber vibration damping material with long fatigue life and preparation method thereof | |
| CN107641228B (en) | Use of organosilanes and rubber compositions and vulcanizates and process for their preparation | |
| CN109929160B (en) | Application of organosilane coupling agent, rubber composition, vulcanized rubber and preparation method and application thereof | |
| CN113462022A (en) | Rubber antioxidant composition and preparation method and application thereof | |
| CN109929149B (en) | Rubber composition for tire side wall of tire, vulcanized rubber, and preparation method and application thereof | |
| CN109929159B (en) | Rubber composition and vulcanized rubber for tire tread as well as preparation method and application of rubber composition and vulcanized rubber | |
| CN110157055B (en) | Sidewall rubber of aircraft tire | |
| CN112239568A (en) | Anti-aging agent composition and application thereof, rubber composition, vulcanized rubber and preparation method thereof | |
| CN111117017A (en) | Rubber-plastic product without short-chain chlorinated paraffin and preparation method thereof | |
| CN109384966B (en) | Rubber composition for tire side wall of tire, vulcanized rubber, and preparation method and application thereof | |
| CN107540963B (en) | Tire inner liner composite material and preparation method thereof | |
| CN109384964B (en) | Rubber composition for tire side wall of tire, vulcanized rubber, and preparation method and application thereof | |
| CN106700164B (en) | A kind of anti-slippery, low-rolling-resistance rubber composition and its tire tread | |
| CN101314651B (en) | Ozone resistant rubber composition | |
| CN112980066A (en) | Low-modulus high-elasticity combined improved chloroprene rubber and preparation method and application thereof | |
| CN109369981B (en) | Rubber composition | |
| CN107573702B (en) | Carbon black disperser and its preparation method and application and rubber composition and vulcanized rubber and preparation method thereof | |
| CN113480859B (en) | Rubber protective wax, and preparation method and application thereof | |
| JP2005232355A (en) | Rubber composition | |
| JPH06220255A (en) | Rubber composition | |
| CN115819858B (en) | Rubber composition based on hydrogenated nitrile rubber and butyl rubber, application thereof, vulcanized rubber, and preparation method and application thereof | |
| CN117070006B (en) | Low-temperature-resistant crystallization-resistant butadiene rubber composition, preparation method thereof and rubber sealing product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210119 |
|
| RJ01 | Rejection of invention patent application after publication |