CN110305366B - Antioxidant stabilizer composition and modified butadiene rubber - Google Patents
Antioxidant stabilizer composition and modified butadiene rubber Download PDFInfo
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- CN110305366B CN110305366B CN201910689710.2A CN201910689710A CN110305366B CN 110305366 B CN110305366 B CN 110305366B CN 201910689710 A CN201910689710 A CN 201910689710A CN 110305366 B CN110305366 B CN 110305366B
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- 239000003381 stabilizer Substances 0.000 title claims abstract description 73
- 229920002857 polybutadiene Polymers 0.000 title claims abstract description 72
- 239000005062 Polybutadiene Substances 0.000 title claims abstract description 67
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 67
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 65
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 21
- -1 m-pentadecylphenyl Chemical group 0.000 claims abstract description 50
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 claims abstract description 24
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- MZHULIWXRDLGRR-UHFFFAOYSA-N tridecyl 3-(3-oxo-3-tridecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCC MZHULIWXRDLGRR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 13
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 6
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 5
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 13
- 229920001971 elastomer Polymers 0.000 abstract description 12
- 230000003647 oxidation Effects 0.000 abstract description 12
- 239000005060 rubber Substances 0.000 abstract description 12
- 230000009471 action Effects 0.000 abstract description 7
- 239000003292 glue Substances 0.000 description 18
- 230000032683 aging Effects 0.000 description 14
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 description 10
- 230000007613 environmental effect Effects 0.000 description 9
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 8
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 7
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000006698 induction Effects 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000003712 anti-aging effect Effects 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OAAIHCBUXRSTSG-UHFFFAOYSA-N [3,5-ditert-butyl-4-hydroxy-2-(6-methylheptyl)phenyl] propanoate Chemical compound CCC(=O)OC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1CCCCCC(C)C OAAIHCBUXRSTSG-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940011871 estrogen Drugs 0.000 description 2
- 239000000262 estrogen Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229940088597 hormone Drugs 0.000 description 2
- 239000005556 hormone Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- AIAMDEVDYXNNEU-UHFFFAOYSA-N 6-methylheptyl propanoate Chemical compound CCC(=O)OCCCCCC(C)C AIAMDEVDYXNNEU-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010049290 Feminisation acquired Diseases 0.000 description 1
- 208000034793 Feminization Diseases 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 231100000507 endocrine disrupting Toxicity 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 230000007368 endocrine function Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
- 238000010092 rubber production Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000036301 sexual development Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/175—Amines; Quaternary ammonium compounds containing COOH-groups; Esters or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/38—Thiocarbonic acids; Derivatives thereof, e.g. xanthates ; i.e. compounds containing -X-C(=X)- groups, X being oxygen or sulfur, at least one X being sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
-
- 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 provides an antioxidant stabilizer composition and modified butadiene rubber, wherein the composition comprises bis (m-pentadecylphenyl) ] pentaerythritol diphosphite, a hindered phenol stabilizer and ditridecyl thiodipropionate in a mass ratio of 1: 0.2-5: 0-1; the hindered phenol stabilizer is selected from one or more of isooctyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tridecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and octadecyl bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] diethyl octadecyl amine. The invention can apply the composition in butadiene rubber under the combined action of the components with the mass ratio, and can improve the oxidation resistance of rubber. The Mooney viscosity of the modified butadiene rubber is 44.2-45.2 Pa.S after being aged for 192 h; OIT is 108.2-112.6 min, and YI is 11.8-15.9.
Description
Technical Field
The invention belongs to the technical field of rubber, and particularly relates to an antioxidant stabilizer composition and modified butadiene rubber.
Background
In the processing and daily use processes of the high polymer material, the high polymer material is easily affected by oxygen, light, heat and metal ion impurities in the air, and free radical reaction occurs, so that the polymer is subjected to color change, cracking and loss of glossiness.
The elasticity, wear resistance and cold resistance of butadiene rubber can be compared with those of natural rubber, and the butadiene rubber is widely applied to the manufacturing industries of automobile tires, rubber products and soles, so that the industrialization process is fast, at present, the butadiene rubber is second only to the second most commonly used synthetic rubber in the world of butadiene rubber, the rubber is aged due to the action of heat and oxygen in air in the production and storage processes, and in the production process of the butadiene rubber, the application of a catalyst, the corrosion of equipment and the addition of various production auxiliaries enable the rubber to contain harmful metal ions such as copper, manganese, cobalt, nickel, iron and the like, the harmful metal ions play a role in catalyzing the oxidation reaction of the rubber, and the aging speed is accelerated. The aging of the butadiene rubber is macroscopically shown as an oxidation crosslinking type, molecular chain degradation also occurs microscopically, the color of the aged butadiene rubber generally turns yellow, the Mooney viscosity changes, the Mooney viscosity is increased when crosslinking occurs, the Mooney viscosity is reduced when degradation occurs, and the instability of the Mooney viscosity seriously affects the processing of raw rubber and the mechanical property and long-term use stability of products. In order to prevent the aging of the butadiene rubber during the post-treatment drying and storage, suitable stabilizers must be added at the end of the polymerization and stability protection must be provided early.
The phosphite antioxidant is a processing stabilizer with excellent performance, typical products of the current industrialization comprise antioxidants 168, TNPP, 626 and the like, wherein 168 and 626 are high-melting solid phosphite antioxidants, the phosphite antioxidant is mainly suitable for plastics, and the defects of poor ageing resistance caused by non-melting, difficult uniform mixing and easy precipitation exist in the application of the phosphite antioxidant in rubber; TNPP is a typical liquid phosphite antioxidant widely applied in rubber, a liquid additive has the advantages of storage tank storage, pipeline transportation and accurate metering, and the TNPP has the problem that nonyl phenol which is one of main synthetic raw materials can cause feminization of downstream male fishes of a sewage treatment plant and is an endocrine disrupter or environmental hormone organic matter with estrogen action. The endocrine disrupting effects of nonyl phenol on humans and wild animals have attracted widespread attention. Nonylphenol is a recognized environmental hormone which mimics estrogen, exerts an effect on sexual development of an organism, interferes with the endocrine function of an organism, and is toxic to reproductive systems. Meanwhile, nonyl phenol is accumulated in organisms through a food chain, so that research shows that even if the discharged concentration is low, the nonyl phenol is extremely harmful. Therefore, the use of TNPP based on nonylphenol is increasingly limited. With the continuous improvement of the environmental protection standard of the European Union, the requirements of the antioxidant on safety, health and environmental protection are higher and higher, and TNPP is facing a severe test because of containing nonyl phenol.
The antioxidant used in the other butadiene rubber for a long time is BHT, the antioxidant BHT also has the problems of safety and environmental protection, the export of butadiene rubber products in China is limited due to the environmental protection problem, and the European Union has already been in the law to prohibit the use of the antioxidant BHT in the production process of the butadiene rubber. Because BHT has small molecular weight and strong volatility, BHT is easy to diffuse and migrate from a polymer to the surface to volatilize when being heated in the mixing and processing process of butadiene rubber, which not only causes serious environmental air pollution and bad harm to field operators, but also leads antioxidant in rubber to be quickly consumed and completely used up, and has no anti-aging stability.
Generally speaking, the stabilizer should have good thermal stability, health, environmental protection, convenience in use and metering controllability besides good oxidation resistance. However, the two antioxidants, TNPP and BHT, which are conventionally used at present have health, safety and environmental protection problems. At present, the problems of safety, health and environment of the existing antioxidant system of the butadiene rubber are urgently needed to be solved, and researches on new stabilizers and compositions of the butadiene rubber are found to be few, and particularly, researches on safe, environment-friendly and green bio-based antioxidants and compositions of the butadiene rubber are less.
Disclosure of Invention
In view of the above, the present invention aims to provide an antioxidant stabilizer composition and a modified butadiene rubber, wherein the antioxidant stabilizer composition can improve the antioxidant property of the butadiene rubber.
The invention provides an antioxidant stabilizer composition, which comprises bis (m-pentadecylphenyl) ] pentaerythritol diphosphite, a hindered phenol stabilizer and ditridecyl thiodipropionate in a mass ratio of 1: 0.2-5: 0-1;
the hindered phenol stabilizer is selected from one or more of isooctyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tridecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) octadecylamine diethyl ester.
Preferably, the antioxidant stabilizer composition comprises bis (m-pentadecylphenyl) ] pentaerythritol diphosphite and isooctyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate in a mass ratio of 1: 0.5-2.
Preferably, the antioxidant stabilizer composition comprises bis (m-pentadecylphenyl) ] pentaerythritol diphosphite and tridecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate in a mass ratio of 1: 1;
or bis (m-pentadecylphenyl) ] pentaerythritol diphosphite and bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid) octadecylamine diethanol ester in a mass ratio of 1: 1.
Preferably, the antioxidant stabilizer composition comprises 1:1:0.5 bis (m-pentadecylphenyl) ] pentaerythritol diphosphite, isooctyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and octadecyl bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] diethyl octadecyl amine.
Preferably, the antioxidant stabilizer composition comprises bis (m-pentadecylphenyl) ] pentaerythritol diphosphite, tridecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and ditridecyl thiodipropionate in a mass ratio of 1:2: 1.
The invention provides a modified butadiene rubber, which comprises butadiene rubber and the antioxidant stabilizer composition in the technical scheme;
the antioxidant stabilizer composition accounts for 0.3-0.6% of the mass of the butadiene rubber.
Preferably, the antioxidant stabilizer composition accounts for 0.6%, 0.5%, 0.4% or 0.3% of the mass of the butadiene rubber.
The invention provides an antioxidant stabilizer composition, which comprises bis (m-pentadecylphenyl) ] pentaerythritol diphosphite, a hindered phenol stabilizer and ditridecyl thiodipropionate in a mass ratio of 1: 0.2-5: 0-1; the hindered phenol stabilizer is selected from one or more of isooctyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tridecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) octadecylamine diethyl ester. The antioxidant stabilizer composition can be applied to the butadiene rubber under the combined action of the components in the mass ratio, and the antioxidant property of the butadiene rubber can be improved. The experimental results show that: adding the antioxidant stabilizer composition accounting for 0.3-0.6% of the mass of the butadiene rubber, wherein the Mooney viscosity of the modified butadiene rubber is 44.2-45.2 Pa.S after aging for 192 hours; the Oxidation Induction Time (OIT) is 108.2-112.6 min, and the Yellow Index (YI) is 11.8-15.9.
Detailed Description
The invention provides an antioxidant stabilizer composition, which comprises bis (m-pentadecylphenyl) ] pentaerythritol diphosphite, a hindered phenol stabilizer and ditridecyl thiodipropionate in a mass ratio of 1: 0.2-5: 0-1;
the hindered phenol stabilizer is selected from one or more of isooctyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tridecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) octadecylamine diethyl ester.
The antioxidant stabilizer composition can be applied to the butadiene rubber under the combined action of the components in the mass ratio, and the antioxidant property of the butadiene rubber can be improved.
In the present invention, the bis (m-pentadecylphenyl) ] pentaerythritol diphosphite has the structure shown in formula I:
the bis (m-pentadecylphenyl) ] pentaerythritol diphosphite (marked as PS-1) with the structure is a bio-based phosphite antioxidant, which comprises three P-O bonds, wherein P shows positive trivalent and can be combined with unstable component hydroperoxide in a polymer, and the novel bio-based phosphite antioxidant has a large molecular weight and good heat-resistant stability.
The hindered phenol stabilizer is selected from one or more of isooctyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (recorded as AO-1), tridecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (recorded as AO-2) and octadecyl bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] diethyl octadecyl amine (recorded as AO-3). The hindered phenol stabilizer can be applied to the butadiene rubber, and can improve the oxidation resistance of the butadiene rubber. Wherein the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) isooctyl alcohol propionate has a structure shown in a formula II:
the beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) tridecyl propionate has the structure of formula III:
bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoic acid) octadecylamine diethanol ester has the structure of formula IV:
in the present invention, the antioxidant stabilizer composition includes ditridecylthiodipropionate (denoted TS-1); the common action of the ditridecyl thiodipropionate, the hindered phenol stabilizer and the bio-based phosphite antioxidant can improve the oxidation resistance of the ditridecyl thiodipropionate in the butadiene rubber.
The mass ratio of bis (m-pentadecylphenyl) ] pentaerythritol diphosphite, hindered phenol stabilizer and ditridecyl thiodipropionate is 1: 0.2-5: 0-1, preferably 1: 0.2-5: 0.5-2.
The antioxidant stabilizer composition comprises bis (m-pentadecylphenyl) ] pentaerythritol diphosphite and beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) isooctyl propionate in a mass ratio of 1: 0.5-2.
In the present invention, the antioxidant stabilizer composition comprises bis (m-pentadecylphenyl) ] pentaerythritol diphosphite and tridecyl β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate in a mass ratio of 1: 1;
or bis (m-pentadecylphenyl) ] pentaerythritol diphosphite and bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid) octadecylamine diethanol ester in a mass ratio of 1: 1.
In the present invention, the antioxidant stabilizer composition comprises 1:1:0.5 bis (m-pentadecylphenyl) ] pentaerythritol diphosphite, isooctyl- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and octadecyl bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] diethyl octadecyl amine.
In the invention, the antioxidant stabilizer composition comprises bis (m-pentadecylphenyl) ] pentaerythritol diphosphite, tridecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and ditridecyl thiodipropionate in a mass ratio of 1:2: 1.
According to the invention, the contents and specific types of the components are controlled, so that the obtained antioxidant stabilizer composition has different oxidation resistance when applied to butadiene rubber.
The invention provides a modified butadiene rubber, which comprises butadiene rubber and the antioxidant stabilizer composition in the technical scheme;
the antioxidant stabilizer composition accounts for 0.3-0.6% of the mass of the butadiene rubber.
In the present invention, the antioxidant stabilizer composition preferably accounts for 0.6%, 0.5%, 0.4% or 0.3% of the mass of the butadiene rubber.
In particular examples, the antioxidant stabilizer composition consists of: 2000ppm AO-1 and 4000ppm PS-1; or 3000ppm AO-1+2000ppm PS-1; or 2000ppm AO-1+1000ppm PS-1; or 2000ppm AO-3+2000ppm PS-1; or 1000ppm AO-3+2000ppm AO-1+2000ppm PS-1; or 2000ppm AO-2+2000ppm PS-1; or 2000ppm AO-2+1000ppm PS-1+1000 TS-1.
The Mooney viscosity, the oxidation induction time and the yellow index of the modified butadiene rubber are measured by the following methods:
taking a testing glue solution from a butadiene rubber production device, measuring the glue content of the butadiene rubber glue solution, respectively putting 1500ml of the glue solution into different 2L big beakers, adding stabilizer compositions with different components into the corresponding big beakers according to the amount of 0.3-0.6% of the mass of dry glue, putting the big beakers containing the glue solution into a constant-temperature water bath kettle at 60 ℃, uniformly stirring at constant temperature, respectively pouring the glue solution added with the stabilizer compositions into a glue boiling kettle, introducing steam into the glue boiling kettle through a steam valve to boil the glue for about 15 minutes, taking out a ring-shaped white butadiene rubber solid, drying on a double-roll mill at 100 ℃ to respectively obtain raw rubber samples with different antioxidant formulas, testing the physicochemical performance of the samples before ageing, then putting the samples at 105 ℃ for ageing test, sampling the physicochemical performance of the samples every two days, and respectively testing the Mooney viscosity, the Oxidation Induction Time (OIT) and the physicochemical performance of the samples every two days, Yellow Index (YI).
The antioxidant stabilizer composition provided by the invention can replace antioxidants BHT and TNPP, can improve the anti-aging performance and product quality of a synthetic butadiene rubber product, and can enlarge the application range of the product. Compared with the traditional antioxidant BHT and TNPP combination, the oxidation induction period of the butadiene rubber modified by the antioxidant stabilizer composition is obviously prolonged, the Mooney viscosity stability is obviously improved, the discoloration resistance is obviously improved, and the comprehensive heat and oxygen aging resistance is obviously improved.
The antioxidant stabilizer composition provided by the invention can improve the anti-aging quality of butadiene rubber, reduce the precipitation of additives, improve the environmental pollution, ensure the safe use of products and meet the requirements of international standards. The antioxidant stabilizer composition has the characteristics of excellent antioxidant efficiency, low toxicity, low volatility and no migration.
To further illustrate the present invention, an antioxidant stabilizer composition and a modified butadiene rubber provided by the present invention will be described in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
Examples 1 to 7
1500ml of glue solution is respectively put into different 2L big beakers, stabilizers with different components shown in the table 1 are added into the corresponding big beakers according to the amount of 0.3-0.6% of the mass of dry glue, the big beakers containing the glue solution are put into a constant-temperature water bath kettle at 60 ℃, after the glue solution with the added stabilizers are uniformly stirred at constant temperature, the glue solution with the added stabilizers is respectively poured into a glue boiling kettle, a steam valve is opened to introduce steam into the glue boiling kettle for glue boiling for about 15 minutes, a ring-shaped white cis-polybutadiene rubber solid is taken out, the white cis-polybutadiene rubber solid is dried on a double-roller mill at 100 ℃, raw rubber samples with different stabilizer formulas, namely modified cis-polybutadiene rubber, are respectively obtained, the physicochemical properties of the samples before non-aging are tested, then the samples are placed at 105 ℃ for aging test, the samples are sampled every two days for testing the physicochemical properties of the samples, the Mooney viscosity, the oxidation induction period (OIT) and the Yellow Index (YI) are respectively tested, and the results are shown in the table 1, which are 48, the modified cis-polybutadiene rubber prepared by the h. And the performance test results after 96h are shown in the table 2, wherein the performance test results after 144h and 192h of modified butadiene rubber aging are shown in the table.
Comparative example 1
In contrast to example 1, the stabilizer formulation was 6000ppm BHT.
Comparative example 2
In contrast to example 1, the stabilizer formulation was 3000ppm BHT +3000ppm TNPP.
TABLE 1 Performance test results of modified butadiene rubbers prepared in inventive examples 1 to 7 and comparative examples 1 to 2 before aging and after aging for 48 hours and 96 hours
TABLE 2 Performance test results of modified butadiene rubber after 144h and 192h aging
The above embodiments can be seen in: the anti-aging effect of the butadiene rubber can be even better than that of the butadiene rubber added with 0.6 percent of conventional antioxidants BHT and TNPP by only adding 0.3 to 0.5 percent of the butadiene rubber.
From the above embodiments, the present invention provides an antioxidant stabilizer composition, comprising bis (m-pentadecylphenyl) ] pentaerythritol diphosphite, a hindered phenol stabilizer and ditridecyl thiodipropionate in a mass ratio of 1: 0.2-5: 0-1; the hindered phenol stabilizer is selected from one or more of isooctyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tridecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) octadecylamine diethyl ester. The antioxidant stabilizer composition can be applied to the butadiene rubber under the combined action of the components in the mass ratio, and the antioxidant property of the butadiene rubber can be improved. The experimental results show that: adding the antioxidant stabilizer composition accounting for 0.3-0.6% of the mass of the butadiene rubber, wherein the Mooney viscosity of the modified butadiene rubber is 44.2-45.2 Pa.S after aging for 192 hours; the Oxidation Induction Time (OIT) is 108.2-112.6 min, and the Yellow Index (YI) is 11.8-15.9.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A modified butadiene rubber comprises butadiene rubber and an antioxidant stabilizer composition;
the antioxidant stabilizer composition accounts for 0.3-0.6% of the mass of the butadiene rubber;
the antioxidant stabilizer composition comprises bis (m-pentadecylphenyl) ] pentaerythritol diphosphite, a hindered phenol stabilizer and ditridecyl thiodipropionate in a mass ratio of 1: 0.2-5: 0-1;
the hindered phenol stabilizer is selected from one or more of isooctyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tridecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate) octadecylamine diethyl ester.
2. The modified butadiene rubber according to claim 1, wherein the antioxidant stabilizer composition comprises bis (m-pentadecylphenyl) ] pentaerythritol diphosphite and isooctyl β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate in a mass ratio of 1:0.5 to 2.
3. The modified butadiene rubber of claim 1, wherein the antioxidant stabilizer composition comprises bis (m-pentadecylphenyl) ] pentaerythritol diphosphite and tridecyl β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate in a mass ratio of 1: 1;
or bis (m-pentadecylphenyl) ] pentaerythritol diphosphite and bis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid) octadecylamine diethanol ester in a mass ratio of 1: 1.
4. The modified butadiene rubber of claim 1, wherein said antioxidant stabilizer composition comprises 1:1:0.5 bis (m-pentadecylphenyl) ] pentaerythritol diphosphite, isooctyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and octadecyl bis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] diethanol ester.
5. The modified butadiene rubber of claim 1, wherein the antioxidant stabilizer composition comprises bis (m-pentadecylphenyl) ] pentaerythritol diphosphite, tridecyl β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionate, and ditridecyl thiodipropionate in a mass ratio of 1:2: 1.
6. The modified butadiene rubber according to claim 1, wherein the antioxidant stabilizer composition is 0.6%, 0.5%, 0.4% or 0.3% by mass of the butadiene rubber.
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