CN103709439B - Antioxidant composition and preparation method thereof and styrene series thermoplastic elastomer and preparation method thereof - Google Patents
Antioxidant composition and preparation method thereof and styrene series thermoplastic elastomer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of antioxidant composition, wherein, this antioxidant composition contains β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, three (2,4-di-tert-butyl-phenyl) phosphorous acid esters and dithiodipropionic acid two lauryl and preparation method.The present invention also discloses a kind of styrene series thermoplastic elastomer, wherein, this styrene series thermoplastic elastomer contains styrene block copolymer and antioxidant composition, and described antioxidant composition is described antioxidant composition provided by the invention and preparation method thereof.This antioxidant composition is used in styrene series thermoplastic elastomer, can significantly improves the ageing-resistant of styrene series thermoplastic elastomer and anti-yellowing property; And the component of this antioxidant composition is all the material of low toxicity, therefore can not cause environmental pollution.
Description
Technical field
The present invention relates to a kind of antioxidant composition and preparation method thereof, and the styrene series thermoplastic elastomer comprising this antioxidant composition and preparation method thereof.
Background technology
Styrene series thermoplastic elastomer is a kind of thermoplastic elastomer that on our times, output is maximum, the most similar to rubber performance.At present, the polymeric matrix of styrene series thermoplastic elastomer is generally styrene block copolymer (StyreneicBlockCopolymers is called for short SBCs), and it mainly contains 4 types, that is: styrene-butadiene-styrene block copolymer (SBS); Styrene isoprene styrene block copolymer (SIS) (SIS); Styrene-ethylene-butylene-styrene block copolymer (SEBS); Styrene ethylene-propylene-styrene type segmented copolymer (SEPS).Wherein, SEBS and SEPS is the hydrogenated copolymer of SBS and SIS respectively.
SBS and SIS is with vinylbenzene, divinyl or isoprene for raw material, adopt organolithium be initiator through anionic solution polymerization method, polymers soln through cohesion desolvation after obtain solid product.Regular industrial is produced and is adopted batchwise polymerization, wet coacervation process.
Owing to there is undersaturated C=C double bond in the molecular chain of styrene block copolymer, therefore in processing and application process, the factor impacts such as the easy light of styrene block copolymer, heat, oxygen occur aging, thus affect the use properties of styrene block copolymer.Usually in styrene block copolymer, protective agent is added to improve the ageing-resistant performance of multipolymer.
As everyone knows, there is with the sole that SBS makes the features such as light weight, good springiness, low-temperature performance are excellent, good looking appearance, and complete processing is simple, easy handling.But the problem of domestic SBS product ubiquity anti-yellowing property difference, therefore can not meet the requirement of producing white senior Sneakers, even just there is its colour changed into yellow phenomenon in some product, have a strong impact on the quality of product in transportation.Therefore, in the urgent need to when guaranteeing antioxygen property, improve the anti-yellowing property of SBS, to adapt to the demand in market.
At present both at home and abroad in SBS product, usually adopt antioxidant property and the xanthochromia performance of adding and improving product based on the additive of antioxidant 264 or TNPP.But the environmental protection policy put into effect due to European Union in recent years and anti-aging agent itself are for the impact of environment, and the use of antioxidant 264 and TNPP is restricted.Such as antioxidant 264, is also called antioxidant 264 or T501, and chemical composition is 2,6 ditertiary butyl p cresol.Antioxidant 264 is less due to its relative molecular mass, and the volatilization that easily distils in using may work the mischief to the HUMAN HEALTH of operator and environment.Although antioxidant 264 is not also forbidden in European Union at present, the feature of antioxidant 264 self determines it and will be substituted gradually.Anti-aging agent TNPP is three (nonyl phenyl) phosphorous acid ester.Intermediate product nonyl phenol residual in TNPP has stronger genotoxicity, and this material has been listed in the restricted substances of EU REACH Legislation, and the use of TNPP or the material containing this material is by restricted.Therefore for styrene series thermoplastic elastomer finds suitable environment-friendly type anti-aging agent, domestic and international all big enterprises problem demanding prompt solution has been become.
" petrochemical technology " (2002,9(3): 129-132) disclose anti-aging agent 1076(β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid octadecanol ester) application in SBS.But the active end group that the ester group of anti-aging agent 1076 is easy and SBS basis glue is residual reacts, and makes basic glue variable color.Therefore be used alone anti-aging agent 1076 and can not meet the performance improving SBS color inhibition.
CN1189513A discloses a kind of rubber antioxidant, its form one or more raw materials of comprising in styrenated phenol, N-sec.-propyl-N '-diphenyl-para-phenylene diamine, o-phthalic acid dibutyl ester and six phosphate ester of cyclohexanhexanol compound formulated.This rubber antioxidant has good chemical stability, does not decompose under high temperature, water-fast extracting, to ozone, heat, oxygen, deflect fatigue, ultraviolet has good protection; Consumption is little, favorable dispersity.But six phosphate ester of cyclohexanhexanol wherein has hormesis to eyes, skin, respiratory tract; O-phthalic acid dibutyl ester is also classified as dangerous product, particularly be classified as the material by REACH regulation limitations by European Union with the dibutyl phthalate of its structural similitude, therefore the rubber antioxidant of this disclosure of the invention has certain toxicity, belongs to staining antioxidant.
CN1201804A discloses a kind of composite rubber anti-ageing agent, it is characterized in that alkenyl arene, acetone, pentanoic being stirred at a certain temperature and being adsorbed on rubber filler.This rubber state anti-aging agent to oxidation, tired, deflect and all have excellent protective effect, heat-proof aging, weathering age excellent performance.But pentanoic has certain toxicity in this anti-aging agent, pollution to a certain degree can be caused to environment.
CN1919904A discloses the preparation method of the oxidation inhibitor of butadiene polymer, it is characterized in that selecting a kind of thioether oxidation inhibitor, or a kind of bisphenols or Hinered phenols antioxidant and a kind of thioether oxidation inhibitor are mixed in proportion, add in mixing tank, under normal temperature, fully mix, obtain oxidation inhibitor SFH-900; The wherein massfraction 10-90% of thioether kind antioxidant; The massfraction 10-90% of bisphenols or Hinered phenols antioxidant.
Therefore, being badly in need of developing can not to environment, and can improve the anti-aging agent of ageing-resistant, the anti-yellowing property of styrene series thermoplastic elastomer.
Summary of the invention
The object of the invention is to environment or the problem of ageing-resistant, anti-yellowing property obviously can not improving styrene series thermoplastic elastomer, antioxidant composition of a kind of environmental protection and preparation method thereof and the polystyrene thermoplastic elastic comprising this antioxidant composition and preparation method thereof to be provided to solve the existing anti-aging agent for polystyrene thermoplastic elastic.
The restriction of more and more stricter environmental requirement is subject to for anti-aging agent, and to the demand of styrene series thermoplastic elastomer with preferably ageing-resistant and anti-yellowing property in market, the present inventor has carried out a large amount of experiments, with attempt to develop a kind of environmental protection and significantly can improve the anti-aging agent of the ageing-resistant of styrene series thermoplastic elastomer and anti-yellowing property.In experimentation, contriver is surprised to find that some hypotoxicities, free of contamination material (as β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester and dithiodipropionic acid two lauryl) carry out composite, unexpected synergy can be obtained, make the complex antiager so obtained can significantly improve the ageing-resistant of styrene series thermoplastic elastomer and anti-yellowing property after for styrene series thermoplastic elastomer, complete the present invention thus.
To achieve these goals, the invention provides a kind of antioxidant composition, wherein, this antioxidant composition contains β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, three (2,4-di-tert-butyl-phenyl) phosphorous acid esters and dithiodipropionic acid two lauryl.
Present invention also offers a kind of preparation method of antioxidant composition organic solution, the method comprises β-(3,5-di-tert-butyl-hydroxy phenyl) mixing of the positive octadecanol ester of propionic acid, three (2,4-di-tert-butyl-phenyl) phosphorous acid esters and dithiodipropionic acid two lauryl.
Present invention also offers a kind of styrene series thermoplastic elastomer, wherein, this styrene series thermoplastic elastomer contains styrene block copolymer and antioxidant composition, and described antioxidant composition is described antioxidant composition provided by the invention.
The present invention also provides a kind of preparation method of styrene series thermoplastic elastomer, the method comprises and being mixed with antioxidant composition by styrene block copolymer, then carry out condensing and drying, wherein, described antioxidant composition is described antioxidant composition provided by the invention.
In described antioxidant composition provided by the invention, β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester and dithiodipropionic acid two lauryl can play synergy, this antioxidant composition is used in styrene series thermoplastic elastomer, can significantly improves the ageing-resistant of styrene series thermoplastic elastomer and anti-yellowing property; And the β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid, three (2,4-di-tert-butyl-phenyl) phosphorous acid esters and dithiodipropionic acid two lauryl is all the material of low toxicity, therefore can not cause environmental pollution.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of antioxidant composition, wherein, this antioxidant composition contains the β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid, three (2,4-di-tert-butyl-phenyl) phosphorous acid esters and dithiodipropionic acid two lauryl.
According to the present invention, β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester and dithiodipropionic acid two lauryl be all the material of the pollution-free environmental protection of hypotoxicity, be often used as antioxidant, wherein dithiodipropionic acid two lauryl even can be used for food.The material of above-mentioned composition anti-aging agent of the present invention can meet the free of contamination environmental requirement of low toxicity well.The more important thing is can there be good synergy between this several material, the composite antioxidant composition obtained can provide well ageing-resistant and color inhibition effect.Wherein, β-(3,5-di-tert-butyl-hydroxy phenyl) structural formula of the positive octadecanol ester of propionic acid is as shown in the formula shown in (1), three (2,4-di-tert-butyl-phenyl) structural formula of phosphorous acid ester is as shown in the formula shown in (2), and the structural formula of dithiodipropionic acid two lauryl is as shown in the formula shown in (3):
formula (1)
formula (2)
formula (3)
According to the present invention, in described antioxidant composition, the content of each composition can carry out selecting and changing in the larger context, under preferable case, with dithiodipropionic acid two lauryl of 100 weight parts for benchmark, β-(3,5-di-tert-butyl-hydroxy phenyl) content of the positive octadecanol ester of propionic acid is 80-150 weight part, is preferably 33.3-100 weight part; The content of three (2,4-di-tert-butyl-phenyl) phosphorous acid ester is 10-100 weight part, is preferably 16.7-75 weight part.
Present invention also offers a kind of preparation method of antioxidant composition, the method comprises β-(3,5-di-tert-butyl-hydroxy phenyl) mixing of the positive octadecanol ester of propionic acid, three (2,4-di-tert-butyl-phenyl) phosphorous acid esters and dithiodipropionic acid two lauryl.
Mix sufficiently uniformly to enable each material in the described antioxidant composition of composition, and be convenient to add use, by β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester and dithiodipropionic acid two lauryl mixing process preferably carry out in presence of organic solvent, with by each substance dissolves of described antioxidant composition in organic solvent, thus make antioxidant composition organic solution.In order to obtain antioxidant composition product, described method can also comprise carries out drying by the organic solution of described antioxidant composition.
Described organic solvent can be alkane or naphthenic hydrocarbon, is preferably hexane or hexanaphthene.
According to the present invention, there is no particular limitation for described organic solvent usage quantity, as long as can dissolve each component of the described antioxidant composition of composition.Under preferable case, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid positive octadecanol ester, three (2,4-di-tert-butyl-phenyl) phosphorous acid esters and total consumption of dithiodipropionic acid two lauryl and the consumption of described organic solvent weight ratio be 1:1-5; Be preferably 1:1-3.
According to the present invention, in described preparation method, with the consumption of dithiodipropionic acid two lauryl of 100 weight parts for benchmark, β-(3,5-di-tert-butyl-hydroxy phenyl) content of the positive octadecanol ester of propionic acid can be 80-150 weight part, is preferably 33.3-100 weight part; The content of three (2,4-di-tert-butyl-phenyl) phosphorous acid ester can be 10-100 weight part, is preferably 16.7-75 weight part.
To the temperature and time of described mixing, there is no particular limitation in the present invention, as long as the various components of composition antioxidant composition can be made to mix, such as, the temperature of described mixing can be 40-70 DEG C, and the time of mixing can be 5-10 minute.
Present invention also offers a kind of styrene series thermoplastic elastomer, wherein, this styrene series thermoplastic elastomer contains styrene block copolymer and antioxidant composition, and described antioxidant composition is described antioxidant composition provided by the invention.
In the present invention, styrene block copolymer refers to and vinylbenzene and divinyl or isoprene monomer raw material is carried out solution polymerization in organic solvent, the copolymerized polymer obtained, this copolymerized polymer can be such as at least one in styrene-butadiene-styrene block copolymer (SBS), styrene isoprene styrene block copolymer (SIS) (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS) and styrene ethylene-propylene-styrene type segmented copolymer (SEPS).The number-average molecular weight of described styrene block copolymer can be 100,000-30 ten thousand, is preferably 200,000-25 ten thousand.
According to the present invention, the amount that can add the described antioxidant composition in described styrene block copolymer can limit especially, can select in the larger context and change.Under preferable case, with styrene block copolymer described in 100 weight parts for benchmark, the content of described antioxidant composition is 0.5-1 weight part, is more preferably 0.6-0.8 weight part.
Present invention also offers a kind of preparation method of styrene series thermoplastic elastomer, the method comprises and being mixed with antioxidant composition by styrene block copolymer, then carry out condensing and drying, wherein, described antioxidant composition is described antioxidant composition provided by the invention.
According to the present invention, preparing in styrene series thermoplastic elastomer process, styrene block copolymer can adopt the method for this area routine to implement with mixing of antioxidant composition, such as, described antioxidant composition is joined obtain mixing in described styrene block copolymer through solution polymerization.Under preferable case, described antioxidant composition adds in described styrene block copolymer with the form being dissolved in the organic solution obtained in organic solvent.The process of described mixing can be carried out in mixing kettle.The time of mixing can be 5-10 minute, and the temperature of mixing can be 10-50 DEG C.
The object of described cohesion is to remove desolventizing.The object of described drying be in order to except anhydrating, solvent etc.Described cohesion and dry implementation process can comprise: the steam passing into 100 DEG C in the mixture obtained by above-mentioned mixing process, operation 30-60 minute, then the product obtained is operated 20-40 minute on plasticator at 100 DEG C and carry out drying, thus the obtained styrene series thermoplastic elastomer containing described styrene block copolymer and described antioxidant composition.
Preparing in styrene series thermoplastic elastomer process, the consumption of described antioxidant composition can carry out selecting and changing in the larger context, as long as described styrene series thermoplastic elastomer can be made to have the ageing-resistant of expectation and anti-yellowing property.Under preferable case, with the consumption of styrene block copolymer described in 100 weight parts for benchmark, the consumption of described antioxidant composition is 0.5-1 weight part; More preferably the content of described antioxidant composition is 0.6-0.8 weight part.When described antioxidant composition adds fashionable with the form of organic solution, the consumption of described antioxidant composition refers to the weight of the antioxidant composition comprised in described organic solution.
Below will be described the present invention by embodiment.
In the following Examples and Comparative Examples, β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid is purchased from Nan Yang, Jiangsu Province Chemical Co., Ltd.; Three (2,4-di-tert-butyl-phenyl) phosphorous acid ester is purchased from Beijing Jiyi Chemicals Co., Ltd.; Dithiodipropionic acid two lauryl is purchased from Yixing City angel synthetic chemistry company limited.
Embodiment 1
The present embodiment is for illustration of the preparation method of antioxidant composition of the present invention.
At 40 DEG C, by β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid positive octadecanol ester 20g, dithiodipropionic acid two lauryl 60g, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester 30g, to be dissolved in 110g hexane and to mix 10 minutes to evenly, obtaining the antioxidant composition X1 be dissolved in hexane.
Embodiment 2
The present embodiment is for illustration of the preparation method of antioxidant composition of the present invention.
At 50 DEG C, by β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid positive octadecanol ester 40g, dithiodipropionic acid two lauryl 40g, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester 10g, be dissolved in 270g hexanaphthene and mix 7 minutes to evenly, obtain the antioxidant composition X2 be dissolved in hexanaphthene.
Embodiment 3
The present embodiment is for illustration of the preparation method of antioxidant composition of the present invention.
At 70 DEG C, by β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid positive octadecanol ester 35g, dithiodipropionic acid two lauryl 50g, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester 23g, be dissolved in 200g hexane and mix 5 minutes to evenly, obtain the antioxidant composition X3 be dissolved in hexane.
Embodiment 4
The present embodiment is for illustration of the preparation method of styrene series thermoplastic elastomer of the present invention.
The hexane organic solution (wherein containing 6g antioxidant composition X1) 12g being dissolved with antioxidant composition X1 adds 1000gSBS(producer to: Yanshan Petrochemical, number-average molecular weight is 230,000) in, after cohesion, drying, obtain styrene series thermoplastic elastomer S1.
Embodiment 5
The present embodiment is for illustration of the preparation method of styrene series thermoplastic elastomer of the present invention.
The hexanaphthene organic solution (wherein containing 8g antioxidant composition X2) 32g being dissolved with antioxidant composition X2 is added to containing 1000gSIS(producer: Yanshan Petrochemical, number-average molecular weight is 200,000) in, after cohesion, drying, obtain styrene series thermoplastic elastomer S2.
Embodiment 6
The present embodiment is for illustration of the preparation method of styrene series thermoplastic elastomer of the present invention.
The hexane organic solution (wherein containing 7g antioxidant composition X3) 21g being dissolved with antioxidant composition X3 is added to containing 1000gSBS(producer: Yanshan Petrochemical, number-average molecular weight is 250,000) in, after cohesion, drying, obtain styrene series thermoplastic elastomer S3.
Embodiment 7
According to the method for embodiment 5, unlike, the hexanaphthene organic solution (wherein containing 10g antioxidant composition X2) being dissolved with antioxidant composition X2 with 40g substitutes the hexanaphthene organic solution (wherein containing 8g antioxidant composition X2) that 32g is dissolved with antioxidant composition X2.Obtain styrene series thermoplastic elastomer S4.
Comparative example 1-3
Styrene series thermoplastic elastomer is prepared according to the method for embodiment 5, unlike, replace antioxidant composition X2 respectively with antioxidant 264, antioxidant 2246 and anti-aging agent 1520, obtain styrene series thermoplastic elastomer DS1-DS3 respectively.
Comparative example 4-6
Styrene series thermoplastic elastomer is prepared according to the method for embodiment 5, unlike, be used alone 50g β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, 50g tri-(2,4-di-tert-butyl-phenyl) phosphorous acid ester and 50g dithiodipropionic acid two lauryl, substitute antioxidant composition X2, obtain styrene series thermoplastic elastomer DS4-DS6 respectively.
Test case 1
The styrene series thermoplastic elastomer prepared by embodiment 4-7 and comparative example 1-6 carries out the test of oxidation induction period, oxidation induction temperature and aging xanthochromia performance respectively in accordance with the following methods, detects as shown in table 1 below.
(1) oxidation induction period
With TA2910 type differential scanning calorimetric analysis instrument, according to the regulation in GB/T19466.6-2009, take the sample that quality is about 5mg, be placed in aluminum dish, pass into nitrogen with 50 ± 5ml/min, control temperature rise rate 10 °/min, be warming up to 140 °.Constant temperature 2min, uses replacement of oxygen nitrogen, and constant temperature is at 140 °, until exothermic maximum signal occurs.The time of start-of-record heat release, the time, longer explanation antioxidant effect was better.
(2) oxidation induction temperature
With TA2910 type differential scanning calorimetric analysis instrument, according to the regulation in GB/T19466.6-2009, take the sample that quality is about 5mg, be placed in aluminum dish, pass into oxygen with 50 ± 5ml/min, control temperature rise rate 10 °/min, temperature programming is until exothermic maximum signal occurs.Record the temperature under exothermic maximum signal, the higher explanation antioxidant effect of temperature is better.
(3) aging xanthochromia performance
S1-S4 and DS1-DS6 is made print, specifies according in ASTMD1148-2007, be placed in thermo-oxidative ageing case respectively, carry out thermo-oxidative ageing in 100 DEG C, observe the discoloration of different time sample.The change of sample color can use variable color meter to test, and uses following formulae discovery aberration: (result of variable color meter test is the changing conditions of aging front and back color, and name is called value of chromatism)
⊿ E=E
u-E
e， ⊿ E is for irradiating rear and pre-irradiation sample aberration, E
ufor the color measured values of pre-irradiation sample, E
efor irradiating the color measured values of rear sample.
Table 1
As can be seen from the data results of table 1, good synergy is there is between the various materials that environmental protection antioxidant composition that low toxicity provided by the invention is pollution-free comprises, the composite styrene series thermoplastic elastomer prepared, has more excellent ageing-resistant performance and anti-yellowing property.
Particularly, embodiment 4-6 is the styrene series thermoplastic elastomer using antioxidant composition provided by the invention to prepare, comparative example 1-3 is the styrene series thermoplastic elastomer using conventional anti-aging agent to prepare, they carry out oxidation induction period, the data results of oxidation induction temperature and aging xanthochromia performance test shows, styrene series thermoplastic elastomer prepared by antioxidant composition provided by the invention can have longer resistance to Coloring Time, longer oxidation induction period and the oxidation induction temperature of Geng Gao, namely have more excellent ageing-resistant and anti-yellowing property.
In embodiment 5, the value of chromatism of 48 hours only has 1.96, and the oxidation induction period at 140 DEG C can reach 60 minutes, and oxidation induction temperature also can reach 183 DEG C, obviously than using the comparative example of conventional protective agent will have better ageing-resistant and anti-yellowing property.
In addition, comparative example 4-6 is the styrene series thermoplastic elastomer that each component antioxidant composition in embodiment 5 contained is used alone preparation, as can be seen from the data results of table 1, all the ageing-resistant of styrene series thermoplastic elastomer and anti-yellowing property can not be obviously improved when these components are used alone, and by by composite for these components and composition that is that obtain can significantly improve the ageing-resistant of styrene series thermoplastic elastomer and anti-yellowing property in embodiment 5.As can be seen here, between each component in described antioxidant composition provided by the invention, improving in the ageing-resistant of styrene series thermoplastic elastomer and anti-yellowing property, there is obvious synergy.
Compared can be found out by styrene series thermoplastic elastomer embodiment 7 and embodiment 5 prepared, styrene series thermoplastic elastomer prepared by embodiment 5 has better ageing-resistant and anti-yellowing property.As can be seen here, with 100 parts by weight of styrene based block copolymers for benchmark, when the content of described antioxidant composition is 0.6-0.8 weight part, styrene series thermoplastic elastomer has more excellent ageing-resistant and anti-yellowing property.
Claims (13)
1. an antioxidant composition, it is characterized in that, this antioxidant composition contains the β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid, three (2,4-di-tert-butyl-phenyl) phosphorous acid esters and dithiodipropionic acid two lauryl; Wherein, with dithiodipropionic acid two lauryl of 100 weight parts for benchmark, the content of β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid is 80-150 weight part, the content of three (2,4-di-tert-butyl-phenyl) phosphorous acid ester is 10-100 weight part.
2. antioxidant composition according to claim 1, wherein, with dithiodipropionic acid two lauryl of 100 weight parts for benchmark, the content of β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid is 80-100 weight part; The content of three (2,4-di-tert-butyl-phenyl) phosphorous acid ester is 16.7-75 weight part.
3. the preparation method of an antioxidant composition, the method comprises β-(3,5-di-tert-butyl-hydroxy phenyl) mixing of the positive octadecanol ester of propionic acid, three (2,4-di-tert-butyl-phenyl) phosphorous acid esters and dithiodipropionic acid two lauryl; Wherein, with the consumption of dithiodipropionic acid two lauryl of 100 weight parts for benchmark, β-(3,5-di-tert-butyl-hydroxy phenyl) consumption of the positive octadecanol ester of propionic acid is 80-150 weight part, the consumption of three (2,4-di-tert-butyl-phenyl) phosphorous acid ester is 10-100 weight part.
4. method according to claim 3, wherein, with the consumption of dithiodipropionic acid two lauryl of 100 weight parts for benchmark, the consumption of β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid is 80-100 weight part; The consumption of three (2,4-di-tert-butyl-phenyl) phosphorous acid ester is 16.7-75 weight part.
5. the method according to claim 3 or 4, wherein, by β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester and dithiodipropionic acid two lauryl mixing process carry out in presence of organic solvent, described organic solvent is alkane or naphthenic hydrocarbon.
6. method according to claim 5, wherein, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid positive octadecanol ester, three (2,4-di-tert-butyl-phenyl) phosphorous acid esters and total consumption of dithiodipropionic acid two lauryl and the consumption of described organic solvent weight ratio be 1:1-5.
7. method according to claim 6, wherein, β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid positive octadecanol ester, three (2,4-di-tert-butyl-phenyl) phosphorous acid esters and total consumption of dithiodipropionic acid two lauryl and the consumption of described organic solvent weight ratio be 1:1-3.
8. a styrene series thermoplastic elastomer, is characterized in that, this styrene series thermoplastic elastomer contains styrene block copolymer and antioxidant composition, and described antioxidant composition is the antioxidant composition described in claim 1 or 2.
9. styrene series thermoplastic elastomer according to claim 8, wherein, with styrene block copolymer described in 100 weight parts for benchmark, the content of described antioxidant composition is 0.5-1 weight part.
10. styrene series thermoplastic elastomer according to claim 9, wherein, with styrene block copolymer described in 100 weight parts for benchmark, the content of described antioxidant composition is 0.6-0.8 weight part.
The preparation method of 11. 1 kinds of styrene series thermoplastic elastomers, the method comprises and being mixed with antioxidant composition by styrene block copolymer, then carry out condensing and drying, wherein, described antioxidant composition is the antioxidant composition described in claim 1 or 2.
12. methods according to claim 11, wherein, with the consumption of styrene block copolymer described in 100 weight parts for benchmark, the consumption of described antioxidant composition is 0.5-1 weight part.
13. methods according to claim 12, wherein, with the consumption of styrene block copolymer described in 100 weight parts for benchmark, the consumption of described antioxidant composition is 0.6-0.8 weight part.
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| 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 |
| CN112239568A (en) * | 2019-07-19 | 2021-01-19 | 中国石油化工股份有限公司 | Anti-aging agent composition and application thereof, rubber composition, vulcanized rubber and preparation method thereof |
| CN115678289B (en) * | 2021-07-27 | 2023-09-01 | 中国石油化工股份有限公司 | Anti-drop sulfur asphalt and preparation method and application thereof |
| CN115678294B (en) * | 2021-07-27 | 2023-09-01 | 中国石油化工股份有限公司 | Anti-stripping agent and preparation method and application thereof |
| CN113861934A (en) * | 2021-11-05 | 2021-12-31 | 东莞市山力高分子材料科研有限公司 | Industrial glue for electronic and electric appliances |
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| CN1492903A (en) * | 2001-02-23 | 2004-04-28 | 阿尔伯麦尔公司 | Granular polymer additives and their preparation |
| WO2007102437A1 (en) * | 2006-03-03 | 2007-09-13 | Asahi Glass Company, Limited | Gap clogging member for vehicles, and plate-like body for vehicle windows with gap clogging member using the same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1492903A (en) * | 2001-02-23 | 2004-04-28 | 阿尔伯麦尔公司 | Granular polymer additives and their preparation |
| WO2007102437A1 (en) * | 2006-03-03 | 2007-09-13 | Asahi Glass Company, Limited | Gap clogging member for vehicles, and plate-like body for vehicle windows with gap clogging member using the same |
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| CN103709439A (en) | 2014-04-09 |
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