CN102167870B - Thermal self-repairing polymer material, and preparation and repairing methods thereof - Google Patents
Thermal self-repairing polymer material, and preparation and repairing methods thereof Download PDFInfo
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- CN102167870B CN102167870B CN 201110048852 CN201110048852A CN102167870B CN 102167870 B CN102167870 B CN 102167870B CN 201110048852 CN201110048852 CN 201110048852 CN 201110048852 A CN201110048852 A CN 201110048852A CN 102167870 B CN102167870 B CN 102167870B
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- 239000002861 polymer material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 29
- -1 2,2,6,6-tetramethylpiperidinooxy Chemical group 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 39
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 239000003444 phase transfer catalyst Substances 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 7
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 6
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 6
- 239000012312 sodium hydride Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 4
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 claims description 4
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 claims description 4
- 239000013077 target material Substances 0.000 claims description 4
- 238000007669 thermal treatment Methods 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims 2
- 238000000746 purification Methods 0.000 claims 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract 4
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical group CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 abstract 3
- 238000001816 cooling Methods 0.000 abstract 1
- 150000003384 small molecules Chemical class 0.000 description 27
- 230000008439 repair process Effects 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 238000009418 renovation Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000002459 sustained effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229920006299 self-healing polymer Polymers 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001723 carbon free-radicals Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 239000012510 hollow fiber Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000003808 methanol extraction Methods 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- VUZNLSBZRVZGIK-UHFFFAOYSA-N 2,2,6,6-Tetramethyl-1-piperidinol Chemical compound CC1(C)CCCC(C)(C)N1O VUZNLSBZRVZGIK-UHFFFAOYSA-N 0.000 description 1
- 238000006959 Williamson synthesis reaction Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000006897 homolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008263 repair mechanism Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Hydrogenated Pyridines (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a thermal self-repairing polymer material, and preparation and repairing methods thereof. The thermal self-repairing polymer material is prepared from 40-60 parts of 2,2,6,6-tetramethylpiperidinooxy (TEMPO) low molecular derivative modified polymer and 60-40 parts of 4-hydroxy-2,2,6,6-tetramethylpiperidinooxy (4-OH-TEMPO) low molecular derivative modified polymer. The preparation method comprises the following steps: dissolving the TEMPO low molecular derivative modified polymer and 4-OH-TEMPO low molecular derivative modified polymer in an organic solvent, and directly pouring the solution in a die to form a film, thereby obtaining the thermal self-repairing polymer material. The repairing method comprises the following steps: in the presence of inert gas, carrying out heat treatment on the damaged material at 110-130 DEG C for 15-30 minutes, and cooling to room temperature, thereby repairing the thermal self-repairing polymer material. The thermal self-repairing polymer material has the advantages of simple preparation process, high repairing capability, short repairing time and the like, and can be repaired many times, thereby prolonging the service life of the polymer material and conforming to the development trend of low-carbon economy.
Description
Technical field
The present invention relates to a kind of hot self-repair type polymer material and preparation and restorative procedure.
Background technology
Polymer materials has that quality is light, mechanical property is good, the structure design adjustable is superior and the plurality of advantages such as handling ease, has become indispensable part in human being's production, the life.But in long-term use procedure, the impact of factor of natural environment and the actual operating conditions such as impact, extruding and stretching owing to be subject to exposing to the weather etc., polymer materials can sustain damage, produce tiny crack or surperficial by scratch such as inside, cause the use properties of material to descend, thereby so that greatly shorten the work-ing life of material.Therefore, if can take simple method to make these damages be able to self-healing, not only can greatly prolong the work-ing life of material, and significant for the exploitation of energy-saving and emission-reduction, low carbon materials, meet less energy-consumption, low emission, the low low-carbon economy trend of polluting for the basis.
In order to develop the self-repair technology of polymer materials, research workers have carried out a large amount of research.Up to the present, the research of self-repair type polymer material mainly contained two large classes: a class is the pre-buried little container (such as hollow fiber, microcapsule etc.) that stores renovation agent in polymer materials; Another kind of is eigenmode self-healing polymers material.The former need guarantee renovation agent in the intact situation of material, can stablize and lossless the existence, requires simultaneously to load the microcapsule of renovation agent or hollow fiber and body material and has good consistency.For eigenmode self-healing polymers material, then be by molecular designing, in material, introduce certain functional structure, utilize its characteristic to make material after producing damage, be recovered molecular structure, thereby need not to add renovation agent, effectively avoid the adding of renovation agent on the impact of material body performance.But present above-mentioned technology all exists the renovation technique conditional request high, or product is made the rehabilitation cost height; The problems such as the multi damage repairing effect is poor.
Summary of the invention
For overcoming above technological deficiency, the invention provides a kind of hot self-repair type polymer material, and this material preparation and restorative procedure further are provided.
The present invention is based on the principle of eigenmode self-healing polymers material, by molecular designing, has proposed a kind of hot self-repair type polymer material that contains thermal reversibility C-ON key.Be about to 2,2,6,6-tetramethyl piperidine-nitrogen-oxide compound (being called for short " TEMPO ") small molecules derivative and 4-hydroxyl-2,2,6,6-tetramethyl piperidine-nitrogen-oxide compound (be called for short " 4-OH-TEMPO ") small molecules derivative obtains the polymkeric substance of TEMPO small molecules Derivatives Modified and the polymkeric substance of 4-OH-TEMPO small molecules Derivatives Modified with the polymkeric substance that side chain contains the reactive chlorine group by the Williamson reaction respectively.These two kinds of polymkeric substance are dissolved in the organic solvent with the certain part by weight blend, then water and cast from the mould, the characteristics such as desolventizing obtains a kind of hot self-repair type polymer material, and it is simple that this material has preparation, and repair ability is high, repair time is short, can realize repeatedly repairing.
The present invention realizes that by following technical measures wherein affiliated raw material umber is parts by weight except specified otherwise.Be convenient statement, 2,2,6,6-tetramethyl piperidine-nitrogen-oxide compound referred to as " TEMPO ".4-hydroxyl-2,2,6,6-tetramethyl piperidine-nitrogen-oxide compound referred to as " 4-OH-TEMPO ".
A kind of hot self-repair type polymer material is comprised of the component of following parts by weight:
40 ~ 60 parts in the polymkeric substance of 2,2,6,6-tetramethyl piperidine-nitrogen-oxide compound (TEMPO) small molecules Derivatives Modified;
4-hydroxyl-2,2,6,60 ~ 40 parts in the polymkeric substance of 6-tetramethyl piperidine-nitrogen-oxide compound (4-OH-TEMPO) small molecules Derivatives Modified.
In above-mentioned hot self-repair type polymer material, described 2,2,6,6-tetramethyl piperidine-nitrogen-oxide compound (TEMPO) small molecules derivative is selected from any in the following structure:
In above-mentioned hot self-repair type polymer material, described 4-hydroxyl-2,2,6,6-tetramethyl piperidine-nitrogen-oxide compound (4-OH-TEMPO) small molecules derivative is selected from any in the following structure:
In above-mentioned hot self-repair type polymer material, described polymkeric substance is selected from any of following material:
The composition of the polymkeric substance of described TEMPO small molecules Derivatives Modified is by weight: TEMPO small molecules derivative 30-60 part, adorned polymkeric substance 25-40 part; The composition of the polymkeric substance of described 4-OH-TEMPO small molecules Derivatives Modified is by weight: 4-OH-TEMPO small molecules derivative 20-50 part, adorned polymkeric substance 20-40 part is good.
The hot self-repair type polymer material preparation of the present invention method may further comprise the steps:
A. the polymkeric substance for preparing TEMPO small molecules Derivatives Modified, under protection of inert gas, add organic solvent in the sodium hydride and make suspension, drip the organic solution of TEMPO small molecules derivative, react and generated TEMPO small molecules derivative Na salt in about 1.5 hours, then add phase-transfer catalyst and the adorned polymkeric substance of 25-40 part, continue reaction 16-48 hour, purifying obtains the polymkeric substance of TEMPO small molecules Derivatives Modified;
B. the polymkeric substance for preparing 4-OH-TEMPO small molecules Derivatives Modified, under protection of inert gas, add organic solvent in the sodium hydride and make suspension, the organic solution that drips 4-OH-TEMPO small molecules derivative is reacted about 1.5 hours generation 4-OH-TEMPO small molecules derivative Na salt, then add phase-transfer catalyst and part adorned polymkeric substance, continue reaction 16-48 hour, purifying obtains the polymkeric substance of 4-OH-TEMPO small molecules Derivatives Modified;
C. prepare target material, the polymkeric substance of TEMPO small molecules Derivatives Modified and the polymkeric substance of 4-OH-TEMPO small molecules Derivatives Modified are dissolved in the organic solvent, then direct pouring is in mould, and film forming obtains hot self-repair type polymer material.
Wherein, described phase-transfer catalyst is hexaoxacyclooctadecane-6-6,15-crown ether-5, any one in the dibenzo-18-crown-6 (DB18C6); The used organic solvent of polymkeric substance of preparation TEMPO and 4-OH-TEMPO small molecules Derivatives Modified is selected from tetrahydrofuran (THF), any in the DMF; Used organic solvent is toluene in the preparation target material step, methylene dichloride, chloroform, any in the tetrahydrofuran (THF).The temperature of this preparation feedback can be room temperature.Suspension among steps A and the B can make by adding 100 parts of organic solvents in 10 ~ 20 parts of sodium hydrides.
The synthetic polymer route of TEMPO small molecules Derivatives Modified is:
The synthetic polymer route of 4-OH-TEMPO small molecules Derivatives Modified is:
The method of repairing may further comprise the steps, and in 110 ~ 130 ℃, in the presence of rare gas element, thermal treatment 15 ~ 30 minutes is cooled to room temperature and gets final product with the material of damage.Its principle is: as shown in Figure 1, in above-mentioned hot self-repair type polymer material, all contain the C-ON covalent linkage of hot reversible responsiveness in the polymkeric substance of the polymkeric substance of TEMPO small molecules Derivatives Modified and 4-OH-TEMPO small molecules Derivatives Modified.After material production damage (such as tiny crack, cut etc.), this material is heat-treated for some time under 110 ~ 130 ℃ temperature, these C-ON covalent linkage are under such temperature condition of heat treatment, and homolysis is macromole carbon radicals, nitroxyl free radical and small molecules carbon radicals, nitroxyl free radical; After being down to room temperature, the macromole carbon radicals that generates under the hot conditions and macromole nitroxyl free radical can be recombinated and then combination generates crosslinked polymer network structure, so that the damage of material is repaired.
With respect to prior art, the present invention has the following advantages: one, the hot self-repair type polymer material structure of gained is simple, dissolves in organic solvent, is easy to synthetic preparation; Two, when material production is damaged, through brief heat treating, can be repaired, repair ability is high, and repair time is short; Three, owing to contain hot reversible responsiveness C-ON covalent linkage in the material, material has repair ability repeatedly.
Description of drawings
Fig. 1 is the repair mechanisms synoptic diagram of the hot self-repair type polymer material of the present invention.
Fig. 2 is the experiment effect figure of the preferred embodiment of the present invention.
Embodiment
Below by embodiment the present invention is specifically described; be necessary to be pointed out that at this; present embodiment only is used for the present invention is further specified; but can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1
1-hydroxyl-2,2,6,6-tetramethyl piperidine (TEMPO-H) are modified the synthetic of poly-p-chloromethyl styrene (PCMS-TEMPO).
Add magnetic stir bar in the 250ml there-necked flask, then logical argon gas 10min takes by weighing sodium hydride 2.0 g (50.0mmol in advance, 60% is scattered in mineral oil) join in the flask, to wherein adding the 20ml anhydrous tetrahydro furan, start induction stirring again, obtain suspension.Take by weighing TEMPO-H (6.0g, 38.2mmol) and be dissolved in the 30ml anhydrous tetrahydro furan, this solution at room temperature is added drop-wise in the middle of the above-mentioned suspension, drip off in the 20min.Afterwards, make the at room temperature about 1.5h of sustained reaction of reaction mixture, until without Bubble formation.The poly-p-chloromethyl styrene (3.3g) that then will weigh up and phase-transfer catalyst hexaoxacyclooctadecane-6-6 (0.28g, 1.05mmol), join fast in the flask, continue logical argon gas 10min, subsequently with reaction flask sealing, make at room temperature sustained reaction 48 hours of reactant.After reaction finishes, the reaction mixture that obtains is added drop-wise in the freezing methyl alcohol of 500ml and precipitates.After the precipitation drying that obtains, purify twice with tetrahydrofuran (THF) dissolving, methanol extraction again, the white powder that obtains is dried to constant weight in 40 ℃ of vacuum drying ovens.
Embodiment 24-hydroxyl-1-(1-phenyl-oxyethyl group)-2,2,6, the poly-p-chloromethyl styrene (PCMS-TEMPO-EOPh) that the 6-tetramethyl piperidine is modified synthetic.
Add magnetic stir bar in the 250ml there-necked flask, then logical argon gas 10min takes by weighing sodium hydride 1.20g (30.0mmol in advance, 60% is scattered in mineral oil) join in the flask, to wherein adding the 20ml anhydrous tetrahydro furan, start induction stirring again, obtain suspension.Take by weighing 4-hydroxyl-1-(1-phenyl-oxyethyl group)-2,2,6,6-tetramethyl piperidine (HO-TEMPO-EOPh) (5.0g, 18.0mmol) be dissolved in the 30ml anhydrous tetrahydro furan, this solution at room temperature is added drop-wise in the middle of the above-mentioned suspension, drip off in the 20min.Afterwards, make the at room temperature about 1.5h of sustained reaction of reaction mixture, until without Bubble formation.Poly-p-chloromethyl styrene (3.3g) and the phase-transfer catalyst hexaoxacyclooctadecane-6-6(0.20g that then will weigh up, 0.75mmol) join fast in the flask, continue logical argon gas 10min, subsequently with the reaction flask sealing, make at room temperature sustained reaction 24 hours of reactant.After reaction finishes, the reaction mixture that obtains is added drop-wise in the freezing methyl alcohol of 500ml and precipitates.After the precipitation drying that obtains, purify twice with tetrahydrofuran (THF) dissolving, methanol extraction again, the white powder that obtains is dried to constant weight in 40 ℃ of vacuum drying ovens.
Embodiment 3Hot self-repair type polymer material preparation.
Weighing 0.10g PCMS-TEMPO and 0.10g PCMS-TEMPO-EOPh, then the toluene solvant that adds 10ml, after polymkeric substance all is dissolved as transparent solution, with this solution direct pouring in glass mold, place and at room temperature to make the solvent film forming of naturally volatilizing, then be placed in 40 ℃ of vacuum drying ovens and thoroughly solvent removed, obtain hot self-repair type polymer material.
Embodiment 4The damage self-repairing of hot self-repair type polymer material.
Adopt microscope that the selfreparing effect of this hot self-repair type polymer material is observed, test again all with for the second time hot repair for the first time and carry out at same material, the repair process of material and repairing effect are illustrated in fig. 2 shown below.
For the first time hot repair is tested again:
Mark criss-cross cut 10 on the surface of material with sharp blade; Then be sealed in the container that is full of argon gas, repair 15min under 125 ℃ of temperature, effect is shown in 11; Again repair 30min under this temperature afterwards, effect is shown in 12; Can see obviously that the cut of material surface heals basically.
For the second time hot repair is tested again:
In order to prove its repeatedly repair ability, make again cut one in the cut position that repairs for the first time, effect is shown in 20; Then be sealed in the container that is full of argon gas, repair 30min under 125 ℃ of temperature, effect is shown in 21; Again repair 30min under this temperature afterwards, effect is shown in 22; The cut on visible material surface almost completely disappears.
Claims (5)
1. hot self-repair type polymer material is comprised of the component of following parts by weight:
40 ~ 60 parts in the polymkeric substance of 2,2,6,6-tetramethyl piperidine-nitrogen-oxide compound small molecules Derivatives Modified;
4-hydroxyl-2,2,6,60 ~ 40 parts in the polymkeric substance of 6-tetramethyl piperidine-nitrogen-oxide compound small molecules Derivatives Modified;
Wherein, described 2,2,6,6-tetramethyl piperidine-nitrogen-oxide compound small molecules derivative is selected from any in the following structure:
Described 4-hydroxyl-2,2,6,6-tetramethyl piperidine-nitrogen-oxide compound small molecules derivative is selected from any in the following structure:
Described polymkeric substance is selected from any of following material:
2. according to hot self-repair type polymer material claimed in claim 1, it is characterized in that, described 2, the composition of the polymkeric substance of 2,6,6-tetramethyl piperidine-nitrogen-oxide compound small molecules Derivatives Modified is by weight: 2,2,6,6-tetramethyl piperidine-nitrogen-oxide compound small molecules derivative 30-60 part, adorned polymkeric substance 25-40 part; Described 4-hydroxyl-2,2,6, the composition of the polymkeric substance of 6-tetramethyl piperidine-nitrogen-oxide compound small molecules Derivatives Modified is by weight: 4-hydroxyl-2,2,6,6-tetramethyl piperidine-nitrogen-oxide compound small molecules derivative 20-50 part, adorned polymkeric substance 20-40 part.
3. hot self-repair type polymer material preparation method claimed in claim 2 is characterized in that, may further comprise the steps:
A. prepare 2, the polymkeric substance of 2,6,6-tetramethyl piperidine-nitrogen-oxide compound small molecules Derivatives Modified, under protection of inert gas, add organic solvent in the sodium hydride and make suspension, drip 2,2,6, the organic solution of 6-tetramethyl piperidine-nitrogen-oxide compound small molecules derivative is reacted generation 2,2 in 1.5 hours, 6, then 6-tetramethyl piperidine-nitrogen-oxide compound small molecules derivative Na salt add phase-transfer catalyst and the adorned polymkeric substance of 25-40 part, continues reaction 16-48 hour, purification obtains 2, the polymkeric substance of 2,6,6-tetramethyl piperidine-nitrogen-oxide compound small molecules Derivatives Modified;
B. prepare 4-hydroxyl-2,2, the polymkeric substance of 6,6-tetramethyl piperidine-nitrogen-oxide compound small molecules Derivatives Modified is under protection of inert gas, add organic solvent in the sodium hydride and make suspension, drip 4-hydroxyl-2,2,6, the organic solution reaction of 6-tetramethyl piperidine-nitrogen-oxide compound small molecules derivative generated 4-hydroxyl-2 in 1.5 hours, 2,6,6-tetramethyl piperidine-nitrogen-oxide compound small molecules derivative Na salt, then add phase-transfer catalyst and adorned polymkeric substance, continue reaction 16-48 hour, purifying obtains 4-hydroxyl-2,2, the polymkeric substance of 6,6-tetramethyl piperidine-nitrogen-oxide compound small molecules Derivatives Modified;
C. prepare target material, with 2, polymkeric substance and the 4-hydroxyl-2 of 2,6,6-tetramethyl piperidine-nitrogen-oxide compound small molecules Derivatives Modified, 2, the polymkeric substance of 6,6-tetramethyl piperidine-nitrogen-oxide compound small molecules Derivatives Modified is dissolved in the organic solvent, and then direct pouring is in mould, film forming obtains hot self-repair type polymer material; Wherein, described phase-transfer catalyst is hexaoxacyclooctadecane-6-6,15-crown ether-5, any one in the dibenzo-18-crown-6 (DB18C6); Preparation 2,2,6,6-tetramethyl piperidine-nitrogen-oxide compound and 4-hydroxyl-2,2,6, the used organic solvent of polymkeric substance of 6-tetramethyl piperidine-nitrogen-oxide compound small molecules Derivatives Modified is selected from tetrahydrofuran (THF), N, any in the N-METHYLFORMAMIDE; Used organic solvent is toluene in the preparation target material step, methylene dichloride, chloroform, any in the tetrahydrofuran (THF).
4. according to preparation method claimed in claim 3, it is characterized in that the temperature of reaction is room temperature.
5. the restorative procedure of hot self-repair type polymer material claimed in claim 1 is characterized in that may further comprise the steps, in the presence of rare gas element, with the damage material in 110 ~ 130 ℃, then thermal treatment 15 ~ 30 minutes be cooled to room temperature.
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| CN103073695B (en) * | 2012-12-27 | 2015-03-11 | 中山大学 | Intrinsic room-temperature self-repairing crystalline polymer |
| CN104211850B (en) * | 2014-09-23 | 2016-08-10 | 厦门大学 | A kind of comb-shaped polymer containing reversible hydrogen bond and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0184203A2 (en) * | 1984-12-05 | 1986-06-11 | ADEKA ARGUS CHEMICAL CO., Ltd. | Vinyl benzyl 2,2,6,6-tetramethyl piperidines |
| CN1277214A (en) * | 2000-06-23 | 2000-12-20 | 复旦大学 | Superbranched polystyrene and its preparation |
| WO2006075445A1 (en) * | 2005-01-11 | 2006-07-20 | The Yokohama Rubber Co., Ltd. | Process for production of modified polymers and modified polymers produced thereby |
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2011
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0184203A2 (en) * | 1984-12-05 | 1986-06-11 | ADEKA ARGUS CHEMICAL CO., Ltd. | Vinyl benzyl 2,2,6,6-tetramethyl piperidines |
| CN1277214A (en) * | 2000-06-23 | 2000-12-20 | 复旦大学 | Superbranched polystyrene and its preparation |
| WO2006075445A1 (en) * | 2005-01-11 | 2006-07-20 | The Yokohama Rubber Co., Ltd. | Process for production of modified polymers and modified polymers produced thereby |
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