CN103254464A - Rubber anti-aging agent, preparation method thereof, and rubber - Google Patents
Rubber anti-aging agent, preparation method thereof, and rubber Download PDFInfo
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- CN103254464A CN103254464A CN2012100403380A CN201210040338A CN103254464A CN 103254464 A CN103254464 A CN 103254464A CN 2012100403380 A CN2012100403380 A CN 2012100403380A CN 201210040338 A CN201210040338 A CN 201210040338A CN 103254464 A CN103254464 A CN 103254464A
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Abstract
The invention provides a rubber anti-aging agent, a preparation method thereof, and rubber. The rubber anti-aging agent comprises tris(2,4-di-tert-butylphenyl)phosphite, dilauryl dithiodipropionate, and 4,4'-thiobis-(3-methyl-6-tert-butyl phenol) and/or 2,2'-methylenebis-(4-methyl-6-tert-butyl-phenol). The rubber anti-aging agent preparation method comprises the step that the tris(2,4-di-tert-butylphenyl)phosphite, dilauryl dithiodipropionate, and 4,4'-thiobis-(3-methyl-6-tert-butyl phenol) and/or 2,2'-methylenebis-(4-methyl-6-tert-butyl-phenol) are well mixed. With the rubber anti-aging agent provided by the invention, prepared rubber has excellent aging resistance and high strength.
Description
Technical field
The present invention relates to a kind of rubber antioxidant and preparation method thereof and a kind of rubber.
Background technology
Rubber antioxidant not only can thermo oxidative aging, anti-ozone ageing, and to cupric ion, light with the aging significant effect that also has such as subdue.At present, the anti-aging agent that is used for rubber item is broadly divided into two kinds of amine and Hinered phenols.The protection effect of amines antioxidants is the most outstanding, also be find the earliest, kind at most, the class anti-aging agent that is most widely used.But amines antioxidants can change the color of rubber or surrounding environment is polluted.At present, amines antioxidants is only for being used for toxicity and the less demanding tire industry of color stain, and can not be used for aspects such as druggist rubber sundries, plastics and fiber.Hinered phenols anti-aging agent contaminative is little, but its anti-old effect is not as amines antioxidants.
CN1189513A discloses a kind of rubber antioxidant, and described rubber antioxidant is that one or more and the six phosphate ester of cyclohexanhexanol in styrenated phenol, N-sec.-propyl-N '-diphenyl-para-phenylene diamine, the dioctyl phthalate (DOP) is compound formulated.This rubber antioxidant has better chemical stability and aging barrier propterty, but has certain toxicity, belongs to staining antioxidant.
CN1201804A discloses a kind of composite rubber anti-ageing agent, and described anti-aging agent is made up of alkenyl arene, acetone and pentanoic.This rubber states that anti-aging agent is cheap, protection effect good, but also has certain toxicity, can cause to a certain degree pollution to environment.
Summary of the invention
The purpose of this invention is to provide a kind of rubber antioxidant with excellent anti-old effect and preparation method thereof, and the rubber that contains described rubber antioxidant.
The invention provides a kind of rubber antioxidant, wherein, described rubber antioxidant contains three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, dithio dipropyl acid two lauryls and 4,4 '-thiobis-(3-methyl 6-t-butyl phenol) and/or 2,2 '-methylene-bis-(4-methyl-6-tert butyl phenol).
The present inventor is unexpected to be found, be used in combination described three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, dithio dipropyl acid two lauryls, 4,4 '-thiobis-(3-methyl 6-t-butyl phenol) and/or 2,2 '-methylene-bis-(4-methyl-6-tert butyl phenol), in the tensile strength that guarantees rubber, can significantly improve the ageing-resistant performance of described rubber.A preferred embodiment of the invention, when described rubber antioxidant also contained Octabenzone and/or 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole, the ageing resistance by ultraviolet light performance of described rubber antioxidant was better, over-all properties is more excellent.
The present invention also provides a kind of preparation method of rubber antioxidant, this method comprises three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, dithio dipropyl acid two lauryls and 4,4 '-thiobis-(3-methyl 6-t-butyl phenol) and/or 2,2 '-methylene-bis-(4-methyl-6-tert butyl phenol) mixes.
In addition, the present invention also provides a kind of rubber that contains above-mentioned rubber antioxidant.
Other features and advantages of the present invention will partly be described in detail in embodiment subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that embodiment described herein only is used for description and interpretation the present invention, is not limited to the present invention.
According to the present invention, described rubber antioxidant contains three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, dithio dipropyl acid two lauryls and 4,4 '-thiobis-(3-methyl 6-t-butyl phenol) and/or 2,2 '-methylene-bis-(4-methyl-6-tert butyl phenol).
Described three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, dithio dipropyl acid two lauryls and 4,4 '-thiobis-(3-methyl 6-t-butyl phenol) and/or 2,2 '-methylene-bis-(4-methyl-6-tert butyl phenol) can play good synergy, and the composite rubber antioxidant that obtains has ageing-resistant performance preferably.Wherein, described three (2, the 4-di-tert-butyl-phenyl) structural formula of phosphorous acid ester is as shown in the formula shown in (1), the structural formula of described dithio dipropyl acid two lauryls is as shown in the formula shown in (2), described 2,2 '-structural formula of methylene-bis-(4-methyl-6-tert butyl phenol) is as shown in the formula shown in (3), described 4,4 '-structural formula of thiobis-(3-methyl 6-t-butyl phenol) is as shown in the formula shown in (4):
According to the present invention, various components contents can be selected and change in the larger context in the described rubber antioxidant, for example, with three (2 of 100 weight parts, the 4-di-tert-butyl-phenyl) phosphorous acid ester is benchmark, and the content of described dithio dipropyl acid two lauryls can be 25-150 weight part, described 4,4 '-thiobis-(3-methyl 6-t-butyl phenol) and 2,2 '-total content of methylene-bis-(4-methyl-6-tert butyl phenol) can be the 200-1300 weight part.Need to prove, in described rubber antioxidant, contain 4 simultaneously, 4 '-thiobis-(3-methyl 6-t-butyl phenol) and 2,2 '-during methylene-bis-(4-methyl-6-tert butyl phenol), described 4,4 '-thiobis-(3-methyl 6-t-butyl phenol) and 2,2 '-total content of methylene-bis-(4-methyl-6-tert butyl phenol) refers to 4,4 '-thiobis-(3-methyl 6-t-butyl phenol) and 2,2 '-the content sum of methylene-bis-(4-methyl-6-tert butyl phenol); In described rubber antioxidant, only contain 4,4 '-thiobis-(3-methyl 6-t-butyl phenol) or 2,2 '-during methylene-bis-(4-methyl-6-tert butyl phenol), described 4,4 '-thiobis-(3-methyl 6-t-butyl phenol) and 2,2 '-total content of methylene-bis-(4-methyl-6-tert butyl phenol) refers to 4,4 '-thiobis-(3-methyl 6-t-butyl phenol) or 2,2 '-content of methylene-bis-(4-methyl-6-tert butyl phenol).
According to the present invention, contain three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, dithio dipropyl acid two lauryls and 4,4 '-thiobis-(3-methyl 6-t-butyl phenol) and/or 2,2 '-rubber antioxidant of methylene-bis-(4-methyl-6-tert butyl phenol) has the rich fatigue aging performance of excellent thermo oxidative aging performance, anti-ozone ageing performance and anti-song, is specially adapted to the additive as the rubber that uses in the environment of weak (for example indoor) at ultraviolet ray intensity.More preferably, described rubber antioxidant contains three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, dithio dipropyl acid two lauryls and 4,4 '-thiobis-(3-methyl 6-t-butyl phenol), perhaps described rubber antioxidant contains three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, dithio dipropyl acid two lauryls, 4,4 '-thiobis-(3-methyl 6-t-butyl phenol) and 2,2 '-methylene-bis-(4-methyl-6-tert butyl phenol).When described 2,2 '-methylene-bis-(4-methyl-6-tert butyl phenol) and 4,4 '-weight ratio of thiobis-(3-methyl 6-t-butyl phenol) is preferably 0.6-8: 1 o'clock, the ageing-resistant performance of the rubber antioxidant that obtains was very excellent.
Under the preferable case, in order further to strengthen the ageing resistance by ultraviolet light performance of described rubber antioxidant, obtain the more excellent rubber antioxidant of over-all properties, under the preferable case, described rubber antioxidant also contains Octabenzone and/or 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole.Wherein, the structural formula of described Octabenzone is as shown in the formula shown in (5), and the structural formula of described 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole is as shown in the formula shown in (6):
The present invention is to the not restriction especially of content of described Octabenzone and 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole, as long as can strengthen the ageing resistance by ultraviolet light performance of described rubber antioxidant, for example, with three (2 of 100 weight parts, the 4-di-tert-butyl-phenyl) phosphorous acid ester is benchmark, and the total content of described Octabenzone and 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole is the 30-200 weight part.Need to prove, when containing Octabenzone and 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole in the described rubber antioxidant simultaneously, the total content of described Octabenzone and 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole refers to the content sum of Octabenzone and 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole; When only containing Octabenzone or 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole in the described rubber antioxidant, the total content of described Octabenzone and 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole refers to the content of Octabenzone or 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole.Under the preferable case, described rubber antioxidant contains Octabenzone and 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole simultaneously.
According to the present invention, although when described rubber antioxidant also contains Octabenzone and 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole simultaneously, the rubber antioxidant that obtains just has good thermo oxidative aging performance, anti-ozone ageing performance, the rich fatigue aging performance of anti-song and ageing resistance by ultraviolet light performance, but in order to obtain the more excellent rubber antioxidant of over-all properties, under the preferable case, the weight ratio of described Octabenzone and 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole is 0.3-3.33: 1.
According to the present invention, the preparation method of described rubber antioxidant comprises three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, dithio dipropyl acid two lauryls and 4,4 '-thiobis-(3-methyl 6-t-butyl phenol) and 2,2 '-methylene-bis-(4-methyl-6-tert butyl phenol) mixes.
Wherein, the consumption of each material preferably makes with three (2 of 100 weight parts, the 4-di-tert-butyl-phenyl) phosphorous acid ester is benchmark, the content of described dithio dipropyl acid two lauryls is the 25-150 weight part, described 4,4 '-thiobis-(3-methyl 6-t-butyl phenol) and 2,2 '-total content of methylene-bis-(4-methyl-6-tert butyl phenol) is the 200-1300 weight part; More preferably, described rubber antioxidant contains three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, dithio dipropyl acid two lauryls and 4,4 '-thiobis-(3-methyl 6-t-butyl phenol), perhaps described rubber antioxidant contains 4 simultaneously, 4 '-thiobis-(3-methyl 6-t-butyl phenol) and 2,2 '-methylene-bis-(4-methyl-6-tert butyl phenol), and described 2,2 '-methylene-bis-(4-methyl-6-tert butyl phenol) and 4,4 '-weight ratio of thiobis-(3-methyl 6-t-butyl phenol) is 0.6-8: 1.
There is no particular limitation to the temperature and time of described mixing in the present invention, as long as the various components of forming rubber antioxidant are mixed, for example, the temperature of described mixing can be 30-70 ℃, and the time of mixing can be 20-40 minute.
According to the present invention, preferably, the preparation method of described rubber antioxidant also comprises three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, dithio dipropyl acid two lauryls, 4,4 '-thiobis-(3-methyl 6-t-butyl phenol) and/or 2,2 '-methylene-bis-(4-methyl-6-tert butyl phenol) and Octabenzone and/or 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole mix.
Wherein, under the preferable case, feasible three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester with 100 weight parts of the consumption of each material is benchmark, and the total content of described Octabenzone and 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole is the 30-200 weight part.More preferably, described Octabenzone and 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole adds simultaneously, and the weight ratio of described Octabenzone and 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole is 0.3-3.33: 1.
In addition, the present invention also provides a kind of rubber that contains above-mentioned rubber antioxidant.The preparation method of described rubber is conventionally known to one of skill in the art, for example, can be for natural rubber and/or synthetic rubber, rubber antioxidant of the present invention, carbon black and promoting agent join in the Banbury mixer and mix, the time of mixing can be 5-20 minute, temperature can be 50-70 ℃, vulcanizing agent is joined in the mixed product then, in mill, mix, the time of mixing can be 5-20 minute, the temperature of mixing can be 35-55 ℃, subsequently the product that obtains is carried out compression molding, and the temperature of compression molding can be 150-180 ℃, the time of compression molding can be 10-30 minute, thereby obtains rubber.
According to the present invention, described synthetic rubber for example can be divinyl rubber and/or styrene-butadiene rubber(SBR).As a rule, with respect to 100 parts by weight of natural rubber and synthetic rubber, the content of described rubber antioxidant can be the 1-5 weight part, is preferably the 1-2.5 weight part.Described carbon black can for example can be carbon black N550, N774 or N330 for the existing various carbon blacks that can be used as rubber accelerator; With respect to 100 parts by weight of natural rubber and synthetic rubber, the content of described carbon black for example can be the 10-70 weight part, elects the 30-50 weight part as.The kind of described vulcanizing agent and consumption are conventionally known to one of skill in the art, and for example, described vulcanizing agent can be selected from one or more in insoluble sulfur, dithio morpholine and four sulfurations, two morpholines; With respect to 100 parts by weight of natural rubber and synthetic rubber, the content of described vulcanizing agent can be the 1-5 weight part, is preferably the 1-2.5 weight part.The kind of described promoting agent and consumption also are conventionally known to one of skill in the art, and for example, described promoting agent can be zinc oxide and/or stearic acid; With respect to 100 parts by weight of natural rubber and synthetic rubber, the content of described promoting agent can be the 2-10 weight part, is preferably the 4-8 weight part.
The present invention is further illustrated below by embodiment.
Preparation embodiment 1
This preparation embodiment is used for explanation rubber antioxidant of the present invention and preparation thereof.
Under room temperature (25 ℃), with three (2 of 12g, the 4-di-tert-butyl-phenyl) 2 of the dithio dipropyl of phosphorous acid ester, 10g acid two lauryls, 45g, 2 '-methylene-bis-(4-methyl-6-tert butyl phenol), 25g 4,4 '-thiobis-(3-methyl 6-t-butyl phenol), the Octabenzone of 5g and 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole of 3g mix, and obtains rubber antioxidant X1.
Preparation embodiment 2
This preparation embodiment is used for explanation rubber antioxidant of the present invention and preparation thereof.
Under room temperature (25 ℃), with three (2 of 10g, the 4-di-tert-butyl-phenyl) 2 of the dithio dipropyl of phosphorous acid ester, 15g acid two lauryls, 15g, 2 '-methylene-bis-(4-methyl-6-tert butyl phenol), 115g 4,4 '-2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole of thiobis-(3-methyl 6-t-butyl phenol) and 3g mixes, and obtains rubber antioxidant X2.
Preparation embodiment 3
This preparation embodiment is used for explanation rubber antioxidant of the present invention and preparation thereof.
Under room temperature (25 ℃), with three (2 of 15g, the 4-di-tert-butyl-phenyl) 4,4 of the dithio dipropyl of phosphorous acid ester, 4g acid two lauryls, 30g '-thiobis-(3-methyl 6-t-butyl phenol) and the Octabenzone of 30g mix, and obtains rubber antioxidant X3.
Preparation embodiment 4
This preparation embodiment is used for explanation rubber antioxidant of the present invention and preparation thereof.
Under room temperature (25 ℃), with three (2 of 20g, the 4-di-tert-butyl-phenyl) 2 of the dithio dipropyl of phosphorous acid ester, 15g acid two lauryls, 30g, 2 '-methylene-bis-(4-methyl-6-tert butyl phenol) and 40g 4,4 '-thiobis-(3-methyl 6-t-butyl phenol) mix, and obtains rubber antioxidant X4.
Preparation embodiment 5
This preparation embodiment is used for explanation rubber antioxidant of the present invention and preparation thereof.
Under room temperature (25 ℃), 2,2 of dithio dipropyl acid two lauryls of three (2,4-di-tert-butyl-phenyl) phosphorous acid ester of 20g, 15g and 80g '-methylene-bis-(4-methyl-6-tert butyl phenol) is mixed, obtain rubber antioxidant X5.
Preparation embodiment 6
This preparation embodiment is used for explanation rubber antioxidant of the present invention and preparation thereof.
Under room temperature (25 ℃), 4,4 of dithio dipropyl acid two lauryls of three (2,4-di-tert-butyl-phenyl) phosphorous acid ester of 20g, 15g and 50g '-thiobis-(3-methyl 6-t-butyl phenol) mixed, obtain rubber antioxidant X6.
Preparation embodiment 7
This preparation embodiment is used for explanation rubber antioxidant of the present invention and preparation thereof.
Method according to embodiment 4 prepares rubber antioxidant, and different is described 2,2 '-add-on of methylene-bis-(4-methyl-6-tert butyl phenol) is 22g, described 4,4 '-add-on of thiobis-(3-methyl 6-t-butyl phenol) is 50g, obtains rubber antioxidant X7.
Embodiment 1
Embodiment 1 is used for the preparation of explanation rubber provided by the invention.
With 80 parts by weight of natural rubber (No. 3 smoked sheets of Thailand), the styrene-butadiene rubber(SBR) of 20 weight parts (Dushanzi petro-chemical corporation of CNPC, BR9000), the carbon black N550 of 16 weight parts (Shanghai Cabot), the zinc oxide of 5 weight parts (Liuzhou zinc product company limited) and the rubber antioxidant X1 of 2 weight parts join in the Banbury mixer, under 55 ℃ of conditions, mixed 10 minutes, be transferred in the mill then and add 1.5 weight part insoluble sulfurs (Science and Technology Ltd. is contained in the Jinchang, Guangzhou, S-80), under 40 ℃ of conditions, mixed 10 minutes, then the mixture that obtains is taken out, under 165 ℃ of conditions, in 50T vulcanizing press (Chengdu Hangfa Hydraulic Construction Co., Ltd.), carry out compression molding, curing time is 15 minutes, obtains thickness and be 2 millimeters rubber S1.
Embodiment 2-7
Embodiment 2-7 is used for the preparation of explanation rubber provided by the invention.
Method according to embodiment 1 prepares rubber, and different is that described rubber antioxidant X1 is replaced by rubber antioxidant X2-X7 respectively, obtains the rubber S2-S7 that thickness is 2 millimeters.
Comparative Examples 1-4
This Comparative Examples is used for the preparation of explanation reference rubber.
Method according to embodiment 1 prepares rubber, and different is, described rubber antioxidant X1 respectively by the commercially available trade mark be respectively 264,4010NA, 4020 and RD replace, obtain the rubber DS1-DS4 that thickness is 2 millimeters.
Test case 1-7
The rubber S1-S7 that embodiment 1-7 is obtained carries out the test of tensile property, ageing-resistant performance and anti-deformation nature respectively in accordance with the following methods.
(1) tensile property test:
According to the 1 type dumbbell shaped cut-off knife of stipulating among the GB/T528-92 rubber S1-S7 being cut into the dumbbell shaped standard film, is 25 ℃ at probe temperature, and pulling speed is under the condition of 500 mm/min, test tensile strength and tensile yield, and the result is as shown in table 1.
(2) ageing-resistant performance test: according to the method for stipulating among the GB3512-83, with rubber S1-S7 100 ℃ of following thermo-oxidative ageings 72 hours, according to the 1 type dumbbell shaped cut-off knife of stipulating among the GB/T528-92 rubber S1-S7 is cut into the dumbbell shaped standard film then, it is 25 ℃ at probe temperature, pulling speed is under the condition of 500 mm/min, adopt tester for elongation (available from good laboratory apparatus company limited in the Nantong, model is 401A) respectively aging forward and backward tensile strength and tensile yield to be tested.
Aging coefficient=(tensile strength * tensile yield after aging) ÷ (tensile strength * tensile yield before aging), the aging coefficient of gained is as shown in table 1.
(3) anti-deformation nature test:
According to the 1 type dumbbell shaped cut-off knife of stipulating among the GB/T528-92 rubber S1-S7 being cut into the dumbbell shaped standard film, is 25 ℃ at probe temperature, and pulling speed is under the condition of 500 mm/min sample to be broken.Sample after the tension fracture is placed 3min, again two portions of fracture is coincide together, measure the distance of coincideing between back two parallel lines, be calculated as follows the setafter break value:
S
b=100 (L
t-L
0)/L
0, wherein, S
bBe setafter break, %; L
tBe the distance between identical back two parallel lines of sample, mm; L
0Be initial trial length, mm.The gained result is as shown in table 1.
Contrast test example 1-4
Method according to test case 1-7 is tested tensile property, ageing-resistant performance and the anti-deformation nature of rubber, and different is that described rubber is the rubber that is prepared by Comparative Examples 1-4.The gained result is as shown in table 1.
Table 1
As can be seen from the above results, the rubber that adopts rubber antioxidant provided by the invention to prepare has comparatively excellent ageing-resistant performance, also has good intensity simultaneously.
Claims (10)
1. rubber antioxidant, it is characterized in that, described rubber antioxidant contains three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, dithio dipropyl acid two lauryls and 4,4 '-thiobis-(3-methyl 6-t-butyl phenol) and/or 2,2 '-methylene-bis-(4-methyl-6-tert butyl phenol).
2. rubber antioxidant according to claim 1, wherein, with three (2 of 100 weight parts, the 4-di-tert-butyl-phenyl) phosphorous acid ester is benchmark, the content of described dithio dipropyl acid two lauryls is the 25-150 weight part, described 4,4 '-thiobis-(3-methyl 6-t-butyl phenol) and 2,2 '-total content of methylene-bis-(4-methyl-6-tert butyl phenol) is the 200-1300 weight part.
3. rubber antioxidant according to claim 2, wherein, described 2,2 '-methylene-bis-(4-methyl-6-tert butyl phenol) and 4,4 '-weight ratio of thiobis-(3-methyl 6-t-butyl phenol) is 0.6-8: 1.
4. according to claim 1,2 or 3 described rubber antioxidants, wherein, described rubber antioxidant also contains Octabenzone and/or 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole.
5. rubber antioxidant according to claim 4, wherein, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester with 100 weight parts is benchmark, and the total content of described Octabenzone and 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole is the 30-200 weight part.
6. the preparation method of a rubber antioxidant, this method comprises three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, dithio dipropyl acid two lauryls and 4,4 '-thiobis-(3-methyl 6-t-butyl phenol) and/or 2,2 '-methylene-bis-(4-methyl-6-tert butyl phenol) mixes.
7. method according to claim 6, wherein, the consumption of each material makes with three (2 of 100 weight parts, the 4-di-tert-butyl-phenyl) phosphorous acid ester is benchmark, the content of described dithio dipropyl acid two lauryls is the 25-150 weight part, described 4,4 '-thiobis-(3-methyl 6-t-butyl phenol) and 2,2 '-total content of methylene-bis-(4-methyl-6-tert butyl phenol) is the 200-1300 weight part; Preferably, 2,2 '-methylene-bis-(4-methyl-6-tert butyl phenol) and 4,4 '-weight ratio of thiobis-(3-methyl 6-t-butyl phenol) is 0.6-8: 1.
8. method according to claim 6, wherein, this method also comprises three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester, dithio dipropyl acid two lauryls, 4,4 '-thiobis-(3-methyl 6-t-butyl phenol) and/or 2,2 '-methylene-bis-(4-methyl-6-tert butyl phenol) and Octabenzone and/or 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole mix.
9. method according to claim 8, wherein, the consumption of each material makes with three (2 of 100 weight parts, the 4-di-tert-butyl-phenyl) phosphorous acid ester is benchmark, and the total content of described Octabenzone and 2-(2-hydroxyl-uncle's 5-octyl phenyl) benzotriazole is the 30-200 weight part.
10. rubber, wherein, described rubber contains any described rubber antioxidant among the claim 1-5.
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| CN103980536A (en) * | 2014-06-05 | 2014-08-13 | 常州市五洲化工有限公司 | Novel rubber aging inhibitor and preparation method thereof |
| CN105440551A (en) * | 2014-08-27 | 2016-03-30 | 中国石油化工股份有限公司 | A styrene thermoplastic elastomer, a preparing method thereof and an anti-aging agent |
| CN105462087A (en) * | 2016-01-25 | 2016-04-06 | 永嘉县伟诚橡胶工贸有限公司 | Rubber anti-aging agent and preparation method thereof |
| CN105754174A (en) * | 2016-03-16 | 2016-07-13 | 安徽海德石油化工有限公司 | Rubber antiager prepared by utilizing petroleum coke |
| 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 |
| CN107955207A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | Rubber antioxidant composition and its preparation method and application |
| CN108948472A (en) * | 2017-05-26 | 2018-12-07 | 宜兴市聚金信化工有限公司 | A kind of novel high-efficiency environment friendly rubber antioxidant |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181072A (en) * | 2011-02-24 | 2011-09-14 | 常州大学 | Preparation method of emulsion antioxidant |
-
2012
- 2012-02-20 CN CN201210040338.0A patent/CN103254464B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181072A (en) * | 2011-02-24 | 2011-09-14 | 常州大学 | Preparation method of emulsion antioxidant |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980536A (en) * | 2014-06-05 | 2014-08-13 | 常州市五洲化工有限公司 | Novel rubber aging inhibitor and preparation method thereof |
| CN103980536B (en) * | 2014-06-05 | 2017-03-29 | 盐城科迈特新材料有限公司 | A kind of rubber antioxidant and preparation method thereof |
| CN105440551A (en) * | 2014-08-27 | 2016-03-30 | 中国石油化工股份有限公司 | A styrene thermoplastic elastomer, a preparing method thereof and an anti-aging agent |
| CN105440551B (en) * | 2014-08-27 | 2018-09-21 | 中国石油化工股份有限公司 | A kind of styrene series thermoplastic elastomer and preparation method thereof and anti-aging agent |
| 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 |
| CN105462087A (en) * | 2016-01-25 | 2016-04-06 | 永嘉县伟诚橡胶工贸有限公司 | Rubber anti-aging agent and preparation method thereof |
| CN105462087B (en) * | 2016-01-25 | 2017-08-25 | 永嘉县伟诚橡胶工贸有限公司 | A kind of rubber antioxidant and preparation method thereof |
| CN105754174A (en) * | 2016-03-16 | 2016-07-13 | 安徽海德石油化工有限公司 | Rubber antiager prepared by utilizing petroleum coke |
| CN107955207A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | Rubber antioxidant composition and its preparation method and application |
| CN107955207B (en) * | 2016-10-14 | 2019-08-20 | 中国石油化工股份有限公司 | Rubber antioxidant composition and its preparation method and application |
| CN108948472A (en) * | 2017-05-26 | 2018-12-07 | 宜兴市聚金信化工有限公司 | A kind of novel high-efficiency environment friendly rubber antioxidant |
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