CN107641325B - Non-migration POSS grafted antioxidant and preparation method thereof - Google Patents
Non-migration POSS grafted antioxidant and preparation method thereof Download PDFInfo
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Abstract
The invention provides a non-migration POSS (polyhedral oligomeric silsesquioxane) grafted anti-aging agent and a preparation method thereof. The invention provides a new anti-aging agent with higher anti-oxidative aging performance and higher anti-migration performance for the aging protection of rubber and other rubber elastomers, and improves the anti-aging efficiency without influencing the structural performance of the rubber and other rubber elastomers.
Description
Technical Field
The invention belongs to the field of rubber antioxidants, and particularly relates to a novel non-migration POSS grafted antioxidant and a preparation method thereof.
Technical Field
Rubber products and elastomers mainly composed of rubber are widely used in various fields of national economy due to their excellent high elasticity, high flexibility and excellent processability. However, rubber products are highly susceptible to degradation during processing and use due to the high degree of unsaturation in the rubber. The aging can cause the performance of the rubber material to be deteriorated, and finally, the service performance is completely lost and even accidents happen. At present, the simplest and most effective anti-aging means is to add an anti-aging agent in the rubber processing process. The most used anti-aging agent is a micromolecular anti-aging agent, and the traditional micromolecular anti-aging agent has the problems of easy volatilization, easy migration and the like in the processing and using processes, so that the concentration of the effective anti-aging agent in a product is reduced, and the long-term protection of a rubber product is not facilitated. And the removed anti-aging agent can pollute the environment and harm the human health. In view of the above disadvantages of the conventional small molecule antioxidants, non-migrating antioxidants have attracted attention. Generally speaking, there are several ways to prepare non-migrating antioxidants: (1) the molecular weight of the anti-aging agent is increased, (2) the anti-aging agent is grafted on a molecular chain of a polymer matrix, and (3) the anti-aging agent is grafted on the surface of a filler. Each of these three approaches has drawbacks and problems: the proportion of effective anti-aging groups is reduced by simply increasing the molecular weight of the anti-aging agent, and the anti-aging agent is not beneficial to uniform dispersion, so that the protection efficiency of the anti-aging agent is reduced; the anti-aging agent is grafted on a polymer matrix molecular chain, which not only influences the uniform dispersion of the anti-aging agent, but also influences the network structure of rubber, so that the anti-aging efficiency is not high, and the rubber performance is influenced; the anti-aging agent is grafted on the surface of the filler, and the method can influence the interaction between the rubber and the filler to a certain extent. Therefore, the development and application of high-performance rubber still urgently need to develop a green environment-friendly anti-aging agent with higher anti-oxidative aging performance and higher anti-migration performance.
Disclosure of Invention
Aiming at the defects of the traditional micromolecular antioxidant and the existing non-migration antioxidant, the invention aims to provide a preparation method of a novel non-migration POSS grafted antioxidant, and provides a novel antioxidant with higher antioxidant aging performance and higher anti-migration performance for aging protection of rubber and other rubber elastomers, so that the aging prevention efficiency is improved while the structural performance of the rubber and other rubber elastomers is not influenced.
The general concept of the invention is: POSS (cage type polysilsesquioxane) consists of an inorganic inner core consisting of a silicon-oxygen framework alternately connected by Si-O, groups R connected by Si atoms on eight vertex angles of the POSS can be reactive or inert groups, and is a special organic-inorganic cage type hybrid molecule, and the structural formula is as follows:
the material can endow the polymer material with a plurality of excellent properties, such as increasing the degradation temperature of the polymer, reducing the degradation rate of the material, improving the dimensional stability of the material and the like. The eight organic functional groups at the eight vertex angles in the POSS molecular structure enable the POSS molecular structure to have good compatibility with polymers, and the eight organic functional groups can be adjusted according to different requirements, so that the POSS molecular structure has different reactivity. The single-activity functional group POSS means that only one group of eight apex angles is a reactive group, and the rest seven groups are inert groups, and the structural formula of the single-activity functional group POSS is shown in the specification
Wherein R1 is one of phenyl, butyl, methyl and cyclohexane, R2 is ester group
Carboxyl group
Hydroxy, acyl bromides
Acid anhydride (A)
Wherein R is an organic structure), epoxy
Organic substituent units of any one of the isoreactive functional groups, e.g.
And the like. According to the invention, the reactive amine group in the amine antioxidant reacts with the reactive group in the single-active functional group POSS, and the amine antioxidant is chemically grafted on POSS molecules, so that the POSS grafted antioxidant is obtained.
The preparation method of the non-migration POSS grafted anti-aging agent comprises the steps of dissolving 5-20 parts by mass of RT base (4-aminodiphenylamine, also known as p-aminodiphenylamine) and 5-20 parts by mass of single-activity functional group POSS in 100 parts by mass of an organic solvent to form a reaction system, removing air in the system by using inert gas, heating under the protection of the inert gas, adding 0.01-0.08 part by mass of a catalyst after the system starts to flow back, stirring and reacting at 100-120 ℃ for 0.5-40 h, removing the organic solvent after the reaction to obtain a solid product, purifying the solid product to remove raw materials which do not participate in the reaction, and performing vacuum drying on the purified product to obtain the non-migration POSS grafted anti-aging agent;
the structural formula of the POSS with the single active functional group is as follows:
wherein R1 is one of phenyl, butyl, methyl and cyclohexane, R2 is ester group
Carboxyl group
Hydroxy (-OH), acyl bromide groups
Acid anhydride group
Epoxy group
An organic substituent unit of a reactive functional group, e.g. of
And the like.
In the above technical solution of the present invention, the organic solvent is preferably one of toluene, tetrahydrofuran, carbon tetrachloride, carbon disulfide, benzene, hexane, chloroform, ethyl acetate, and dichloromethane.
In the above technical solution of the present invention, the catalyst is preferably one of platinum, palladium and nickel.
In the above-mentioned embodiment of the present invention, the organic solvent is preferably removed by one of rotary evaporation, distillation under reduced pressure, distillation and freeze-drying.
In the above technical solution of the present invention, the solid product is preferably purified by one of solution extraction, centrifugal separation and column separation.
The invention provides the non-migration POSS grafted anti-aging agent prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a new anti-aging agent for the aging protection of rubber and other rubber elastomers.
2. The non-migration POSS grafted antioxidant provided by the invention has excellent migration resistance and thermal-oxidative aging resistance, can greatly prolong the oxidation induction time of rubber by applying the POSS grafted antioxidant to the existing rubber, has extremely excellent migration resistance, and does not influence the structural performance of the rubber.
4. The non-migration POSS grafted antioxidant provided by the invention has various excellent performances of single-activity functional group POSS, such as improvement of heat resistance of materials, increase of compatibility of rubber and the antioxidant, improvement of atomic oxygen resistance and the like.
5. The non-migration POSS grafted antioxidant provided by the invention has a determined chemical structure and high purity, namely, a molecule of antioxidant is chemically grafted on a molecule of POSS.
Drawings
FIG. 1 is an infrared characterization of the non-migrating POSS grafted antioxidant prepared in example 1;
FIG. 2 is a nuclear magnetic silicon spectrum of a non-migrating POSS grafted antioxidant prepared in example 1;
FIG. 3 is a graph of the oxidative induction period test of NR/RTPO in application example 1;
FIG. 4 is a graph of the oxidation induction period as a function of extraction time for the NR/RTPO composite of application example 1.
Detailed Description
The non-migratory POSS graft antioxidant and the preparation method thereof of the present invention are further illustrated by the following examples. It is to be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as many insubstantial modifications and variations of the invention may be made by those skilled in the art in light of the teachings herein.
In the following application examples, the oxidation induction time was measured on the prepared compounded rubber by the method specified in ISO 11357-6, 2002. Under the condition of water bath at 50 ℃, the compounded rubber is immersed in distilled water, the water is changed every 12 hours, the compounded rubber is extracted, and the oxidation induction time of the extracted rubber is used as the evaluation of the migration condition of the antioxidant.
Example 1
Dissolving 9 parts by mass of heptaphenyl epoxy POSS and 5 parts by mass of RT base together in 100 parts by mass of anhydrous toluene to form a reaction system, removing air in the system by adopting nitrogen, starting heating under the protection of nitrogen, adding 0.01 part by mass of platinum catalyst through a micro-injector after the system starts to reflux, heating to 120 ℃, stirring and reacting for at least 36 hours, removing the solvent after the reaction is finished to obtain a solid product, performing Soxhlet extraction on the obtained solid product by using methanol as the solvent, removing the RT base which does not participate in the grafting reaction, and drying the solid product obtained after the extraction in vacuum to obtain the non-migration POSS grafted antioxidant (RTPO). The structural formula of the heptaphenyl epoxy POSS is as follows:
infrared characterization of RTPO was performed, and the results are shown in FIG. 1 at 2957cm-1And 2934cm-1The absorption peak appeared in (A) is attributed to methyleneThe C-H extension in the structure vibrates, and the methylene structure is part of the AGE molecular structure. 1358cm-1A new absorption peak appears, which is the characteristic absorption of C-N stretching vibration and is a part of the RT base structure, and 2254cm-1At a position of 882cm-1The nearby vibration absorption peak attributed to Si-H disappears, indicating that the Si-H structure in the monohydrogen POSS successfully carries out addition reaction with double bonds. In an RTPO infrared spectrogram, the absorption vibration absorption peak of the Si-O-Si cage type structure and the absorption peak position of the monosubstituted benzene ring are basically unchanged.
Nuclear magnetic characterization of RTPO and results are shown in FIG. 2, where29The Si-NMR spectrum showed that the absorption peak of the silicon atom in the Si-H structure at-82.95 ppm disappeared, indicating that the Si-H structure was absent. Three absorption peaks appear in the chemical shift range of-76 to-80 ppm, corresponding to-78.17, -77.77 and-77.67 ppm respectively, and the integrated area ratio of the three peaks is 4:1:3, which is consistent with the ratio of the number of silicon atoms of the three chemical environments in the cage structure. Wherein, the doublet near-77.77 ppm corresponds to the absorption peak of the silicon atom directly chemically grafted with the anti-aging agent, and the silicon atom is influenced by the grafted anti-aging agent, and the chemical potential shift moves in a low field and is split into a doublet structure.
Example 2
Dissolving 14 parts by mass of heptamethyl epoxy POSS and 10 parts by mass of RT base together in 100 parts by mass of anhydrous toluene to form a reaction system, removing air in the system by adopting nitrogen, starting heating under the protection of nitrogen, adding 0.03 part by mass of nickel catalyst through a micro-injector after the system starts to reflux, heating to 100 ℃, stirring and reacting for 36 hours, removing the solvent of the anhydrous toluene after the reaction is finished to obtain a solid product, performing Soxhlet extraction on the obtained solid product by using methanol as a solvent, removing the RT base which does not participate in the grafting reaction, and drying the extracted solid product in vacuum to obtain the non-migration POSS graft antioxidant (RTPO).
The structural formula of the heptamethyl epoxy POSS is as follows:
example 3
Dissolving 20 parts by mass of heptabutyl epoxy POSS and 15 parts by mass of RT base together in 100 parts by mass of anhydrous toluene to form a reaction system, removing air in the system by adopting nitrogen, starting heating under the protection of nitrogen, adding 0.03 part by mass of nickel catalyst through a micro-injector after the system starts to reflux, heating to 100 ℃, stirring and reacting for at least 36 hours, removing the solvent after the reaction is finished to obtain a solid product, performing Soxhlet extraction on the obtained solid product by using methanol as the solvent, removing the RT base which does not participate in the grafting reaction, and drying the solid product obtained after the extraction in vacuum to obtain the non-migration POSS grafted antioxidant (RTPO). The structural formula of the heptabutyl epoxy POSS is as follows:
example 4
Dissolving 15 parts by mass of heptabutyl monocarboxyl POSS and 6 parts by mass of RT base together in 100 parts by mass of anhydrous tetrahydrofuran to form a reaction system, removing air in the system by adopting argon gas, starting heating under the protection of argon gas, adding 0.06 part by mass of palladium catalyst through a micro-injector after the system starts to reflux, heating to 110 ℃, stirring and reacting for 32 hours, removing the solvent after the reaction is finished to obtain a solid product, performing Soxhlet extraction on the obtained solid product by taking acetic acid as the solvent, removing the RT base which does not participate in the grafting reaction, and drying the extracted solid product in vacuum to obtain the non-migration POSS grafted antioxidant (RTPO).
The structural formula of the heptabutyl monocarboxyl POSS is as follows:
example 5
Dissolving 12 parts by mass of heptabutyl monoacyl bromide POSS and 5 parts by mass of RT base together in 100 parts by mass of anhydrous carbon tetrachloride to form a reaction system, removing air in the system by adopting argon gas, starting heating under the protection of argon gas, adding 0.05 part by mass of nickel catalyst through a micro-injector after the system starts to reflux, heating to 110 ℃, stirring and reacting for 34 hours, removing the solvent after the reaction is finished to obtain a solid product, performing Soxhlet extraction on the obtained solid product by using formic acid as the solvent, removing the RT base which does not participate in the grafting reaction, and drying the extracted solid product in vacuum to obtain the non-migration POSS grafted antioxidant (RTPO).
The structural formula of the heptabutyl monoacyl bromide POSS is as follows:
application example 1
Adding 5 parts by mass of an anti-aging agent RTPO into 100 parts by mass of Natural Rubber (NR), uniformly dispersing the anti-aging agent RTPO in the natural rubber by a conventional rubber processing and mixing method, adding 2 parts by mass of a vulcanizing agent and 8 parts by mass of a vulcanization aid, and carrying out compression molding and vulcanization molding at 143 ℃ for 18min to obtain the NR/RTPO composite rubber material.
FIG. 3 is a graph showing the oxidation induction period test curve of NR/RTPO, and it can be found that the oxidation induction period of the pure natural rubber composite material is only 6.8min, while the oxidation induction period of the NR/RTPO composite material is 33.8 min. The longer the oxidation induction period is, the better the heat and oxygen aging resistance of the material is. FIG. 4 is a curve of the oxidation induction period of the NR/RTPO composite material along with the extraction time, wherein the oxidation induction time is still kept for 29min after 168h of extraction and is far longer than that of the pure natural rubber composite material.
Application example 2
Adding 10 parts by mass of an anti-aging agent RTPO into 100 parts by mass of Natural Rubber (NR), uniformly dispersing the anti-aging agent RTPO in the natural rubber by a conventional rubber processing and mixing method, adding 2 parts by mass of a vulcanizing agent and 8 parts by mass of a vulcanization aid, and carrying out compression molding and vulcanization molding at 143 ℃ for 18min to obtain the NR/RTPO composite rubber material.
The oxidation induction time of the material is 46.9min, and the oxidation induction time of the material is kept for 41.2min after 168h of extraction.
Application example 3
Adding 10 parts by mass of an anti-aging agent RTPO into 100 parts by mass of styrene butadiene rubber, uniformly dispersing the anti-aging agent RTPO in the styrene butadiene rubber by a conventional rubber processing and mixing method, adding 2 parts by mass of a vulcanizing agent and 7 parts by mass of a vulcanization aid, and carrying out compression molding and vulcanization molding at 151 ℃ for 30min to obtain the SBR/RTPO composite rubber material.
The oxidation induction time of the material is 77min, and the oxidation induction time is kept for 60min after 168h of extraction.
Application example 4
Adding 5 parts by mass of the antioxidant RTPO prepared in the example 1 into 100 parts of Styrene Butadiene Rubber (SBR), uniformly dispersing the antioxidant RTPO into the SBR by a conventional rubber processing and mixing method, adding 2 parts by mass of a vulcanizing agent and 7 parts by mass of a vulcanization aid, and carrying out compression molding and vulcanization molding at 151 ℃ for 30min to obtain the SBR/RTPO composite rubber material. The oxidation induction time of the material is 53min, and the oxidation induction time of the material is still kept for 44min after 168h of extraction.
Comparative example 1
Respectively adding 10 parts by mass of RTPO and 10 parts by mass of white carbon black/4010 NA into styrene-butadiene rubber, wherein the 4010NA content is the same as that of a graft anti-aging agent in the RTPO, uniformly dispersing the materials into the styrene-butadiene rubber by a conventional rubber processing and mixing method, adding 2 parts by mass of a vulcanizing agent and 7 parts by mass of a vulcanizing aid, and carrying out compression molding and vulcanization molding at 151 ℃ for 30min to obtain the SBR/silica/4010NA composite rubber material and the SBR/RTPO composite rubber material.
The obtained SBR/silica/4010NA composite rubber material and the SBR/RTPO composite phase rubber material are respectively subjected to an oxidation induction time test and a heat resistance test under an air condition, and the results are as follows:
1. the oxidation induction time test shows that the oxidation induction time of SBR/4010NA is 42min, and the oxidation induction time of SBR/RTPO is 77 min. After 168 hours of extraction, the oxidation induction time of SBR/4010NA is 34min, and the oxidation induction time of SBR/RTPO is as high as 60min, which shows that the RTPO prepared by the invention has high oxidation and aging resistance and excellent anti-aging effect.
2. The heat resistance test under the air condition finds that the thermal-oxidative degradation temperature of SBR/RTPO is improved by about 20 ℃, but the thermal-oxidative degradation temperature of SBR/4010NA is not improved, which shows that the RTPO prepared by the invention not only has excellent extraction resistance and oxidation and aging resistance, but also can obviously improve the thermal-oxidative degradation temperature of SBR and improve the heat resistance of rubber materials.
Claims (6)
1. A preparation method of a non-migration POSS grafted antioxidant is characterized by comprising the following steps: dissolving 5-20 parts by mass of RT base and 5-20 parts by mass of single-activity functional group POSS together in 100 parts by mass of organic solvent to form a reaction system, heating the reaction system under the protection of inert gas until reflux begins, adding 0.01-0.08 part by mass of catalyst, stirring and reacting for 0.5-40 h at 100-120 ℃, removing the organic solvent after the reaction is finished to obtain a solid product, purifying the solid product to remove raw materials which do not participate in the reaction, and performing vacuum drying on the purified product to obtain the non-migration POSS grafted antioxidant; the structural formula of the POSS with the single active functional group is as follows:
wherein R is1Is one of phenyl, butyl, methyl and cyclohexane, R2Is an organic substitution unit containing one active functional group of ester group, carboxyl group, hydroxyl group, acyl bromide group, acid anhydride group and epoxy group.
2. The method of claim 1, wherein the organic solvent is one of toluene, tetrahydrofuran, carbon tetrachloride, carbon disulfide, benzene, hexane, chloroform, ethyl acetate, and methylene chloride.
3. The method for preparing the non-migratory POSS graft aging inhibitor as claimed in claim 1 or 2, wherein the catalyst is one of platinum, palladium and nickel.
4. The method for producing a non-migratory POSS graft antioxidant as claimed in claim 1 or 2, wherein the organic solvent is removed by one of rotary evaporation, distillation under reduced pressure and freeze-drying.
5. The method for producing a non-migratory POSS grafted antioxidant as set forth in claim 1 or 2, wherein the purification of the solid product is performed by one of solution extraction, centrifugal separation and column separation.
6. The non-migratory POSS grafted antioxidant prepared by the method of any one of claims 1 to 5.
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| CN110156919B (en) * | 2018-02-10 | 2020-07-28 | 北京化工大学 | Rubber antioxidant and preparation method thereof |
| CN110982282B (en) * | 2019-12-26 | 2022-01-04 | 江门市胜鹏化工实业有限公司 | Fluorosilicone rubber composition and preparation method thereof |
| CN113354929B (en) * | 2021-06-07 | 2022-07-12 | 万华化学（宁波）有限公司 | Low-precipitation biodegradable PLA alloy, preparation method thereof and straw material |
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