CN110218330A - A kind of selfreparing modified silicon rubber and preparation method thereof - Google Patents
A kind of selfreparing modified silicon rubber and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to technical field of polymer materials, and in particular to a kind of selfreparing modified silicon rubber and preparation method thereof.Dynamic covalent bond and polyamide structure and silicon oxygen chemistry of silicones key be not only used as selfreparing unit but also be used as activeness and quietness unit in the polyimide modified silicon rubber of selfreparing of the invention, synthesize the high intensity with repair function, high tenacity copolymer, in addition it can be reacted inside system without cosolvent, this greatly avoids selfreparing silastic material and brings environmental problem caused by the release of volatilizable object (VOC) during making and using；Method prepared by the present invention is simple and efficient, and reaction condition is controllable, and low energy consumption, environment friendly and pollution-free, and in subsequent industrialized production, process operability is higher.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to a kind of selfreparing modified silicon rubber and its preparation side
Method.
Background technique
Organic siliconresin is the poly- silicon oxygen of cross-linking type thermosetting property using Si-O-Si to connect organic group on main chain, silicon atom
Alkane system.Special the Nomenclature Composition and Structure of Complexes assigns silicone resin and possesses splendid heat resistance and weatherability, due to its is light, wear-resisting,
Easy processing, it is easily molded the advantages that, industry, life etc. multiple fields have been more and more widely used.Its product relates generally to
Insullac, coating, adhesive, plastics, fire retardant, anti-blushing agent, micro mist and ladder polymer etc. are spun in electronic apparatus, light industry
It knits, build, medical treatment, the fields such as space flight have a wide range of applications.But organosilicon material is in molding process and in the external world
Under the influence of the environmental factors such as stress, inevitably it is easy by extraneous mechanical damage, the accumulation of this damage is final
It will cause material failure, cause material to lose corresponding function, to seriously limit reliability and the service life of product, this will be big
The big maintenance and alternative costs for improving material.For the visible crack of material, often welded using traditional mechanical connection, plastics
It is repaired with the methods of being glued, but this is often difficult to reach the original comprehensive performance of material again, and takes time and effort, effect
It is often ideal not to the utmost, and to solve the problems, such as this, so that organosilicon material is had self-reparing capability is then a highly effective solution
Certainly scheme.
Currently, self-repair material can be divided into two major classes according to the difference for repairing supply mode, i.e. foreign aid's type and intrinsic
Type.Foreign aid's type self-repair material of renovation agent is wrapped up with microcapsules or doughnut to repair environmental damage, therefore there is polymerization
The problem of renovation agent exhausts in object matrix, and can only often repair primary.However, Intrinsical selfreparing is then by polymer
The reversible dynamic chemical process of chemical bond (non-covalent bond or dynamic covalent bond) realizes the crack forming mechanism of polymeric inner.Therefore,
Compared to foreign aid's type self-repair material, in the external lefts such as light or heat bottom right, Intrinsical selfreparing ideally be can be realized infinitely
Secondary circulation reparation.
In general, introducing the dynamic reversible covalent bond or reversible non-covalent key phase of reciprocal characteristics in polymer chain structure
The structural unit of interaction is the main method for creating selfreparing high molecular material.However, on the one hand, existing selfreparing high score
The selfreparing mechanism of sub- material is relatively single, can not obtain the material for having both comprehensive performance well with ideal selfreparing effect；Separately
On the one hand, the structural unit with the interaction of reversible non-covalent key is typically necessary when introducing high score chain in reaction system
Cosolvent is added to realize in the inside, this will lead to selfreparing high molecular material and brings volatilizable object during making and using
(VOC) release and energy consumption and environmental problem；It is a kind of with solvent-free environment-protection and multiple selfreparing to how to prepare in recent years
The organic siliconresin of characteristic is of great significance, this is just becoming the big research hotspot on polymeric material field.
Summary of the invention
The object of the present invention is to provide a kind of selfreparing modified silicon rubbers and preparation method thereof, and the silicon rubber of preparation has both excellent
Different mechanical property and stable self-regeneration characteristic can reach the function of self-regeneration when impaired by heating.
To achieve the above object, the following technical solution that the present invention takes:
A kind of selfreparing modified silicon rubber, structural formula are as follows:
Wherein, m=70-150,1≤n≤10,1≤x≤10,
Further, a kind of preparation method of selfreparing modified silicon rubber, specifically comprises the following steps:
Step 1: using p-phenylenediamine and pyromellitic dianhydride as reaction raw materials, maleic anhydride is end-capping reagent, prepares oligomeric acyl
Imines obtains product I, and structural formula is as follows:
Wherein: 1≤n≤10；
Step 2: the poly- of double chlorine sealing ends is prepared using double hydroxy-terminated polysiloxane silicone oil and dichlorodimethylsilane as raw material
Siloxanes silicone oil, structural formula are as follows:
Wherein, m=70-150；
Step 3: the polysiloxanes silicone oil and furfuryl alcohol of the double chlorine sealing end obtained using step 2 obtain product II as raw material,
Structural formula is as follows:
Step 4: product I and product II as raw material, are prepared polyimide modified silicon rubber, structural formula is as follows:
Wherein, 1≤x≤10.
Further, a kind of preparation method of selfreparing modified silicon rubber, specifically comprises the following steps::
Step 1:
1.0 parts and 0.5-0.9 parts of pyromellitic dianhydride of phenylenediamine is added in dimethyl acetamide, is stirred at room temperature anti-
It answers 5-8h, is added maleic anhydride 0.5-0.1 part, triethylamine 1.5-2.0 parts and acetic anhydride 1.5-2.0 is added in the reaction was continued 3-4h
Part, 60 DEG C are warming up to, 8-10h is reacted.Reaction solution is poured into petroleum ether, a large amount of solid precipitatings, filtering, by consolidating for acquisition occurs
Body is washed 3 times with 5wt% sodium bicarbonate aqueous solution, and deionized water is washed three times, dry, prepares product I.
Step 2:
2 parts of dichlorodimethylsilane is added into solvent ethyl acetate, 4-6 parts of triethylamine does acid binding agent, is placed in
Under condition of ice bath, double 1 part of silicone oil of hydroxy-terminated polysiloxanes are then added dropwise by constant pressure funnel in stirring, are dripped
Recession is warming up to 60 DEG C after going ice bath to react 2-4h again the reaction was continued after 0.5-1h that reaction was completed, precipitating is filtered to remove, by filtrate
Revolving removes ethyl acetate, then is washed 2 times with hexamethylene, dries, and obtains the polysiloxanes silicone oil of double chlorine sealing ends；
Step 3:
Under condition of ice bath, pass through the acetic acid for the polysiloxanes silicone oil that constant pressure funnel is blocked to double chlorine in stirring
0.5 part of furfuryl alcohol is added dropwise in ethyl ester solution, drips after recession goes ice bath to react 2-4h again, after being warming up to 60 DEG C of reaction 0.5-1h
Reaction was completed, stops stirring, and revolving removes solvent, and is washed 2 times with hexamethylene, and drying obtains product II；
Step 4:
Under inert gas protection, product I and product II are added in reaction unit, slowly increase temperature until mixing
Uniformly, 2-3h is reacted after being continuously heating to certain temperature, is cooled to room temperature after reaction, solid matter is washed with ethyl acetate
It washs 2 times, drying, which derives from, repairs polyimide modified silicon rubber.
Further, the molar ratio of product I and product II is 1:2-2.2 in step 4 described above.
Further, mixing temperature described above is 50-60 DEG C.
Further, reaction temperature described above is 100-110 DEG C.
The present invention have it is following the utility model has the advantages that
(1) Diels-Alder dynamic covalent bond and polyamide knot in the polyimide modified silicon rubber of selfreparing of the invention
Structure had not only been used as selfreparing unit but also had been used as enhancement unit, synthesized the high-intensitive copolymer with repair function；Simultaneously in silicon rubber
After being destroyed, the silicon oxygen chemistry of silicones key contained in structure is acted on from migration and self assembly by silicon oxygen silicon, makes up impaired material
Expect surface simultaneously, moreover it is possible to the toughness of reinforcing material, therefore the silicon rubber not only possesses autonomous repair function, but also possesses very high
Intensity and toughness.
(2) the polysiloxanes silicone oil (product II) for double chlorine sealing end that furfuryl alcohol of the invention replaces is liquid condition, and horse is added
Carry out acid anhydrides as end-capping reagent, can effectively control the molecular weight (product I) of polyimides, be allowed to fusible under heating conditions,
Therefore it when carrying out DA cross-linking reaction, can be reacted inside system without cosolvent, this greatly avoids selfreparing silicon
Rubber material brings environmental problem caused by the release of volatilizable object (VOC) during making and using.
(3) silicon rubber prepared by the present invention is linear structure, has good ductility, knot when giving 110 DEG C or more
The Diels-Alder dynamic covalent bond contained in structure can crack in a heated condition, have excellent self-repair function, and should
Composite silicon rubber is reviewed one's lessons by oneself compared to general silicon rubber, there is very high intensity and toughness (tensile strength and fracture toughness), draw
It stretches intensity and reaches as high as 14MPa, elongation at break reaches as high as 700%.
(4) method prepared by the present invention is simple and efficient, and reaction condition is controllable, and low energy consumption, environment friendly and pollution-free, in subsequent work
During industry metaplasia produces, process operability is higher.
Detailed description of the invention
Fig. 1 is the product I nuclear magnetic spectrogram that embodiment 1 synthesizes.
Fig. 2 is the product II nuclear magnetic spectrogram that embodiment 1 synthesizes.
Fig. 3 is the Total Reflection Infrared spectrogram for the silicon rubber that embodiment 1 synthesizes.
Fig. 4 is the scratch removal figure of composite material prepared by the embodiment of the present invention 4.
Specific embodiment
Presently in connection with embodiment, the present invention is described in further detail.
Embodiment 1
A kind of preparation method of selfreparing modified silicon rubber, specifically comprises the following steps::
Step 1:
1.0 parts and 0.5 part of pyromellitic dianhydride of phenylenediamine is added in dimethyl acetamide, reaction is stirred at room temperature
5h is added 0.1 part of maleic anhydride, the reaction was continued 3h, is added 1.5 parts and 1.5 parts of acetic anhydride of triethylamine, is warming up to 60 DEG C, reaction
8h.Reaction solution is poured into petroleum ether, a large amount of solid precipitatings occurs, filtering is water-soluble with 5wt% sodium bicarbonate by the solid of acquisition
Liquid washs 3 times, and deionized water is washed three times, dry, product I is prepared, with CDCl3Make solvent, nuclear-magnetism characteristic absorption spectrogram
(as shown in Figure 1): δ=8.32~8.35 (a, 2H), δ=7.84~7.88 (b, 4H), δ=7.35~7.39 (c, 8H)；
Step 2:
2 parts of dichlorodimethylsilane is added into solvent ethyl acetate, 4 parts of triethylamine does acid binding agent, is placed in ice
Under the conditions of bath, double 1 part of silicone oil of hydroxy-terminated polysiloxanes are then added dropwise by constant pressure funnel in stirring, after dripping
Remove ice bath react again be warming up to 60 DEG C after 2h the reaction was continued 0.5h after reaction was completed, be filtered to remove precipitating, filtrate revolving removed
Ethyl acetate is removed, then is washed 2 times with hexamethylene, is dried, the polysiloxanes silicone oil of double chlorine sealing ends is obtained；
Step 3:
Under condition of ice bath, pass through the acetic acid for the polysiloxanes silicone oil that constant pressure funnel is blocked to double chlorine in stirring
0.5 part of furfuryl alcohol is added dropwise in ethyl ester solution, drips after recession goes ice bath to react 2h again, terminates after being warming up to 60 DEG C of reaction 0.5h
Reaction stops stirring, and revolving removes solvent, and is washed 2 times with hexamethylene, and drying obtains product II, with CDCl3Make solvent, core
Magnetic characteristic absorption spectrogram (as shown in Figure 2): δ=7.55~7.59 (a, 2H), δ=6.39~6.43 (b, 4H), δ=4.88~
4.91 (c, 4H), δ=0.13~0.16 (d, the peak of main chain methyl)；
Step 4:
It is in molar ratio that 1:2.1 is added in reaction unit by product I and product II, slowly under nitrogen gas protection
Increase temperature be 50 DEG C until be uniformly mixed, be continuously heating to be 100 DEG C after react 3h, be cooled to room temperature after reaction, will
Solid matter is washed 2 times with ethyl acetate, and drying, which derives from, repairs polyimide modified silicon rubber, is detected by Total Reflection Infrared
(Fig. 3), the infrared spectroscopy of silastic structure is in 1775cm-1The DA addition product characteristic absorption peak that place occurs；1252cm-1For
C-O-C stretching vibration peak on the DA ring of generation；1096cm-1For the absorption peak of C-O-C outside ring；1719cm-1Place occurs very
The stretching vibration of carbonyl (C=O) in apparent amide molecule；1264cm-1Place is the absorption peak of Si-CH3 on siloxanes；
1055cm-1Place is the absorption peak of Si-O-Si.
Embodiment 2
A kind of preparation method of selfreparing modified silicon rubber, specifically comprises the following steps::
Step 1:
1.0 parts and 0.6 part of pyromellitic dianhydride of phenylenediamine is added in dimethyl acetamide, reaction is stirred at room temperature
6h is added 0.3 part of maleic anhydride, the reaction was continued 4h, is added 1.8 parts and 1.8 parts of acetic anhydride of triethylamine, is warming up to 60 DEG C, reaction
8h.Reaction solution is poured into petroleum ether, a large amount of solid precipitatings occurs, filtering is water-soluble with 5wt% sodium bicarbonate by the solid of acquisition
Liquid washs 3 times, and deionized water is washed three times, dry, prepares product I.
Step 2:
2 parts of dichlorodimethylsilane is added into solvent ethyl acetate, 5 parts of triethylamine does acid binding agent, is placed in ice
Under the conditions of bath, double 1 part of silicone oil of hydroxy-terminated polysiloxanes are then added dropwise by constant pressure funnel in stirring, after dripping
Remove ice bath react again be warming up to 60 DEG C after 3h the reaction was continued 0.8h after reaction was completed, be filtered to remove precipitating, filtrate revolving removed
Ethyl acetate is removed, then is washed 2 times with hexamethylene, is dried, the polysiloxanes silicone oil of double chlorine sealing ends is obtained；
Step 3:
Under condition of ice bath, pass through the acetic acid for the polysiloxanes silicone oil that constant pressure funnel is blocked to double chlorine in stirring
0.5 part of furfuryl alcohol is added dropwise in ethyl ester solution, drips after recession goes ice bath to react 3h again, terminates after being warming up to 60 DEG C of reaction 0.8h
Reaction stops stirring, and revolving removes solvent, and is washed 2 times with hexamethylene, and drying obtains product II；
Step 4:
In molar ratio it is that 1:2 is added in reaction unit by product I and product II under nitrogen gas protection, slowly rises
High-temperature be 55 DEG C until be uniformly mixed, be continuously heating to be 105 DEG C after react 2.5h, be cooled to room temperature after reaction, will
Solid matter is washed 2 times with ethyl acetate, and drying, which derives from, repairs polyimide modified silicon rubber.
Embodiment 3
A kind of preparation method of selfreparing modified silicon rubber, specifically comprises the following steps::
Step 1:
1.0 parts and 0.9 part of pyromellitic dianhydride of phenylenediamine is added in dimethyl acetamide, reaction is stirred at room temperature
8h is added 0.5 part of maleic anhydride, the reaction was continued 3h, is added 2.0 parts and 2.0 parts of acetic anhydride of triethylamine, is warming up to 60 DEG C, reaction
8h.Reaction solution is poured into petroleum ether, a large amount of solid precipitatings occurs, filtering is water-soluble with 5wt% sodium bicarbonate by the solid of acquisition
Liquid washs 3 times, and deionized water is washed three times, dry, prepares product I.
Step 2:
2 parts of dichlorodimethylsilane is added into solvent ethyl acetate, 6 parts of triethylamine does acid binding agent, is placed in ice
Under the conditions of bath, double 1 part of silicone oil of hydroxy-terminated polysiloxanes are then added dropwise by constant pressure funnel in stirring, after dripping
Remove ice bath react again be warming up to 60 DEG C after 4h the reaction was continued 1h after reaction was completed, be filtered to remove precipitating, filtrate rotated and is removed
Ethyl acetate, then washed 2 times with hexamethylene, it dries, obtains the polysiloxanes silicone oil of double chlorine sealing ends；
Step 3:
Under condition of ice bath, pass through the acetic acid for the polysiloxanes silicone oil that constant pressure funnel is blocked to double chlorine in stirring
0.5 part of furfuryl alcohol is added dropwise in ethyl ester solution, drips after recession goes ice bath to react 4h again, terminates instead after being warming up to 60 DEG C of reaction 1h
It answers, stops stirring, revolving removes solvent, and is washed 2 times with hexamethylene, and drying obtains product II；
Step 4:
It is in molar ratio that 1:2.2 is added in reaction unit by product I and product II, slowly under nitrogen gas protection
Increase temperature be 60 DEG C until be uniformly mixed, be continuously heating to be 110 DEG C after react 3h, be cooled to room temperature after reaction, will
Solid matter is washed 2 times with ethyl acetate, and drying, which derives from, repairs polyimide modified silicon rubber.
In order to study the self-reparing capability of composite material, after the composite material hot pressing for randomly selecting embodiment 1-3 preparation,
Its surface carries out scratch experiment with blade, its repairing effect is detected using optical microscopy.As shown in figure 4, contrast material is certainly
Before reparation, it can be seen that batten scratch is disappearing substantially after selfreparing is handled, and only can just observe under an optical microscope
To remaining thin trace.
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (6)
1. a kind of selfreparing modified silicon rubber, which is characterized in that the structural formula of the polyimide modified silicon rubber of selfreparing is as follows:
Wherein, m=70-150,1≤n≤10,1≤x≤10.
2. a kind of preparation method of the polyimide modified silicon rubber of selfreparing according to claim 1, which is characterized in that packet
Include following steps:
Step 1: using p-phenylenediamine and pyromellitic dianhydride as reaction raw materials, maleic anhydride is end-capping reagent, and it is sub- to prepare oligomeric acyl
Amine obtains product I, and structural formula is as follows:
Wherein: 1≤n≤10；
Step 2: the poly- silicon oxygen of double chlorine sealing ends is prepared using double hydroxy-terminated polysiloxane silicone oil and dichlorodimethylsilane as raw material
Alkane silicone oil, structural formula are as follows:
Wherein, m=70-150；
Step 3: the polysiloxanes silicone oil and furfuryl alcohol of the double chlorine sealing end obtained using step 2 obtain product II, structure as raw material
Formula is as follows:
Step 4: product I and product II as raw material, are prepared polyimide modified silicon rubber, structural formula is as follows:
Wherein, 1≤x≤10.
3. a kind of preparation method of selfreparing modified silicon rubber according to claim 1, which is characterized in that including walking as follows
It is rapid:
Step 1:
1.0 parts and 0.5-0.9 parts of pyromellitic dianhydride of phenylenediamine is added in dimethyl acetamide, reaction 5- is stirred at room temperature
8h is added maleic anhydride 0.5-0.1 part, the reaction was continued 3-4h, and triethylamine 1.5-2.0 part and acetic anhydride 1.5-2.0 parts, liter is added
Temperature reacts 8-10h to 60 DEG C.Reaction solution is poured into petroleum ether, a large amount of solid precipitatings occurs, the solid of acquisition is used in filtering
5wt% sodium bicarbonate aqueous solution washs 3 times, and deionized water is washed three times, dry, prepares product I；
Step 2:
2 parts of dichlorodimethylsilane is added into solvent ethyl acetate, 4-6 parts of triethylamine does acid binding agent, is placed in ice bath
Under the conditions of, double 1 part of silicone oil of hydroxy-terminated polysiloxanes are then added dropwise by constant pressure funnel in stirring, drip recession
It is warming up to 60 DEG C after going ice bath to react 2-4h again the reaction was continued after 0.5-1h that reaction was completed, be filtered to remove precipitating, filtrate is rotated
Ethyl acetate is removed, then is washed 2 times with hexamethylene, is dried, the polysiloxanes silicone oil of double chlorine sealing ends is obtained；
Step 3:
Under condition of ice bath, pass through the ethyl acetate for the polysiloxanes silicone oil that constant pressure funnel is blocked to double chlorine in stirring
0.5 part of furfuryl alcohol is added dropwise in solution, drips after recession goes ice bath to react 2-4h again, terminates after being warming up to 60 DEG C of reaction 0.5-1h
Reaction stops stirring, and revolving removes solvent, and is washed 2 times with hexamethylene, and drying obtains product II；
Step 4:
Under inert gas protection, product I and product II are added in reaction unit, slowly increase temperature until mixing is equal
It is even, 2-3h is reacted after being continuously heating to certain temperature, is cooled to room temperature after reaction, solid matter is washed with ethyl acetate
2 times, drying, which derives from, repairs polyimide modified silicon rubber.
4. a kind of preparation method of selfreparing modified silicon rubber according to claim 3, which is characterized in that the step 4
The molar ratio of middle product I and product II is 1:2-2.2.
5. a kind of preparation method of selfreparing modified silicon rubber according to claim 3, which is characterized in that the mixing temperature
Degree is 50-60 DEG C.
6. a kind of preparation method of selfreparing modified silicon rubber according to claim 3, which is characterized in that the reaction temperature
Degree is 100-110 DEG C.
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| CN111662455A (en) * | 2020-06-18 | 2020-09-15 | 航天特种材料及工艺技术研究所 | Polysiloxane modified bismaleimide monomer, heat-repairing bismaleimide resin composition and preparation method |
| CN114231032A (en) * | 2021-11-08 | 2022-03-25 | 国网北京市电力公司 | Silicone rubber insulating material, silicone rubber insulator, and preparation method and application thereof |
| WO2023035192A1 (en) * | 2021-09-07 | 2023-03-16 | 山东大学 | Self-healing organosilicon polymer material, and preparation method therefor and use thereof |
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| CN111662455B (en) * | 2020-06-18 | 2022-05-24 | 航天特种材料及工艺技术研究所 | Polysiloxane modified bismaleimide monomer, heat-repairing bismaleimide resin composition and preparation method |
| WO2023035192A1 (en) * | 2021-09-07 | 2023-03-16 | 山东大学 | Self-healing organosilicon polymer material, and preparation method therefor and use thereof |
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