CN108484912A - A kind of eugenol based high-temp-resistant self-healing polymers and preparation method thereof - Google Patents
A kind of eugenol based high-temp-resistant self-healing polymers and preparation method thereof Download PDFInfo
- Publication number
- CN108484912A CN108484912A CN201810210458.8A CN201810210458A CN108484912A CN 108484912 A CN108484912 A CN 108484912A CN 201810210458 A CN201810210458 A CN 201810210458A CN 108484912 A CN108484912 A CN 108484912A
- Authority
- CN
- China
- Prior art keywords
- reaction
- ether
- formula
- polymer
- methyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
- C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of eugenol based high-temp-resistant self-healing polymers and preparation method thereof, the technical solution devise first it is a kind of being used to prepare the monomeric compound of polymer, and give the preparation method using eugenol as primary raw material.Based on this monomer, first with dithiols compound carry out it is light-initiated under sulfydryl alkene click-reaction, structure obtains oligomer, oxidative coupling reaction is carried out with the oligomer again and obtains linear polymer, then the linear polymer is reacted with diisocyanate under catalytic condition, is finally obtained a kind of with good self-reparing capability and heat safe polymer.Polymer designed by the present invention makes full use of this renewable resource of eugenol, has many advantages, such as that raw material is cheap and easy to get, reaction condition is mild, meets Atom economy.Such polymer can carry out multiple selfreparing, and material shows superpower high-temperature stability, has a extensive future in terms of functional material after by small damage under illumination condition.
Description
Technical field
The present invention relates to technical field of polymer chemistry, and in particular to a kind of eugenol based high-temp-resistant self-healing polymers and
Preparation method.
Background technology
In recent years, the unsustainable property of fossil resource causes the crisis of global resources and the energy.Seek other alternative moneys
Source and the energy (such as solar energy, nuclear energy, wind energy), become the main method solved the problems, such as.The resource for coming from animals and plants, because of it
Renewable and sustainability becomes in recent years important one of research hotspot.Eugenol is a kind of renewable resource cheap and easy to get,
Content accounts for about 90% in caryophyllus oil.It has obtained some practical applications in fields such as medicine, fragrance.In Material Field, profit
Relevant functional polymer is designed with the design feature of eugenol, is also had attracted increasing attention.
Material in use, due to fatigue or external destruction, will produce micro-crack equivalent damage, this will shorten material
Service life can even lead to a disaster.Using dynamic key or supermolecule interaction design self-repair material, become research heat in recent years
Point.Material with self-healing properties, it will greatly improve service life and safety.Self-repair material realizes self-repair function
There are mainly four types of methods：(1) thermal compression welding technology；(2) reversible high cross-linked polymer；(3) liquid core fibre technology；(4) micro- glue
Capsule technology.In self-repair material, selfreparing high molecular material has the advantage that：(1) site-specific nature is caused poly- by crackle
It closes, it is with strong points, it is efficient；(2) it automates, without artificial observation, saves monitoring cost；(3) material lifetime is improved；(4)
Eliminate material maintenance cost；(5) thinking is provided for material intelligence；(6) environment friendly avoids outer doping to environment
Influence.
Heat-resistant polymer material is to refer to be used for a long time between 250~300 DEG C, or can be resistant to love instantaneous high-temperature
Material.This kind of material has irreplaceable role in high-technology field.For example, in aerospace field, material is both required
Material wants light intensity high, is resistant to high temperature again.
Invention content
The invention solves a technical problem be to provide a kind of new high temperature resistant self-healing polymers.
Another technical problem to be solved by the present invention is that how to realize the efficient of above-mentioned new high temperature resistant self-healing polymers
It prepares.
The invention solves another technical problem be that conventional self-healing polymers material prepares that cost of material is high, prepares
Complex process.
The invention solves another technical problem be conventional self-healing polymers material heat-resisting ability and selfreparing
It is ineffective.
To realize that the above technical purpose, the present invention use following technical scheme：
In order to using eugenol prepare high temperature resistant can selfreparing high molecular material, the present invention provides a kind of structure formula (I)
Compound
Present invention simultaneously provides two kinds of preparation methods of the compound of structure formula (I), and steps are as follows for the method：
Method one：The eugenol that 2 times are measured is reacted under alkaline condition with the compound of structure formula (II), obtains structural formula
(I) compound.
Wherein X is Cl, one kind in Br, I.In reaction required alkali can be inorganic base such as KOH, NaOH, LiOH,
Na2CO3、K2CO3、Cs2CO3、NaHCO3、KHCO3One or more of；Can also be organic base, such as triethylamine, pyridine, N- alkane
Phenylpiperidines, diisopropylethylamine (DIPEA), 11-7- alkene (DBU) of 1,8- diazabicylos [5.4.0], tetramethylethylenediamine
(TMEDA), (systematic naming method 4- diazabicyclos [2,2,2] are pungent for five methyl diethylentriamine (PMDETA), triethylenediamine
Alkane, DABCO), the one or more of 4-dimethylaminopyridine (DMAP).The solvent of the reaction can be selected from water, dichloromethane,
Ether, diisopropyl ether, methyl tertiary butyl ether(MTBE), methanol, ethyl alcohol, normal propyl alcohol, isopropanol, tetrahydrofuran, glycol dimethyl ether
(DME), 1,4- dioxane, acetone, 2- butanone, ethyl acetate, butyl acetate, chloroform, carbon tetrachloride, 1,2- dichloroethanes,
One or more of 1,1,1- trichloroethanes, acetonitrile, benzonitrile, dimethyl sulfoxide (DMSO), N,N-dimethylformamide.The reaction
Temperature can be preferably room temperature to the reflux temperature of solvent from 0 DEG C to the reflux temperature of solvent.
Method two：The eugenol that 2 times are measured is reacted under alkaline condition with the compound of structure formula (III), obtains structure
The compound of formula (I).
In the compound of structure formula (III), the definition of X is identical with structure formula (II) compound.Required in reaction
Alkali can be inorganic base such as KOH, NaOH, LiOH, Na2CO3、K2CO3、Cs2CO3、NaHCO3、KHCO3One or more of；
Can also be organic base, such as triethylamine, pyridine, N- Alkylpiperidines, diisopropylethylamine (DIPEA), 1,8- diazabicylos
[5.4.0] 11-7- alkene (DBU), tetramethylethylenediamine (TMEDA), five methyl diethylentriamine (PMDETA), triethylene
One kind or several of diamines (systematic naming method 4- diazabicyclos [2,2,2] octane, DABCO), 4-dimethylaminopyridine (DMAP)
Kind.The solvent of the reaction can be selected from water, dichloromethane, ether, diisopropyl ether, methyl tertiary butyl ether(MTBE), methanol, ethyl alcohol, positive third
Alcohol, isopropanol, tetrahydrofuran, glycol dimethyl ether (DME), 1,4- dioxane, acetone, 2- butanone, ethyl acetate, acetic acid fourth
Ester, chloroform, carbon tetrachloride, 1,2- dichloroethanes, 1,1,1- trichloroethanes, acetonitrile, benzonitrile, dimethyl sulfoxide (DMSO), N, N- diformazans
One or more of base formamide.The reaction temperature can be preferably room temperature to solvent from 0 DEG C to the reflux temperature of solvent
Reflux temperature.
Preparation side the present invention also provides the compound of structure formula (I) as monomer progress high temperature resistant self-healing polymers
Method.In high temperature resistant self-healing polymers preparation, two sulphur of the compound of structure formula (I) and slightly excessive structure formula (IV)
Alcohol compound carry out it is light-initiated under sulfydryl-alkene click-reaction, obtain the low polymer of structure formula (V), see following reaction formula
1.In structure formula (IV), R1Can be C2-C20Alkyl, naphthenic base, benzyl；N is the integer more than or equal to 2.Structure formula (V)
Middle R1Definition it is identical with structure formula (IV).In the low polymer of preparation structure formula (V), photoinitiator used can be
Benzophenone, 4- methyl benzophenones, 2 methyl benzophenone, 4,4 '-dimethyl benzophenones, 4,4 '-dihydroxy hexichol first
Ketone, 2,4 dihydroxyl benzophenone, Michler's keton, 4,4 '-two (thiopurine methyltransferase) benzophenone, 2- hydroxy-2-methyl -1- phenylacetones
(1173), 1- hydroxycyclohexyl phenyl ketones (184), 2- methyl -2- (4- morpholinyls) -1- [4- (methyl mercapto) phenyl] -1- third
Ketone (907), 2,4,6- trimethylbenzoy-diphenies phosphine oxide (TPO), 2,4,6- trimethylbenzoyl phenyl phosphonic acids second
Ester (TPO-L), 2- dimethylamino -2- benzyls -1- [4- (4- morpholinyls) phenyl] -1- butanone (IHT-PI 910), 2- hydroxyls -2-
Methyl-1-[4- (2- hydroxyl-oxethyls) phenyl]-1- acetone (659), benzoin dimethylether, benzoin ethyl ether, is rested in peace at styrax
Fragrant isopropyl ether, benzoin isobutyl ether, diphenylethan, α, alpha, alpha-dimethyl oxygroup-α-phenyl acetophenone, one kind in thioxanthone or several
Kind, the usage amount of photoinitiator is not higher than 5%.The solvent of the reaction can be selected from dichloromethane, ether, diisopropyl ether, methyl
Tertbutyl ether, tetrahydrofuran, glycol dimethyl ether (DME), 1,4- dioxane, acetone, 2- butanone, ethyl acetate, acetic acid fourth
Ester, chloroform, carbon tetrachloride, 1,2- dichloroethanes, 1,1,1- trichloroethanes, acetonitrile, benzonitrile, dimethyl sulfoxide (DMSO), N, N- diformazans
One or more of base formamide, benzene,toluene,xylene.The reaction temperature can be excellent from 0 DEG C to the reflux temperature of solvent
Room temperature is selected as to the reflux temperature of solvent.
The synthesis of the low polymer of 1 structure formula (V) of reaction equation
The present invention also provides the methods that the oligomer of structure formula (V) prepares linear polymer (VI) by oxidative coupling.Line
In type polymer (VI), n is the integer more than or equal to 2, and m is the integer more than or equal to 2.Required oxidation in oxidation reaction
Agent can be hydrogen peroxide, iodine, chlorosulfuric acid, oxygen.Solvent can be selected from dichloromethane, chloroform, ether, diisopropyl required for reaction
Ether, methyl tertiary butyl ether(MTBE), tetrahydrofuran, glycol dimethyl ether (DME), 1,4- dioxane, acetone, 2- butanone, ethyl acetate,
Butyl acetate, chloroform, carbon tetrachloride, 1,2- dichloroethanes, acetonitrile, benzonitrile, dimethyl sulfoxide (DMSO), N,N-dimethylformamide,
One or more of benzene,toluene,xylene.The reaction temperature can be preferably room temperature to from 0 DEG C to the reflux temperature of solvent
The reflux temperature of solvent.
The present invention also provides the linear polymers of structure formula (VI) to prepare high temperature resistant self-healing polymers by addition reaction
(VII) method.In high temperature resistant self-healing polymers preparation, linear polymer (VI) is with diisocyanate in catalysis item
It is reacted under part, generates the polyurethane (VII) with cross-linked structure.In the polymer of structure formula (VII), the definition of m, n
It is identical as structure formula (VI), R2For C2-C15Alkyl, naphthenic base, phenyl etc..Used catalyst can be N, N- diformazans in reaction
Basic ring hexylamine, bis- (2- dimethylaminoethyls) ethers, N, N, N', N'- tetramethylethylenediamines (TMEDA), triethylamine, N, N- dimethyl
Benzylamine, N-ethylmorpholine, N-methylmorpholine, N, N '-diethyl piperazine, triethanolamine, dibutyl tin laurate.
In polymer (VII), due to there are dynamic disulfide bond, showing the self-repairability under illumination condition
Energy；In addition high temperature resistance may be shown, is passed through because of aromatic ring even sulfone, sulfoxide structure, the material containing rigidity in molecule
TGA measures its Td5It is 400 DEG C or so, Td10It is 1000 DEG C or so, Td50It is 1300 DEG C or so.
The present invention provides a kind of eugenol based high-temp-resistant self-healing polymers and preparation method thereof, and the technical solution is first
Devise it is a kind of being used to prepare the monomeric compound of polymer, and give the preparation method using eugenol as primary raw material.With
Based on this monomeric compound, light-initiated lower sulfydryl-alkene click-reaction is first carried out with dithiols compound, build obtain it is low
Polymers, then oxidative coupling reaction is carried out with the oligomer and obtains linear polymer, then by the linear polymer and diisocyanate
Ester reacts under catalytic condition, finally obtains a kind of with good self-reparing capability and heat safe polymer.Set by the present invention
The polymer of meter makes full use of this renewable resource of eugenol, has that raw material is cheap and easy to get, reaction condition is mild, meets original
The advantages that subeconomy.Such polymer can carry out multiple selfreparing, and material after by small damage under illumination condition
Material shows superpower high-temperature stability, has a extensive future in terms of functional material.
Specific implementation mode
With reference to embodiment, the present invention is further explained.It should be understood that these embodiments are merely to illustrate the present invention, and
It is not used in and limits the scope of the invention.The following example test method without specific conditions, usually according to normal condition, or
The condition that person provides or suggests according to manufacturer.Unless otherwise indicated outer, all professions used herein and scientific terminologies with
Meaning familiar to those skilled in the art is identical.In addition any method and material similar or impartial to this method all can be used for
In the method for the present invention.
The preparation of 1 1,3- of embodiment, bis- cloves phenolic group -2- propyl alcohol (I)
Using eugenol, epoxychloropropane as raw material.
Eugenol (3.28g, 20mmol), epoxychloropropane (0.93g, 10mmol), sodium hydroxide are added in reaction bulb
(0.88g, 22mmol), ethyl alcohol 20ml is stirred and is warming up to 70 DEG C of reaction 5h.It is cooling, dilute hydrochloric acid tune pH=2-3 is added, with two
Chloromethanes extracts 3 times, merges organic phase, and anhydrous sodium sulfate is dry, is concentrated to give weak yellow liquid product 2.46g, yield 64%.
1H-NMR(CDCl3,δppm):6.94-6.88(m,2H),6.74-6.70(m,4H),6.03-5.89(m,2H),
5.09-5.03(m,4H),4.38-4.34(m,1H),4.19-4.14(m,4H),3.83(s,6H),3.43-3.39(m,1H),
3.34-3.30(m,4H).
The preparation of 2 1,3- of embodiment, bis- cloves phenolic group -2- propyl alcohol (I)
Using eugenol, epoxy bromopropane as raw material.
Eugenol (3.28g, 20mmol), epoxy bromopropane (1.37g, 10mmol), potassium hydroxide are added in reaction bulb
(0.96g, 22mmol), isopropanol 20ml is stirred and is warming up to 80 DEG C of reaction 3h.It is cooling, dilute hydrochloric acid tune pH=2-3 is added, uses
Ether extracts 3 times, merges organic phase, and anhydrous sodium sulfate is dry, is concentrated to give weak yellow liquid product 2.93g, yield 71%.
1H NMR characterize datas are same as Example 1.
The preparation of 3 1,3- of embodiment, bis- cloves phenolic group -2- propyl alcohol (I)
Using eugenol, bis- bromo- 2- propyl alcohol of 1,3- as raw material.
Eugenol (3.28g, 20mmol), bis- bromo- 2- propyl alcohol (2.18g, 10mmol) of 1,3-, acetonitrile are added in reaction bulb
20mL, Anhydrous potassium carbonate (2.76g, 20mmol).20h is stirred at room temperature in reactant.Dilute sulfuric acid tune pH=2-3 is added, uses second
Acetoacetic ester extracts 3 times, merges organic phase, and anhydrous calcium chloride is dry, is concentrated to give weak yellow liquid product 2.65g, yield 69%.
1H NMR characterize datas are same as Example 1.
Embodiment 4 carries out the preparation of oligomer (Va) using sulfydryl-alkene reaction
1,3-, bis- cloves phenolic group -2- propyl alcohol (I) (3.84g, 10mmol), 1,6- ethanthiol are added in reaction bulb
(1.65g, 11mmol), benzophenone (0.01g), tetrahydrofuran 20ml make solvent, the illumination under the ultraviolet lamp of 365nm at room temperature
1h.The sodium hydroxide solution that 1M is added after having reacted washs 2-3 time, wash 2 times, is concentrated under reduced pressure and removes solvent and on a small quantity
Monomer obtains oligomer (Va) (3.02g).GPC measures molecular weight Mn=2470Da.
Embodiment 5 carries out the preparation of oligomer (Vb) using sulfydryl-alkene reaction
1,3-, bis- cloves phenolic group -2- propyl alcohol (I) (3.84g, 10mmol), 1,2- dithioglycol are added in reaction bulb
(1.04g, 11mmol), benzoin methyl ether (0.02g), Isosorbide-5-Nitrae-dioxane 20ml makees solvent, at room temperature in the ultraviolet lamp of 365nm
Lower illumination 1h.The potassium hydroxide solution that 1M is added after having reacted washs 2 times, washes 3 times, is concentrated under reduced pressure and removes solvent and few
The monomer of amount obtains oligomer (Vb) (2.64g).GPC measures molecular weight Mn=2190Da.
Embodiment 6 carries out the preparation of oligomer (Vc) using sulfydryl-alkene reaction
1,3-, bis- cloves phenolic group -2- propyl alcohol (I) (3.84g, 10mmol), Isosorbide-5-Nitrae-two (thiopurine methyltransferase) benzene are added in reaction bulb
(1.87g, 11mmol), thioxanthone (0.015g), dichloromethane 20ml make solvent, at room temperature the light under the ultraviolet lamp of 365nm
According to 1h.The lithium hydroxide solution that 1M is added after having reacted washs 2 times, washes 2 times, and the monomer that solvent and remnants are boiled off under decompression obtains
To oligomer (Vb) (3.57g).GPC measures molecular weight Mn=2680Da.
7 oligomer of embodiment (Va) autoxidation reaction prepares linear polymer (VIa)
Oligomer (Va) (0.64g), elemental iodine (10mg) are added in a there-necked flask, and is dissolved in 20ml tetrahydrofurans.
Reaction solution high degree of agitation 10h at 25 DEG C.Then 60 DEG C are warming up to, continues to stir 5h.It is cooling, excessive first is added in reaction solution
Alcohol, and filter to obtain linear polymer (VIa) 0.6g.GPC measures molecular weight Mn=10270Da.
8 oligomer of embodiment (Vb) autoxidation reaction prepares linear polymer (VIb)
The addition oligomer (Vb) (0.72g) in a there-necked flask, 30% hydrogen peroxide (2.0g), sodium iodide (3.2g), and it is molten
In 20mL dimethyl sulfoxide (DMSO)s.The first high degree of agitation 7h at 30 DEG C of reaction solution.Then 80 DEG C are warming up to, continues to stir 3h.It is cooling,
Excessive methanol is added in reaction solution, and filters to obtain linear polymer (VIb) 0.68g.GPC measures molecular weight Mn=9740Da.
Embodiment 9, which is reacted using linear polymer (VIa) with hexamethylene diisocyanate (HDI), prepares cross-linked polymer
(VIIa)
The addition linear polymer (VIa) (0.53g) in the there-necked flask of 50ml, 1, hexamethylene-diisocyanate (0.20g), three
Ethamine (10mg), tetrahydrofuran 20ml make solvent.Reaction solution return stirring 8h.It is cooling, excessive methanol, and mistake is added in reaction solution
Filter to obtain faint yellow cross-linked polymer (VIIa) 0.46g.
Embodiment 10, which is reacted using linear polymer (VIa) with isophorone diisocyanate (IPDI), prepares cross-linked polymeric
Object (VIIb)
Linear polymer (VIa) (0.53g), isophorone diisocyanate (0.23g), TMEDA are added in reaction bulb
(20mg), acetone 20ml make solvent.Reaction solution return stirring 15h.It is cooling, excessive methanol is added in reaction solution, and filter yellow
Color cross-linked polymer (VIIb) 0.51g.
Embodiment 11, which is reacted using linear polymer (VIb) with toluene di-isocyanate(TDI) (TDI), prepares cross-linked polymer
(VIIc)
Linear polymer (VIb) (0.52g), toluene di-isocyanate(TDI) (TDI) are added in the there-necked flask of 50ml
(0.22g), dibutyl tin laurate (15mg), glycol dimethyl ether 20ml make solvent.Reaction solution return stirring 12h.It is cooling,
Excessive methanol is added in reaction solution, and filters to obtain faint yellow cross-linked polymer (VIIc) 0.43g.
The heatproof of 12 cross-linked polymer of embodiment (VIIa) is tested
The heatproof test of cross-linked polymer (VIIa) is carried out by thermogravimetric analysis (TGA).Its T is measured by TGAd5For
400 DEG C or so, Td10It is 1000 DEG C or so, Td50It is 1300 DEG C.Show that VIIa as a kind of pure organic polymer, has non-
The high temperature resistance of Chang Qiang.
The self-healing properties of 13 cross-linked polymer of embodiment (VIIa) are tested
Film is made in cross-linked polymer (VIIa) on a glass substrate, it is micro- then to mark width about 30 on film with blade
The cut of rice is simultaneously taken pictures with SEM.It takes pictures after the scored portion ultraviolet light 30 minutes of 365nm, then with SEM, from photo
Find out that cut disappears；The cut of about 30 microns of width is marked on film with blade and is taken pictures with SEM for the second time, repeats the step of front
Suddenly, second is carried out to repair；Then third time repeats step, carries out third time reparation.
The embodiments of the present invention have been described in detail above, but content is only the preferred embodiment of the present invention,
It is not intended to limit the invention.All all any modification, equivalent and improvement etc. done in the application range of the present invention, should all
It is included within protection scope of the present invention.
Claims (10)
- A kind of molecular structure such as formula 1. (1) compound represented,
- 2. the preparation method of compound described in a kind of claim 1, it is characterised in that this method is to be by eugenol and structural formulaCompound or structural formula beCompound with 2:1 molar ratio mixes, in alkaline solution environment Reaction；Wherein X is selected from one of Cl, Br or I.
- 3. preparation method according to claim 2, it is characterised in that：The solute of the alkaline solution is inorganic base or organic Alkali, the inorganic base are selected from KOH, NaOH, LiOH, Na2CO3、K2CO3、Cs2CO3、NaHCO3、KHCO3One or more of which, The organic base is selected from triethylamine, pyridine, N- Alkylpiperidines, diisopropylethylamine, 1,8- diazabicylos [5.4.0] 11- The one of which of 7- alkene, tetramethylethylenediamine, five methyl diethylentriamine, triethylenediamine, 4-dimethylaminopyridine Or it is a variety of；The solvent of the alkaline solution is selected from water, dichloromethane, ether, diisopropyl ether, methyl tertiary butyl ether(MTBE), methanol, second Alcohol, normal propyl alcohol, isopropanol, tetrahydrofuran, glycol dimethyl ether (DME), 1,4- dioxane, acetone, 2- butanone, acetic acid second Ester, butyl acetate, chloroform, carbon tetrachloride, 1,2- dichloroethanes, 1,1,1- trichloroethanes, acetonitrile, benzonitrile, dimethyl sulfoxide (DMSO), The one or more of which of N,N-dimethylformamide；The temperature of the reaction is 0 DEG C of reflux temperature to solvent.
- 4. a kind of molecular structure oligomer as shown in formula (2),In formula (2), R1Selected from C2-C20Alkyl, naphthenic base or benzyl；N is the integer more than or equal to 2.
- 5. compound described in claim 1 is used to prepare the application of oligomer described in claim 4 as monomer, it is characterised in that The application be by dithiols compound shown in compound shown in formula (1) and excessive structure such as formula (3) carry out it is light-initiated under Sulfydryl-alkene click-reaction；In formula (3), R1Selected from C2-C20Alkyl, naphthenic base or benzyl；In the reaction, photoinitiator Dosage not higher than preparing the 5% of raw material gross mass, the photoinitiator is selected from benzophenone, 4- methyl benzophenones, 2- first Base benzophenone, 4,4 '-dimethyl benzophenones, 4,4 '-dihydroxy benaophenonels, 2,4 dihydroxyl benzophenone, Michler's keton, 4,4 '-two (thiopurine methyltransferase) benzophenone, 2- hydroxy-2-methyl -1- phenylacetones, 1- hydroxycyclohexyl phenyl ketones, 2- methyl - 2- (4- morpholinyls) -1- [4- (methyl mercapto) phenyl] -1- acetone, 2,4,6- trimethylbenzoy-diphenies phosphine oxide, 2,4, 6- trimethylbenzoyl phenyls phosphinic acid ethyl ester, 2- dimethylamino -2- benzyls -1- [4- (4- morpholinyls) phenyl] -1- butanone, 2- Hydroxy-2-methyl -1- [4- (2- hydroxyl-oxethyls) phenyl] -1- acetone, styrax, benzoin dimethylether, benzoin ethyl ether, peace The fragrant isopropyl ether of breath, benzoin isobutyl ether, diphenylethan, α, alpha, alpha-dimethyl oxygroup-α-phenyl acetophenone, thioxanthone one of which Or it is a variety of；The solvent of the reaction is selected from dichloromethane, ether, diisopropyl ether, methyl tertiary butyl ether(MTBE), tetrahydrofuran, ethylene glycol Dimethyl ether, 1,4- dioxane, acetone, 2- butanone, ethyl acetate, butyl acetate, chloroform, carbon tetrachloride, 1,2- dichloroethanes, Wherein the one of 1,1,1- trichloroethanes, acetonitrile, benzonitrile, dimethyl sulfoxide (DMSO), N,N-dimethylformamide, benzene,toluene,xylene Kind is a variety of；The temperature of the reaction is 0 DEG C of reflux temperature to solvent；
- 6. a kind of molecular structure linear polymer as shown in formula (4),In formula (4), R1Selected from C2-C20Alkyl, naphthenic base or benzyl；N is the integer more than or equal to 2；M is more than or equal to 2 Integer.
- 7. oligomer described in claim 4 is used to prepare the application of linear polymer described in claim 6, it is characterised in that this is answered With being that oligomer shown in formula (2) is carried out oxidative coupling reaction；In the oxidative coupling reaction oxidant be selected from hydrogen peroxide, The one or more of which of iodine, chlorosulfuric acid, oxygen；In the oxidative coupling reaction solvent be selected from dichloromethane, chloroform, ether, Diisopropyl ether, methyl tertiary butyl ether(MTBE), tetrahydrofuran, glycol dimethyl ether, 1,4- dioxane, acetone, 2- butanone, acetic acid second Ester, butyl acetate, chloroform, carbon tetrachloride, 1,2- dichloroethanes, acetonitrile, benzonitrile, dimethyl sulfoxide (DMSO), N, N- dimethyl formyls The one or more of which of amine, benzene,toluene,xylene；The temperature of the oxidative coupling reaction is 0 DEG C of reflux temperature to solvent Degree.
- 8. a kind of molecular structure high temperature resistant self-healing polymers as shown in formula (5),In formula (5), R1Selected from C2-C20Alkyl, naphthenic base or benzyl；R2Selected from C2-C15Alkyl, naphthenic base or phenyl；N is Integer more than or equal to 2；M is the integer more than or equal to 2.
- 9. linear polymer described in claim 6 is used to prepare the application of high temperature resistant self-healing polymers described in claim 8, It is characterized in that the application is to react linear polymer shown in formula (4) under catalytic condition with diisocyanate.
- 10. application according to claim 9, it is characterised in that catalyst used in the reaction is selected from N, N- dimethyl Cyclohexylamine, bis- (2- dimethylaminoethyls) ethers, N, N, N', N'- tetramethylethylenediamines, triethylamine, N, N- dimethyl benzylamines, N- second Base morpholine, N-methylmorpholine, N, N '-diethyl piperazine, triethanolamine, dibutyl tin laurate one or more of which.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810210458.8A CN108484912A (en) | 2018-03-14 | 2018-03-14 | A kind of eugenol based high-temp-resistant self-healing polymers and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810210458.8A CN108484912A (en) | 2018-03-14 | 2018-03-14 | A kind of eugenol based high-temp-resistant self-healing polymers and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108484912A true CN108484912A (en) | 2018-09-04 |
Family
ID=63339379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810210458.8A Pending CN108484912A (en) | 2018-03-14 | 2018-03-14 | A kind of eugenol based high-temp-resistant self-healing polymers and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108484912A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111607086A (en) * | 2020-05-27 | 2020-09-01 | 南雄中科院孵化器运营有限公司 | High-thermal-conductivity remoldable liquid crystal elastomer composite material and preparation method and application thereof |
| CN112851903A (en) * | 2021-01-12 | 2021-05-28 | 浙江多邦新材料有限公司 | Preparation method of organic silicon modified waterborne polyurethane and product thereof |
| CN113956438A (en) * | 2021-11-22 | 2022-01-21 | 中国林业科学研究院林产化学工业研究所 | Preparation method of bio-based self-repairing flame-retardant material with high dielectric property |
| CN114163598A (en) * | 2021-12-24 | 2022-03-11 | 中国林业科学研究院林产化学工业研究所 | Self-repairing polyurethane derived from bio-based polyol and preparation method thereof |
| CN115873252A (en) * | 2022-11-11 | 2023-03-31 | 河南省科学院化学研究所有限公司 | Urethane-based elastomer and preparation method thereof |
| WO2025009701A1 (en) * | 2023-07-06 | 2025-01-09 | 삼성에스디아이 주식회사 | Curable composition, cured layer manufactured using composition and display device including cured layer |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB859456A (en) * | 1958-03-07 | 1961-01-25 | Bataafsche Petroleum | Improvements in or relating to the production of polyglycidyl ethers of tetrakis (alkyl-substituted hydroxyphenyl) alkanes |
| US3210376A (en) * | 1962-08-02 | 1965-10-05 | Johnson & Son Inc S C | Bisphenolic lactones |
| US3542759A (en) * | 1964-01-31 | 1970-11-24 | Pharmacia Ab | Copolymerizates of polyhydroxy and bifunctional compounds reacted with alkylene oxides and process of preparation |
| US3784584A (en) * | 1971-03-26 | 1974-01-08 | Ciba Geigy Corp | Methylolglycidyl ethers |
| CN101429273A (en) * | 2008-12-17 | 2009-05-13 | 湘潭大学 | Process for producing wind electricity grade of bisphenol F epoxy resin |
| CN105924623A (en) * | 2016-04-29 | 2016-09-07 | 河北大学 | Eugenol epoxy resin and preparing method and application thereof |
-
2018
- 2018-03-14 CN CN201810210458.8A patent/CN108484912A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB859456A (en) * | 1958-03-07 | 1961-01-25 | Bataafsche Petroleum | Improvements in or relating to the production of polyglycidyl ethers of tetrakis (alkyl-substituted hydroxyphenyl) alkanes |
| US3210376A (en) * | 1962-08-02 | 1965-10-05 | Johnson & Son Inc S C | Bisphenolic lactones |
| US3542759A (en) * | 1964-01-31 | 1970-11-24 | Pharmacia Ab | Copolymerizates of polyhydroxy and bifunctional compounds reacted with alkylene oxides and process of preparation |
| US3784584A (en) * | 1971-03-26 | 1974-01-08 | Ciba Geigy Corp | Methylolglycidyl ethers |
| CN101429273A (en) * | 2008-12-17 | 2009-05-13 | 湘潭大学 | Process for producing wind electricity grade of bisphenol F epoxy resin |
| CN105924623A (en) * | 2016-04-29 | 2016-09-07 | 河北大学 | Eugenol epoxy resin and preparing method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| CHUANJIE CHENG等: "Renewable eugenol-based functional polymers with self-healing and high temperature resistance properties", 《JOURNAL OF POLYMER RESEARCH》 * |
| 赵应龙等编著: "《防腐保温保冷工程设计与施工手册》", 31 October 1996, 石油大学出版社 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111607086A (en) * | 2020-05-27 | 2020-09-01 | 南雄中科院孵化器运营有限公司 | High-thermal-conductivity remoldable liquid crystal elastomer composite material and preparation method and application thereof |
| CN112851903A (en) * | 2021-01-12 | 2021-05-28 | 浙江多邦新材料有限公司 | Preparation method of organic silicon modified waterborne polyurethane and product thereof |
| CN113956438A (en) * | 2021-11-22 | 2022-01-21 | 中国林业科学研究院林产化学工业研究所 | Preparation method of bio-based self-repairing flame-retardant material with high dielectric property |
| CN113956438B (en) * | 2021-11-22 | 2024-09-13 | 中国林业科学研究院林产化学工业研究所 | Preparation method of bio-based self-repairing flame-retardant material with high dielectric property |
| CN114163598A (en) * | 2021-12-24 | 2022-03-11 | 中国林业科学研究院林产化学工业研究所 | Self-repairing polyurethane derived from bio-based polyol and preparation method thereof |
| CN114163598B (en) * | 2021-12-24 | 2023-11-21 | 中国林业科学研究院林产化学工业研究所 | Bio-based polyol derived self-repairing polyurethane and preparation method thereof |
| CN115873252A (en) * | 2022-11-11 | 2023-03-31 | 河南省科学院化学研究所有限公司 | Urethane-based elastomer and preparation method thereof |
| CN115873252B (en) * | 2022-11-11 | 2024-04-16 | 河南省科学院化学研究所有限公司 | Urethane-based elastomer and preparation method thereof |
| WO2025009701A1 (en) * | 2023-07-06 | 2025-01-09 | 삼성에스디아이 주식회사 | Curable composition, cured layer manufactured using composition and display device including cured layer |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108484912A (en) | A kind of eugenol based high-temp-resistant self-healing polymers and preparation method thereof | |
| CN102597156B (en) | Methods of using hydrofluoroethers as heat transfer fluids | |
| ITMI20000003A1 (en) | PROCESS FOR THE PREPARATION OF PERFLUOROPOLES OXY CHILENI WITH OXYDRYL TERMINALS | |
| CN109456298A (en) | A kind of loop coil class diol compound and loop coil class polycarbonate and preparation method thereof | |
| CN103274908A (en) | Bisphenol monomer containing bi-tert-butyl and fluorenyl structure, and preparation method and application thereof | |
| CN109796581B (en) | Narrow-band conjugated polymer containing low polyethylene glycol side chain structure and preparation method and application thereof | |
| CN116239626B (en) | Fluorine modified borate, preparation method thereof and brake fluid containing fluorine modified borate | |
| CN106478381B (en) | A method of bis ether fluorenes is prepared by catalyzing epoxyethane | |
| KR101417305B1 (en) | Polymer electrolyte membrane chemically bonded by ionic liquid and fuel cell using the same | |
| CN113248787B (en) | Plasticizer and preparation method and application thereof | |
| CN101962434B (en) | Alkali-soluble hyperbranched photosensitive organic silicon prepolymer and preparation method thereof | |
| KR101379361B1 (en) | Polymer electrolyte membrane comprising ionic liquid having sulfonic acid group, and method for preparing the same | |
| KR102695260B1 (en) | Alternating copolymer and preparation method thereof | |
| Schönberger et al. | Synthesis and characterization of novel (sulfonated) poly (arylene ether) s with pendent trifluoromethyl groups | |
| Chen et al. | Synthesis and properties of novel phosphorus‐containing poly (ether ether ketone ketone) s | |
| CN113336946B (en) | Nopol bio-based silicon-containing oxetane monomer and preparation method thereof | |
| PL122547B1 (en) | Process for manufacturing novel /co/ polycarbonates | |
| CA2703710A1 (en) | Ionically conductive polymer for use in electrochemical devices | |
| Xu et al. | Synthesis and characterization of novel poly (sulfone siloxane) s with good solubility and recyclability based on siloxane units | |
| CN110981756A (en) | Hexafluoroisopropyl acrylate monomer and preparation method thereof | |
| CN116082129B (en) | Method for preparing Galvanic oxygen radical by oxidizing hydrogen peroxide | |
| CN102533277B (en) | Poly-fluorine polycyclic liquid crystal compound as well as preparation method and application thereof | |
| CN115850666A (en) | Trithiophene alkyl sulfonic acid polymer, and preparation method and application thereof | |
| KR101693997B1 (en) | Copolymer for manufacturing membrane of a fuel cell and membrane of a fuel cell | |
| CN109734897A (en) | A kind of preparation method containing DOPO structural polyether ether ketone thin-walled cable material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180904 |