CN107641325A - Non-migrating type POSS grafting age resistor and preparation method thereof - Google Patents
Non-migrating type POSS grafting age resistor and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of non-migrating type POSS grafting age resistor and preparation method thereof, reacted using the active group in the active amine in amines antioxidants and single active function groups POSS, by amines antioxidants chemical graft on POSS molecules, so as to obtain POSS grafting age resistor.The present invention provides the age resistor of a kind of new higher oxygen aging resistance and higher ability of resisting to migration for the aging protection of rubber and other rubber elastomers, does not influence to improve anti-aging efficiency while rubber and other rubber elastomer structural behaviours.
Description
Technical field
The invention belongs to rubber antioxidant field, more particularly to a kind of new non-migrating type POSS grafting age resistor and its system
Preparation Method.
Technical background
Rubber and elastomer based on rubber is with its excellent high resiliency, high-flexibility and excellent processability
It can be widely used among the every field of national economy.But because rubber has high degree of unsaturation, therefore rubber
Aging easily occurs during processing and use.Aging can deteriorate elastomeric material performance, finally completely lose use
Performance even leads to a disaster.At present, most simple and effective anti-aging means are exactly that age resistor is added during rubber processing.Make
Small molecule age resistor with most age resistor, and traditional small molecule age resistor exist during processing and use it is volatile,
The problems such as easy to migrate, effective age resistor concentration in product is caused to reduce, this is unfavorable for the permanent protection of rubber.And migrate
The age resistor gone out also pollutes the environment and is detrimental to health.In view of the disadvantages mentioned above of traditional small molecule age resistor, non-migrating
Type age resistor causes the attention of people.In general, preparing non-migrating type age resistor mainly has following several ways：(1) increase
The molecular weight of big age resistor, (2) graft on age resistor on the strand of polymeric matrix, and age resistor is grafted on filler by (3)
Surface.Shortcoming and problem is individually present in these three modes：Simple increase age resistor molecular weight can make effective anti-aging group ratio
Reduce and be unfavorable for the dispersed of age resistor, cause the protection efficiency of age resistor to reduce；Age resistor is grafted on into polymer
The dispersed of age resistor can be not only influenceed on substrate molecule chain, can also influence the network structure of rubber, therefore anti-aging efficiency
It is not high, it can also influence rubber performance；Age resistor is grafted on into filler surface, this method can influence to a certain extent rubber with
The interaction of filler.Therefore, exploitation one kind is still badly in need of in the development and application of high-performance rubber has higher oxygen aging resistance
And the green age resistor of higher ability of resisting to migration.
The content of the invention
For the deficiency of traditional small molecule age resistor and existing non-migrating type age resistor, it is an object of the invention to provide one kind
The preparation method of new non-migrating type POSS grafting age resistor, one kind is provided for the aging protection of rubber and other rubber elastomers
New higher oxygen aging resistance and the age resistor of higher ability of resisting to migration, not influence rubber and other rubber elastomer knots
Anti-aging efficiency is improved while structure performance.
The present general inventive concept：POSS (cage modle polysilsesquioxane) forms nothing by the Si-O silica skeletons alternately connected
Machine kernel, the group R that Si atoms are connected on its eight drift angles can be reactivity or inertia group, be a kind of special
Organic and inorganic cage modle hybrid molecule, structural formula are：
It can assign polymeric material many excellent performances, such as improve depolymerization temperature, reduce material degradation
Speed, improve dimension stability etc..Eight organo-functional groups of eight vertex make it with polymerizeing in POSS molecular structures
Thing has good compatibility, and according to different can need that eight organo-functional groups are adjusted, and has POSS molecules
Different reactivities.It is reactive group that single active function groups POSS, which refers in the groups of eight drift angles only one, and remaining seven
Individual is inertia group, and its structural formula is
Wherein R1 is one kind in phenyl, butyl, methyl, cyclohexyl, and R2 is to contain ester groupCarboxylHydroxyl, acylbromideAcid anhydrides (Wherein R is organic structure), epoxyThe organic substitution unit of any one in isoreactivity functional group, such as Deng.The present invention utilizes the active amine in amines antioxidants and the active group in single active function groups POSS
Reaction, by amines antioxidants chemical graft on POSS molecules, so as to obtain POSS grafting age resistor.
The preparation method of non-migrating type POSS grafting age resistor provided by the invention, by the 4-aminodiphenylamine (4- of 5~20 mass parts
Aminodiphenylamine, also known as mutual-amido two polyaniline) with single active function groups POSS of 5~20 mass parts 100 mass parts are dissolved in jointly
Organic solvent in form reaction system, after the air in inert gas exclusion system, start under inert gas shielding
Heating, the catalyst of 0.01~0.08 mass parts is added after system starts backflow, then the stirring reaction at 100~120 DEG C
0.5~40h, reaction remove organic solvent after terminating and obtain solid product, and purification removing is carried out to solid product and is not engaged in instead
The raw material answered, the product after purification is dried in vacuo, and has both obtained non-migrating type POSS grafting age resistor；
The structural formula of single active function groups POSS is as follows：
Wherein R1 is one kind in phenyl, butyl, methyl, cyclohexyl, and R2 is to contain ester groupCarboxylHydroxyl (- OH), acylbromide groupAnhydride groupEpoxide groupIn a kind of active function groups organic substitution unit, such as Deng.
In the above-mentioned technical proposal of the present invention, the organic solvent is preferably toluene, tetrahydrofuran, carbon tetrachloride, two
One kind in nitric sulfid, benzene, hexane, chloroform, ethyl acetate and dichloromethane.
In the above-mentioned technical proposal of the present invention, the catalyst is preferably one kind in platinum, palladium and nickel.
In the above-mentioned technical proposal of the present invention, the preferred rotary evaporation of mode of organic solvent, vacuum distillation, distillation are removed
With one kind in freeze-drying.
In the above-mentioned technical proposal of the present invention, the preferred solution extracting of mode, the centrifugation point that are purified to solid product
From with one kind in post separation.
The present invention provides non-migrating type POSS grafting age resistor prepared by the above method.
Compared with prior art, the invention has the advantages that：
1. the present invention provides a kind of new age resistor for the aging protection of rubber and other rubber elastomers.
2. non-migrating type POSS grafting age resistor provided by the invention has excellent ability of resisting to migration and thermo oxidative aging
Performance, POSS grafting age resistor is applied in existing rubber, can significantly extend the oxidation induction time of rubber, and
With extremely excellent ability of resisting to migration, while the structural behaviour of rubber in itself is not influenceed.
4. non-migrating type POSS grafting age resistor provided by the invention has single active function groups POSS a variety of superiority concurrently
Can, the heat resistance of material is such as improved, increases rubber and the compatibility of age resistor and anti-atomic oxygen performance etc..
5. non-migrating type POSS grafting age resistor provided by the invention has the chemical constitution determined, purity is high, i.e., one point
Chemical graft has a molecule age resistor on sub- POSS.
Brief description of the drawings
Fig. 1 is the IR Characterization figure that non-migrating type POSS prepared by embodiment 1 is grafted age resistor；
Fig. 2 is the nuclear-magnetism silicon spectrogram that non-migrating type POSS prepared by embodiment 1 is grafted age resistor；
Fig. 3 is the oxidation induction period test curve of NR/RTPO in application examples 1；
Fig. 4 is the oxidation induction period of NR/RTPO composites in application examples 1 with the change curve of extraction times.
Embodiment
Age resistor and preparation method thereof is grafted below by embodiment to non-migrating type POSS of the present invention to make further
Explanation.It is necessarily pointed out that following examples are served only for that the present invention is further described, it is impossible to are interpreted as to this
The limitation of invention protection domain, the person skilled in the art in the field can make some according to present disclosure and nonessential change
Enter and adjust.
In following application examples, ISO 11357-6 are used to the compounded rubber prepared, method as defined in 2002 is tested
Oxidation induction time.Under 50 DEG C of water bath condition, compounded rubber is immersed in distilled water, changes within every 12 hours a water, it is right
Compounded rubber is stripped, the evaluation using the oxidation induction time of the rubber after extracting as age resistor migration situation.
Embodiment 1
Seven phenyl epoxy POSS of 9 mass parts and 5 mass parts 4-aminodiphenylamine are dissolved in the dry toluene of 100 mass parts jointly
Middle formation reaction system, using the air in nitrogen exclusion system, begin to warm up under nitrogen protection, after system starts backflow
The platinum catalyst of 0.01 mass parts is added by micro syringe, and is heated to 120 DEG C of stirring reaction at least 36h, reaction terminates
Solvent is removed afterwards and obtains solid product, gained solid product is subjected to soxhlet type by solvent of methanol, removing is not engaged in connecing
The 4-aminodiphenylamine of branch reaction, gained solid product after extracting is dried in vacuo, that is, obtains non-migrating type POSS grafting age resistor
(RTPO).Seven phenyl epoxy POSS structural formula is：
IR Characterization is carried out to RTPO, Fig. 1 is as a result seen, in 2957cm-1And 2934cm-1The absworption peak that place occurs belongs to
C-H stretching vibrations in methylene based structures, methylene based structures are the parts in AGE molecular structures.1358cm-1Place also occurs
New absworption peak, this is the characteristic absorption of C-N stretching vibrations, is the part in 4-aminodiphenylamine structure, and 2254cm-1Place and
882cm-1The neighbouring vibration absorption peak for belonging to Si-H is disappeared, and the Si-H structures success in instruction sheet hydrogen POSS is carried out with double bond
Addition reaction.In RTPO infrared spectrums, the suction for absorbing vibration absorption peak and monosubstituted phenyl ring of Si-O-Si cagelike structures
Peak position is received not change substantially.
Nuclear-magnetism sign is carried out to RTPO, Fig. 2 is as a result seen, at it29It can see in Si-NMR test spectrograms, -82.95ppm
Silicon atom absworption peak in the Si-H structures at place disappears, and illustrates without Si-H structures.In -76~-80ppm chemical shift ranges
There is absworption peak at three, correspond to -78.17, -77.77 and -77.67ppm respectively, and the integral area ratio at these three peaks is 4:
1:3, this is consistent with the ratio between silicon atom number of three kinds of chemical environments in cagelike structure.Wherein, it is bimodal right near -77.77ppm
What is answered is the absworption peak for the silicon atom that direct chemical graft has age resistor, and silicon atom is influenceed by grafting age resistor at this, changes
Degree, which is shifted to low field movement and split, is divided into two peak structure.
Embodiment 2
By seven methyl epoxy POSS of 14 mass parts and 10 mass parts 4-aminodiphenylamine be dissolved in jointly 100 mass parts without water beetle
Reaction system is formed in benzene, using the air in nitrogen exclusion system, is then begun to warm up under nitrogen protection, the system for the treatment of starts
The Raney nickel of 0.03 mass parts is added after backflow by micro syringe, and is heated to 100 DEG C of stirring reaction 36h, reaction knot
Solvent dry toluene is removed after beam and obtains solid product, gained solid product is subjected to soxhlet type by solvent of methanol, removed
The 4-aminodiphenylamine of graft reaction is not engaged in, gained solid product after extracting is dried in vacuo, had both obtained non-migrating type POSS grafting
Age resistor (RTPO).
Seven methyl epoxy POSS structural formulas are：
Embodiment 3
By seven butyl epoxy POSS of 20 mass parts and 15 mass parts 4-aminodiphenylamine be dissolved in jointly 100 mass parts without water beetle
Reaction system is formed in benzene, using the air in nitrogen exclusion system, is begun to warm up under nitrogen protection, the system for the treatment of starts to flow back
The Raney nickel of 0.03 mass parts is added by micro syringe afterwards, and is heated to 100 DEG C of stirring reaction at least 36h, reaction knot
Solvent is removed after beam and obtains solid product, gained solid product is subjected to soxhlet type by solvent of methanol, removing is not engaged in
The 4-aminodiphenylamine of graft reaction, gained solid product after extracting is dried in vacuo, had both obtained non-migrating type POSS grafting age resistor
(RTPO).Seven butyl epoxy POSS structural formulas are：
Embodiment 4
Seven butyl mono carboxylic POSS of 15 mass parts and the 4-aminodiphenylamine of 6 mass parts are dissolved in the anhydrous of 100 mass parts jointly
Reaction system is formed in tetrahydrofuran, using the air in argon gas exclusion system, is begun to warm up under argon gas protection, the system for the treatment of is opened
Begin to add the palladium catalyst of 0.06 mass parts by micro syringe after backflow, and be heated to 110 DEG C of stirring reaction 32h, react
Solvent is removed after end and obtains solid product, gained solid product is subjected to soxhlet type by solvent of acetic acid, removing is not joined
With the 4-aminodiphenylamine of graft reaction, gained solid product after extracting is dried in vacuo, that is, obtains non-migrating type POSS grafting age resistor
(RTPO)。
Seven butyl mono carboxylic POSS structural formulas are：
Embodiment 5
Seven butyl list acylbromide POSS of 12 mass parts and the 4-aminodiphenylamine of 5 mass parts are dissolved in the anhydrous of 100 mass parts jointly
Reaction system is formed in carbon tetrachloride, using the air in argon gas exclusion system, is begun to warm up under argon gas protection, the system for the treatment of is opened
Begin to add the Raney nickel of 0.05 mass parts by micro syringe after backflow, and be heated to 110 DEG C of stirring reaction 34h, react
Solvent is removed after end and obtains solid product, gained solid product is subjected to soxhlet type by solvent of formic acid, removing is not joined
With the 4-aminodiphenylamine of graft reaction, gained solid product after extracting is dried in vacuo, that is, obtains non-migrating type POSS grafting age resistor
(RTPO)。
Seven butyl list acylbromide POSS structural formulas are：
Application examples 1
The age resistor RTPO of 5 mass parts is added in 100 parts of natural rubbers (NR), compounding process is processed by traditional rubber
It is dispersed in natural rubber, adds the vulcanizing agent of 2 mass parts and the vulcanization aid of 8 mass parts, then in 143 DEG C of conditions
Lower progress 18min is molded sulfidization molding, obtains NR/RTPO composite rubber materials.
Fig. 3 is NR/RTPO oxidation induction period test curve, can be drawn by figure, the oxygen of pure natural rubber composite
Change induction period and there was only 6.8min, and the oxidation induction time of NR/RTPO composites is 33.8min.Oxidation induction period is longer, says
The thermo oxidative aging performance of bright material is better.Fig. 4 is that the oxidation induction period of NR/RTPO composites is bent with the change of extraction times
Line, its oxidation induction time still maintains 29min after extracting 168h, and the oxidation much larger than pure natural rubber composite induces
Phase.
Application examples 2
The age resistor RTPO of 10 mass parts is added in 100 parts of natural rubbers (NR), mixing side is processed by traditional rubber
Method is dispersed in natural rubber, adds the vulcanizing agent of 2 mass parts and the vulcanization aid of 8 mass parts, then in 143 DEG C of bars
18min molding sulfidization moldings are carried out under part, obtain NR/RTPO composite rubber materials.
The oxidation induction time of the material is 46.9min, and its oxidation induction time still maintains after extracting 168h
41.2min。
Application examples 3
The age resistor RTPO of 10 mass parts is added in 100 parts of butadiene-styrene rubber, processing compounding process by traditional rubber will
It is dispersed in butadiene-styrene rubber, adds the vulcanizing agent of 2 mass parts and the vulcanization aid of 7 mass parts, then under the conditions of 151 DEG C
30min molding sulfidization moldings are carried out, obtain SBR/RTPO composite rubber materials.
The oxidation induction time of the material is 77min, and its oxidation induction time still maintains 60min after extracting 168h.
Application examples 4
Age resistor RTPO prepared by the embodiment 1 of 5 mass parts is added in 100 parts of butadiene-styrene rubber (SBR), passes through conventional rubber
Glue processing compounding process is dispersed in butadiene-styrene rubber, and the vulcanization for adding the vulcanizing agent and 7 mass parts of 2 mass parts helps
Agent, 30min molding sulfidization moldings are carried out under the conditions of 151 DEG C, obtain SBR/RTPO composite rubber materials.The oxidation of the material lures
It is 53min to lead the time, and its oxidation induction time still maintains 44min after extracting 168h.
Comparative example 1
White carbon/4010NA of the RTPO of 10 mass parts, 10 mass parts is added in butadiene-styrene rubber respectively, wherein 4010NA
Content with RTPO be grafted age resistor content it is identical, by traditional rubber process compounding process be dispersed in butylbenzene
In rubber, the vulcanizing agent of 2 mass parts and the vulcanization aid of 7 mass parts are added, then 30min molding sulphur is carried out under the conditions of 151 DEG C
Chemical conversion type, obtain SBR/silica/4010NA composite rubber materials and SBR/RTPO composite rubber materials.
Gained SBR/silica/4010NA composite rubber materials and SBR/RTPO compound phases elastomeric material are subjected to oxygen respectively
Change heat resistance under induction time test and air conditionses to test, it is as a result as follows：
1st, oxidation induction time test finds that SBR/4010NA oxidation induction time is 42min, and SBR/RTPO oxygen
Change induction time is 77min.After extracting 168h, SBR/4010NA oxidation induction time is 34min, and SBR/RTPO oxidation
Induction time is up to 60min, illustrates that RTPO produced by the present invention has high oxygen aging resistance, and there is excellent anti-aging to imitate
Fruit.
2nd, heat resistance test is found under air conditionses, about 20 DEG C of SBR/RTPO thermal-oxidative degradations temperature raising, and SBR/
4010NA thermal-oxidative degradation temperature has no raising, illustrates RTPO produced by the present invention except old with excellent anti-extracting, antioxygen
Change performance and it is outer, SBR thermal-oxidative degradation temperature can also be significantly improved, improve the heat resistance of elastomeric material.
Claims (6)
- A kind of 1. preparation method of non-migrating type POSS grafting age resistor, it is characterised in that：By the 4-aminodiphenylamine of 5~20 mass parts with Single active function groups POSS of 5~20 mass parts is dissolved in the organic solvent of 100 mass parts jointly forms reaction system, in inertia Under gas shield, reaction system is heated to starting the catalyst that backflow adds 0.01~0.08 mass parts, then 100~120 0.5~40h of stirring reaction at DEG C, reaction remove organic solvent after terminating and obtain solid product, and carrying out purification to solid product removes Go to be not engaged in the raw material reacted, the product after purification is dried in vacuo, both obtained non-migrating type POSS grafting age resistor； The structural formula of single active function groups POSS is as follows：Wherein R1For one kind in phenyl, butyl, methyl and cyclohexyl, R2For containing ester group, carboxyl, hydroxyl, acylbromide group, A kind of organic substitution unit of active function groups in anhydride group and epoxide group.
- 2. non-migrating type POSS is grafted the preparation method of age resistor according to claim 1, it is characterised in that described organic molten Agent is one kind in toluene, tetrahydrofuran, carbon tetrachloride, carbon disulfide, benzene, hexane, chloroform, ethyl acetate and dichloromethane.
- 3. the preparation method of non-migrating type POSS grafting age resistor according to claim 1 or claim 2, it is characterised in that the catalysis Agent is one kind in platinum, palladium and nickel.
- 4. the preparation method of non-migrating type POSS grafting age resistor according to claim 1 or claim 2, it is characterised in that remove organic The mode of solvent is one kind in rotary evaporation, vacuum distillation and distillation and freeze-drying mode.
- 5. the preparation method of non-migrating type POSS grafting age resistor according to claim 1 or claim 2, it is characterised in that produced to solid The mode that thing is purified is one kind in solution extracting, centrifugation and post separation mode.
- 6. the non-migrating type POSS grafting age resistor being prepared using any claim methods described in Claims 1 to 5.
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| CN110982282A (en) * | 2019-12-26 | 2020-04-10 | 陈志强 | Fluorosilicone rubber composition and preparation method thereof |
| CN113354929A (en) * | 2021-06-07 | 2021-09-07 | 万华化学（宁波）有限公司 | Low-precipitation biodegradable PLA alloy, preparation method thereof and straw material |
| CN114573944A (en) * | 2022-03-31 | 2022-06-03 | 金发科技股份有限公司 | High-gloss high-surface-hardness ABS (acrylonitrile-butadiene-styrene) composite material as well as preparation method and application thereof |
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| 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 |
| CN114573944A (en) * | 2022-03-31 | 2022-06-03 | 金发科技股份有限公司 | High-gloss high-surface-hardness ABS (acrylonitrile-butadiene-styrene) composite material as well as preparation method and application thereof |
| CN114573944B (en) * | 2022-03-31 | 2023-11-03 | 金发科技股份有限公司 | High-gloss high-surface-hardness ABS composite material and preparation method and application thereof |
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