CN102516488B - Polymer type anti-oxidant, preparation method thereof, and application thereof - Google Patents
Polymer type anti-oxidant, preparation method thereof, and application thereof Download PDFInfo
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- CN102516488B CN102516488B CN 201110401223 CN201110401223A CN102516488B CN 102516488 B CN102516488 B CN 102516488B CN 201110401223 CN201110401223 CN 201110401223 CN 201110401223 A CN201110401223 A CN 201110401223A CN 102516488 B CN102516488 B CN 102516488B
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Abstract
The invention relates to the field of a polymer type anti-oxidant, and provides a polymer type anti-oxidant, a preparation method thereof, and an application thereof. According to the invention, under the effect of a catalyst dibutyltin dilaurate, hydroxyl-terminated polybutadiene and isophorone diisocyanate are subject to a reaction under a temperature of 30 to 50 DEG C, such that an adduct is synthesized; the adduct is subject to a reaction with a low-molecular bisphenol anti-oxidant under a temperature of 60 to 80 DEG C, such that the polymer type anti-oxidant is prepared. The thermal oxidative aging resistance of the polymer type anti-oxidant is better than that of the corresponding low-molecular bisphenol anti-oxidant. Also, the polymer type anti-oxidant has an excellent extraction resistance. The anti-oxidant can be widely applied in rubber materials.
Description
Technical field
The present invention relates to polymer-type oxidation inhibitor field, specifically a kind of polymer-type oxidation inhibitor and its preparation method and application.
Background technology
Macromolecular material easily is subject to the effect of heat, oxygen, ozone, mechanical force etc. in storage, processing, use procedure, the variation of meeting recurring structure and performance loses use value gradually, and this phenomenon is called the aging of macromolecular material.Particularly in rubber molecular chain owing to containing a large amount of two keys, the thermo-oxidative ageing problem is more outstanding.In order to suppress, stop or delay the generation of oxidizing reaction, usually add some can delay the oxidation inhibitor of deterioration by oxidation.At present the most frequently used oxidation inhibitor has phenols, amine, contains Phosphorus and the oxidation inhibitor such as sulfur-bearing class, and wherein hindered phenol and arylamine are the most effective two class primary antioxidants.Yet, because traditional oxidation inhibitor molecular weight is relatively low, can be subjected to heat effect in the course of processing, or along with the passing of duration of service, can be constantly by volatilizing, moving and gone out to atmosphere, soil and waters by solvent extraction, cause the pollution to environment, thereby human health is caused potential impact.Simultaneously, after the oxidation inhibitor loss, rubber item thermo oxidative aging ability reduces greatly.In the season of sweltering heat, doughnut produces high temperature in the process of moving, causes the oxidation inhibitor loss, and greatly reduced the work-ing life of tire.
The low molecule oxidation inhibitor of tradition easily volatilizees in order to solve, migration and the poor difficult problem of resistant to extraction performance, the method of the high antioxygens of some preparations, low migration, low volatility and low extracting oxidation inhibitor has been proposed, wherein, preparation polymer-type oxidation inhibitor is one of most important method.Has good dispersiveness as the polymer-type oxidation inhibitor by natural rubber graft N-(4-aminodiphenylmethane) acrylamide preparation in rubber matrix, and antioxidant property and resistant to extraction performance are better than hanging down accordingly molecule oxidation inhibitor (Synthesis, characterization, and evaluation of natural rubber-graft-
N-(4-aminodiphenyl methane) acrylamide as an antioxidant:Journal of Applied Polymer Science, 2006,101 (2): 843-849).The heat resistanceheat resistant oxygen performance of cardanol grafted natural rubber is better than cardanol (Synthesis and characterization of cardanol-grafted natural rubber-the solution technique:Journal of Applied Polymer Science, 2007,105 (3): 1280-1288).With 4-hydroxyl-2, the 6-DI-tert-butylphenol compounds is grafted to the polymer-type oxidation inhibitor that obtains on the hydroxy-terminated polybutadienes molecular chain and is better than corresponding low molecule oxidation inhibitor, and the resistant to extraction performance is better than low molecule oxidation inhibitor (Synthesis and performance of phenolic polybutadiene-bound stabilizers, Journal of Applied Polymer Science, 2003,87 (6): 885-889).Yet, preparation polymer-type oxidation inhibitor mainly will have the low molecular compound grafting of antioxygenation or be connected in polymer molecular chain by radical polymerization at present, because the low molecular compound with antioxygenation has inhibition to radical polymerization, thereby reaction conditions is harsher, and in the polymer-type oxidation inhibitor that obtains, the low molecular compound relative content is less, antioxygenic effect is not ideal, is difficult to realize large-scale industrial production.
Summary of the invention
The object of the invention is to the defective for the prior art existence, a kind of have good thermo oxidative aging effect and the polymer-type oxidation inhibitor of resistant to extraction performance are provided.
The present invention also aims to provide the preparation method of described polymer-type oxidation inhibitor.
Purpose of the present invention also relates to the application of described polymer-type oxidation inhibitor in rubber (natural rubber, styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber and paracril etc.).
The preparation method of a kind of polymer-type oxidation inhibitor of the present invention, under the effect of catalyzer dibutyl tin laurate, isophorone diisocyanate first reacts synthetic affixture with hydroxy-terminated polybutadienes in organic solvent, then is prepared into polymer-type oxidation inhibitor with low molecule bisphenols oxidation inhibitor reaction.
Described organic solvent is toluene, tetrahydrofuran (THF), normal hexane, octane or normal heptane.
Described low molecule bisphenols oxidation inhibitor is 2,2 '-thiobis (4-methyl-6-tert-butylphenol) or 2,2 '-methylene bis (4-methyl-6-tert-butylphenol).
More specifically, the preparation method of polymer-type oxidation inhibitor of the present invention comprises the steps:
(1) hydroxy-terminated polybutadienes is dissolved in organic solvent, temperature is risen to 30-50 ℃, add appropriate catalyzer dibutyl tin laurate, in 10-50min, isophorone diisocyanate is added drop-wise in reaction system, insulation reaction 3-6h, the affixture of acquisition hydroxy-terminated polybutadienes and isophorone diisocyanate;
(2) temperature with above-mentioned hydroxy-terminated polybutadienes and isophorone diisocyanate affixture rises to 60-80 ℃, add appropriate catalyzer dibutyl tin laurate, then drip low molecule bisphenols oxidation inhibitor solution, time for adding 10-50min, then insulation reaction 4-12h;
(3) after reaction is completed, add excessive methanol to reaction system, product is precipitated out, after removing supernatant liquid, and more than 5 times, obtain at last polymer-type oxidation inhibitor through toluene dissolving, methanol extraction and filtration cycle operation.
The parts by weight of above-mentioned raw materials are as follows:
Hydroxy-terminated polybutadienes 40-70;
Dibutyl tin laurate 1-3;
Low molecule bisphenols oxidation inhibitor 10-40;
Organic solvent (not containing the separating-purifying part) 80-140.
Described polymer-type oxidation inhibitor joins in the rubber such as natural rubber, styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber and paracril, by mechanically milling and sulfuration, can prepare the cross-linked rubber with excellent thermo oxidative aging performance and resistant to extraction performance.Particularly, the application of described polymer-type oxidation inhibitor in rubber comprises the steps:
(1) first with rubber (natural rubber, styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber and paracril etc.) thin-pass in mill, then compounding process adds Synergist S-421 95 and polymer-type oxidation inhibitor routinely, adds at last sulphur.Mixing evenly after slice, obtain containing the rubber unvulcanizate of polymer-type oxidation inhibitor;
(2) after rubber unvulcanizate was parked 24h, cure conditions vulcanized compressing tablet routinely on vulcanizing press.After the cross-linked rubber that obtains is parked 24h, carry out the physical and mechanical properties test.
The parts by weight of above-mentioned raw materials are as follows:
Rubber 100;
Calcium carbonate 30;
Stearic acid 2;
Zinc oxide 5;
Short CZ 1.5;
Short DM 0.5;
Sulphur 1.5;
Polymer-type oxidation inhibitor 4-15.
The present invention compared with prior art has following advantage:
(1) the polymer-type oxidation inhibitor of the present invention's preparation has excellent antioxidant property, and it is better than corresponding low molecule oxidation inhibitor to rubber (natural rubber, styrene-butadiene rubber(SBR), cis-1,4-polybutadiene rubber and paracril etc.) thermo oxidative aging performance.
(2) the polymer-type oxidation inhibitor of the present invention's preparation has excellent resistant to extraction performance.Cross-linked rubber aging coefficient after the boiling water extracting of the polymer-type oxidation inhibitor of use the present invention preparation descends very little, and uses the aging coefficient of corresponding low molecule oxidation inhibitor significantly to descend.
(3) polymer-type oxidation inhibitor preparation technology of the present invention is fairly simple, and reaction conditions is gentleer, and process is easily controlled, and is convenient to scale operation, has a good application prospect.
Embodiment
Embodiment 1
(number-average molecular weight is 1.8-2.5 * 10 for Cray Willie (Guangzhou) chemical industry company limited, trade mark LBH2000 to add the 10.00g hydroxy-terminated polybutadienes in the 100mL four-hole boiling flask that mechanical stirring, prolong, thermometer, nitrogen access port are housed
3) and 5.00g toluene, after stirring, temperature is risen to 40 ℃, add the 0.01g dibutyl tin laurate, the isophorone diisocyanate with 2.02g in 30min is added drop-wise in above-mentioned reactant, and insulation reaction 270min is prepared into affixture.Subsequently, the affixture temperature is risen to 75 ℃, add the 0.31g dibutyl tin laurate, the solution with 3.26g 2,2 '-thiobis (4-methyl-6-tert-butylphenol) and 10.00g toluene in 30min is added drop-wise in above-mentioned affixture, insulation reaction 360min.Reaction adds excessive methanol to reaction system after finishing, and product is precipitated out, and after removing supernatant liquid, obtains faint yellow milk.And through toluene dissolving, methanol extraction and filtration cycle operation 5 times, after vacuum-drying, obtain polymer-type oxidation inhibitor hydroxy-terminated polybutadienes and connect 2,2 '-thiobis (4-methyl-6-tert-butylphenol).
The application of polymer-type oxidation inhibitor in natural rubber:
First with natural rubber thin-pass 6 times (roll spacing 0.5mm) in mill, compounding process adds the polymer-type oxidation inhibitor (wherein 2 of Synergist S-421 95 and 8 parts of above-mentioned preparations routinely again, 2 '-content of thiobis (4-methyl-6-tert-butylphenol) structural unit is about 1 part), add at last sulphur.Rubber unvulcanizate vulcanizes on 25 tons of hydraulic flat vulcanizers after parking 24h, curing temperature is 143 ℃, curing time is 8 minutes, after room temperature is parked 24h, natural rubber vulcanized rubber before and after extracting is carried out physical and mechanical properties and heatproof air aging performance test through the sample after sulfuration, aging condition is 100 ℃ * 24h.Wherein the preparation of extracting sample is that the cross-linked rubber sample is soaked in extracting 24h in 100 ℃ of boiling water.Experimental result is as shown in table 1.
Can see from table 1, add 1 part 2,2 '-aging coefficient of the natural rubber vulcanized rubber of thiobis (4-methyl-6-tert-butylphenol) is that 0.53(sees comparative example 1), and add polymer-type oxidation inhibitor hydroxy-terminated polybutadienes and connect 2,2 '-aging coefficient of thiobis (4-methyl-6-tert-butylphenol) brings up to 0.56.This show the polymer-type oxidation inhibitor thermo oxidative aging performance of above-mentioned preparation be better than 2,2 '-thiobis (4-methyl-6-tert-butylphenol).After 100 ℃ of boiling water extracting 24h, add 2,2 '-aging coefficient of the natural rubber vulcanized rubber of thiobis (4-methyl-6-tert-butylphenol) drops to 0.40(from 0.53 and sees comparative example 1), and add polymer-type oxidation inhibitor only drop to 0.55 from 0.56.Show polymer-type oxidation inhibitor hydroxy-terminated polybutadienes connect 2,2 '-the resistant to extraction performance of thiobis (4-methyl-6-tert-butylphenol) obviously be better than hanging down accordingly molecule bisphenols oxidation inhibitor 2,2 '-thiobis (4-methyl-6-tert-butylphenol).
Embodiment 2
According to the method in embodiment 1 and processing condition, the temperature of reaction of hydroxy-terminated polybutadienes and isophorone diisocyanate is increased to 45 ℃, affixture and 2,2 '-temperature of reaction of thiobis (4-methyl-6-tert-butylphenol) is down to 60 ℃, 2,2 '-consumption of thiobis (4-methyl-6-tert-butylphenol) is increased to 6.53g.Experimental result is as shown in table 1.Can see, the polymer-type oxidation inhibitor of preparation has excellent thermo oxidative aging performance and resistant to extraction performance.
Embodiment 3
According to the method in embodiment 1 and processing condition, 2,2 '-thiobis (4-methyl-6-tert-butylphenol) becomes 2,2 '-methylene bis (4-methyl-6-tert-butylphenol), its consumption is 3.10g; Affixture and 2,2 '-methylene bis (4-methyl-6-tert-butylphenol) reaction in, the consumption of dibutyl tin laurate is down to 0.23g, temperature of reaction increases to 80 ℃, the polymer-type oxidation inhibitor hydroxy-terminated polybutadienes connection 2,2 of preparation '-methylene bis (4-methyl-6-tert-butylphenol) consumption in natural rubber is 6 parts.Experimental result is as shown in table 1.
Can find out, add 1 part 2,2 '-aging coefficient of the natural rubber vulcanized rubber of methylene bis (4-methyl-6-tert-butylphenol) is 0.54, drop to 0.37(and see comparative example 2 after 100 ℃ of boiling water extracting 24h), connect 2 and add polymer-type oxidation inhibitor hydroxy-terminated polybutadienes, 2 '-aging coefficient of the natural rubber vulcanized rubber of methylene bis (4-methyl-6-tert-butylphenol) is 0.69, only drops to 0.62 after 100 ℃ of boiling water extracting 24h.This show polymer-type oxidation inhibitor hydroxy-terminated polybutadienes connect 2,2 '-methylene bis (4-methyl-6-tert-butylphenol) has excellent thermo oxidative aging performance and resistant to extraction performance.
Embodiment 4
According to the method in embodiment 3 and processing condition, but 2,2 '-methylene bis (4-methyl-6-tert-butylphenol) consumption increases to 6.20g; Affixture and 2,2 '-methylene bis (4-methyl-6-tert-butylphenol) reaction in, the consumption of dibutyl tin laurate increases to 0.29g, temperature of reaction is down to 75 ℃.Experimental result is as shown in table 1.Can find out, the polymer-type oxidation inhibitor of preparation has excellent thermo oxidative aging performance and resistant to extraction performance.
Comparative example 1
In order to illustrate that the prepared polymer-type oxidation inhibitor hydroxy-terminated polybutadienes of the present invention connects 2,2 '-advantage of thiobis (4-methyl-6-tert-butylphenol), with corresponding low molecule bisphenols oxidation inhibitor 2,2 '-thiobis (4-methyl-6-tert-butylphenol) as a comparative example.
First with natural rubber thin-pass 6 times (roll spacing 0.5mm) in mill, more routinely compounding process add Synergist S-421 95 and 1 part low molecule bisphenols oxidation inhibitor 2,2 '-thiobis (4-methyl-6-tert-butylphenol), add at last sulphur.Rubber unvulcanizate vulcanizes on 25 tons of hydraulic flat vulcanizers after parking 24h, curing temperature is 143 ℃, curing time is 8 minutes, after room temperature is parked 24h, natural rubber vulcanized rubber before and after extracting is carried out physical and mechanical properties and heatproof air aging performance test through the sample after sulfuration, aging condition is 100 ℃ * 24h.Wherein a cross-linked rubber sample that is prepared as of extracting sample is soaked in extracting 24h in 100 ℃ of boiling water.Experimental result is as shown in table 1.
Comparative example 2
In order to illustrate that the prepared polymer-type oxidation inhibitor hydroxy-terminated polybutadienes of the present invention connects 2,2 '-advantage of methylene bis (4-methyl-6-tert-butylphenol), according to the method in comparative example 1 and processing condition, low molecule bisphenols oxidation inhibitor 2,2 '-thiobis (4-methyl-6-tert-butylphenol) becomes 2,2 '-methylene bis (4-methyl-6-tert-butylphenol) is as a comparative example.Experimental result is as shown in table 1.
Testing method
1. the tensile strength of rubber and tensile yield are measured according to GB/T 528-2009.
2. the thermo oxidative aging performance of rubber test: carry out according to GB 3512-2001, aging temperature is 100 ℃, and digestion time is 48h.
Rubber as aging evaluation index, as aging coefficient, adopts formula (1) to calculate aging coefficient (K) with the tensile product conservation rate with " tensile product " (f=tensile strength * tensile yield).
In formula: the tensile product after the f-sample is aging;
f
0Tensile product before-sample is aging.
The aging coefficient of natural rubber vulcanized rubber before and after 100 ℃ of boiling water extractings of table 1
Claims (4)
1. the preparation method of a polymer-type oxidation inhibitor, it is characterized in that, under the effect of catalyzer dibutyl tin laurate, isophorone diisocyanate first reacts synthetic affixture with hydroxy-terminated polybutadienes in organic solvent, then is prepared into polymer-type oxidation inhibitor with low molecule bisphenols oxidation inhibitor reaction;
Described organic solvent is toluene, tetrahydrofuran (THF), normal hexane, octane or normal heptane;
Described low molecule bisphenols oxidation inhibitor is 2,2 '-thiobis (4-methyl-6-tert-butylphenol) or 2,2 '-methylene bis (4-methyl-6-tert-butylphenol).
2. polymer-type oxidation inhibitor preparation method according to claim 1 is characterized in that comprising the following steps:
(1) hydroxy-terminated polybutadienes is dissolved in organic solvent, temperature is risen to 30-50 ℃, add appropriate catalyzer dibutyl tin laurate, in 10-50min, isophorone diisocyanate is added drop-wise in reaction system, insulation reaction 3-6h, the affixture of acquisition hydroxy-terminated polybutadienes and isophorone diisocyanate;
(2) temperature with above-mentioned hydroxy-terminated polybutadienes and isophorone diisocyanate affixture rises to 60-80 ℃, add appropriate catalyzer dibutyl tin laurate, then drip low molecule bisphenols oxidation inhibitor solution, time for adding 10-50min, then insulation reaction 4-12h;
(3) after reaction is completed, add excessive methanol to reaction system, reaction product is precipitated out, after removing supernatant liquid, and more than 5 times, obtain at last polymer-type oxidation inhibitor through toluene dissolving, methanol extraction and filtration cycle operation;
The parts by weight of above-mentioned raw materials are as follows:
Hydroxy-terminated polybutadienes 40-70;
Dibutyl tin laurate 1-3;
Low molecule bisphenols oxidation inhibitor 10-40;
Organic solvent 80-140.
3. the polymer-type oxidation inhibitor for preparing of the described method of claim 1 or 2.
4. the application of the described polymer-type oxidation inhibitor of claim 3 in rubber, is characterized in that comprising the steps:
(1) first with rubber thin-pass in mill, then compounding process adds Synergist S-421 95 and polymer-type oxidation inhibitor routinely, adds at last sulphur; Mixing evenly after slice, obtain containing the rubber unvulcanizate of polymer-type oxidation inhibitor;
(2) after rubber unvulcanizate was parked 24h, cure conditions vulcanized compressing tablet routinely on vulcanizing press; After the cross-linked rubber that obtains is parked 24h, carry out the physical and mechanical properties test; Described Synergist S-421 95 comprises calcium carbonate, stearic acid, zinc oxide, short CZ and short DM;
The parts by weight of above-mentioned raw materials are as follows:
Rubber 100;
Calcium carbonate 30;
Stearic acid 2;
Zinc oxide 5;
Short CZ 1.5;
Short DM 0.5;
Sulphur 1.5;
Polymer-type oxidation inhibitor 4-15.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130978B (en) * | 2012-12-17 | 2014-09-10 | 华南理工大学 | Macromolecule hindered phenol antioxidant, preparation method of macromolecule hindered phenol antioxidant, and application of macromolecule hindered phenol antioxidant |
| CN109111604B (en) * | 2018-07-20 | 2020-09-25 | 苏州热工研究院有限公司 | Self-repairing rubber material and preparation method thereof |
| CN109306046A (en) * | 2018-09-27 | 2019-02-05 | 上海应用技术大学 | A kind of hindered phenol macromonomer of polyphenol structure and preparation method thereof |
| CN109438660A (en) * | 2018-09-27 | 2019-03-08 | 上海应用技术大学 | A kind of hindered phenol macromonomer and its preparation method and application |
| CN109280233B (en) * | 2018-10-15 | 2021-07-20 | 浙江鼎天交通设施股份有限公司 | Rubber deceleration strip and preparation method thereof |
| CN116903951B (en) * | 2023-09-12 | 2023-12-05 | 上海睿聚环保科技有限公司 | Regenerated high-density polyethylene for marine fishing net and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006027385A1 (en) * | 2004-09-09 | 2006-03-16 | Tesa Ag | Functionalised polymers or contact adhesive masses |
| CN1958636A (en) * | 2006-10-21 | 2007-05-09 | 福州大学 | Material formula of polyurethane of enzymolysis lignin, and preparation method |
| CN101358030A (en) * | 2008-09-05 | 2009-02-04 | 中国石油兰州石油化工公司 | Method for preparing high performance urethane elastomer for thermal barrier coating |
| CN101798405A (en) * | 2010-03-12 | 2010-08-11 | 江苏工业学院 | Nickel-system polybutadiene rubber composite anti-aging agent with anti-yellowing efficiency |
-
2011
- 2011-12-07 CN CN 201110401223 patent/CN102516488B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006027385A1 (en) * | 2004-09-09 | 2006-03-16 | Tesa Ag | Functionalised polymers or contact adhesive masses |
| CN1958636A (en) * | 2006-10-21 | 2007-05-09 | 福州大学 | Material formula of polyurethane of enzymolysis lignin, and preparation method |
| CN101358030A (en) * | 2008-09-05 | 2009-02-04 | 中国石油兰州石油化工公司 | Method for preparing high performance urethane elastomer for thermal barrier coating |
| CN101798405A (en) * | 2010-03-12 | 2010-08-11 | 江苏工业学院 | Nickel-system polybutadiene rubber composite anti-aging agent with anti-yellowing efficiency |
Non-Patent Citations (7)
| Title |
|---|
| Jirl Podesva.Stabilization of polyurethanes based on liquid OH-telechelic polybutadienes Comparison of commercial and polymer-bound antioxidants.《Polymer Degradation and Stability》.2009,第94卷第647-650页. |
| Jirl Podesva.Synthesis and performance of phenolic polybutadiene bound stabilizers.《Journal of Applied Polymer Science》.2002,第87卷第885-889页. |
| Jirl Podesva.Synthesis,Characterization,and Evaluation of Natural Rubber-graft-N-(4-Aminodiphenyl methane)Acrylamide as an Antioxidant.《Journal of Applied Polymer Science》.2005,第101卷第843-849页. |
| Stabilization of polyurethanes based on liquid OH-telechelic polybutadienes Comparison of commercial and polymer-bound antioxidants;Jirl Podesva;《Polymer Degradation and Stability》;20090114;第94卷;第647-650页 * |
| Synthesis and performance of phenolic polybutadiene bound stabilizers;Jirl Podesva;《Journal of Applied Polymer Science》;20020325;第87卷;第885-889页 * |
| Synthesis,Characterization,and Evaluation of Natural Rubber-graft-N-(4-Aminodiphenyl methane)Acrylamide as an Antioxidant;Jirl Podesva;《Journal of Applied Polymer Science》;20051222;第101卷;第843-849页 * |
| 邹国铭.橡胶的成型加工.《高分子材料加工工艺学》.中国纺织出版社,2000,第11-12页. * |
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