CN106188387A - A kind of Tri-n-butyltin methacrylate azobenzene polymer with optical Response and synthetic method - Google Patents
A kind of Tri-n-butyltin methacrylate azobenzene polymer with optical Response and synthetic method Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
- C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
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Abstract
The present invention relates to a kind of Tri-n-butyltin methacrylate azobenzene polymer with optical Response and synthetic method；Diphenyl diimide is dissolved in dichloromethane, under the conditions of 0 DEG C, is added drop-wise to, containing methacrylic acid, in the system of catalyst 4 dimethylamino naphthyridine, be passed through air in nitrogen eliminating system；Dripping in system by dehydrant dicyclohexylcarbodiimide subsequently, 0 DEG C is reacted 25 hours, is warming up to 25 DEG C, reacts 12 24 hours, obtain the azo monomer that olefin group is contained in one end；By methyl methacrylate, initiator A IBN adds in container, and oxygen in logical nitrogen eliminating system drips the azo monomer of preparation in step 1 in system, reacts at 60 90 DEG C, react end in 38 hours, obtain Tri-n-butyltin methacrylate azobenzene polymer.The preparation method of the present invention is simple, and azobenzene polymer material has good optical Response, and stability is high, provides method for synthesizing methylmethacrylate class azobenzene polymer.
Description
Technical field
The present invention relates to a kind of Tri-n-butyltin methacrylate azobenzene polymer with optical Response and synthetic method, its
Information stores, photoswitch, photochromic material, surface relief grating, liquid crystal material, sensor, organic effect film crystal
The fields such as pipe are all with a wide range of applications.Belong to Macroscopic single crystal preparation field.
Background technology
The advantages such as luminous energy has cleanliness without any pollution, it is not necessary to Medium Propagation, it is easy to controls and uses, wide material sources, therefore, closely
Over a little years, luminous energy can be efficiently translated into the material of mechanical energy and increasingly be paid close attention to by scholar.Azobenzene and its derivatives
The polymeric material of good photo absorption property as photoresponse chromophore and ordered liquid crystal structure, can be had for preparation
(Haifeng Yu,“Recent Advances in Photoresponsive Liquid-Crystalline Polymers
Containing Azobenzene Chromophores,”J.Mater.Chem.C 2,no.17(2014):3047–54,doi:
10.1039/C3TC31991A.).When containing flexible molecule chain (e.g., alkyl chain) in azobenzene polymer, azobenzene molecule passes through
Covalent bond effect is connected in strand, and azobenzene molecule can show liquid crystal property.Azo is irradiated with the light of suitable wavelength
During polymer, this type flexible material can show light-operated performance, such as Photo alignment, photochemical transformations and photoinduced molecule
Synergy movement (Alexis Goulet-Hanssens and Christopher J.Barrett, " Photo-Control of
Biological Systems with Azobenzene Polymers,”Journal of Polymer Science,Part
A:Polymer Chemistry 51,no.14(2013):3058–70,doi:10.1002/pola.26735.)。
At present, there have been the method much preparing diphenyl diimide liquid crystal polymer by the method for covalence graft, this kind of azo
Benzene polymer tool optical drive (e.g., UV light, blue-green, polarized light etc.), its main chain usually contains type siloxane, vinyl,
The flexible molecule chains such as acrylic compounds (Kyung Min Lee et al., " Photomechanical Mechanism and
Structure-Property Considerations in the Generation of Photomechanical Work
in Glassy,Azobenzene Liquid Crystal Polymer Networks,”J.Mater.Chem.22,no.2
(2012):691–98,doi:10.1039/C1JM14017E.).The optical Response of azobenzene polymer is by soft segment and azo
Segment together decides on.Therefore, synthesis has the azobenzene polymer material of more excellent photo absorption property needs to explore.Methyl-prop
The methyl methacrylate part of e pioic acid methyl ester class azobenzene polymer provides molecule chain flexibility, and azo structure then can be right
Light produces response, makes material list reveal good optical Response (Alexey Bobrovsky et al., " Effect of
Molecular Structure on Chiro-Optical and Photo-Optical Properties of Smart
Liquid Crystalline Polyacrylates,”Macromolecules 46,no.11(June 11,2013):4276–
84,doi:10.1021/ma401010t.)。
Summary of the invention
It is an object of the invention to provide preparation and there is the Tri-n-butyltin methacrylate azo of quickly optical Response (in 5s)
The synthetic method of polymer: the material of gained has excellent mechanical property, good size and chemical stability, and excellent is soft
Toughness and Lightness, meanwhile, this material also has quick photo absorption property.Therefore, this material, at photoswitch, liquid crystal material, passes
Sensor, the field such as organic effect thin film transistor (TFT) is all with a wide range of applications.Belong to Macroscopic single crystal preparation field.
A kind of Tri-n-butyltin methacrylate azobenzene polymer with optical Response, its structure is as follows:
The synthetic method of the Tri-n-butyltin methacrylate azobenzene polymer with optical Response of the present invention；Step is as follows:
(1) synthesis of azo monomer: be dissolved in dichloromethane by diphenyl diimide, under the conditions of 0 DEG C, is added drop-wise to containing methyl
Acrylic acid, in the system of catalyst DMAP, is passed through air in nitrogen eliminating system；Subsequently by dehydrant two hexamethylene
Base carbodiimide drips in system, and 0 DEG C is reacted 2-5 hour, is warming up to 25 DEG C, reacts 12-24 hour, obtain one end and contain alkene
The azo monomer of hydrocarbyl group；
(2) by methyl methacrylate, initiator A IBN adds in container, and oxygen in logical nitrogen eliminating system, to system
In middle dropping step 1, the azo monomer of preparation, reacts at 60-90 DEG C, reacts end in 3-8 hour, obtain methacrylic acid
Methyl ester class azobenzene polymer.
Described diphenyl diimide is 4-(4-nitrophenylazo)-1-naphthols or 4-[(4-ethoxyl phenenyl) azo] naphthols.
Described diphenyl diimide monomer and the mol ratio of methacrylic acid are 2:1～1:5.
Described diphenyl diimide monomer and the preferred molar ratio of methacrylic acid are 1:1.
Described DMAP and the molal weight of dicyclohexylcarbodiimide are than for 1:5～20.
The azo monomer of described synthesis and methyl methacrylate are by mole mass ratio 1:10-1:100.Preferably synthetic
Azo monomer and methyl methacrylate mass ratio are 1:15.
The addition of initiator A IBN is that methyl methacrylate adds the 1～5% of weight/mass percentage composition.
The present invention prepares one end by esterification and has the novel azo benzene monomer of olefin group, then synthesizing methyl third
E pioic acid methyl ester class azobenzene polymer；Preparation method is simple, and productivity is high, and reaction condition is gentle.Methacrylic acid is contained with one end
The azo monomer of hydroxyl carries out esterification, then is had the idol of optical Response by copolymerisation preparation with methyl methacrylate
Pyridine polymer.Under ultraviolet light irradiates, can quickly occur Texturized, quick recoverable under dark surrounds, methyl-prop
E pioic acid methyl ester provides flexible molecule chain, makes polymer have quick optical Response.This invention may be used for preparing various with azo
For the methyl methacrylate type azobenzene polymer of side chain, open at light controlled material, light oriented material, information storage material, light
Pass, light-induced surface grating material, light probe, photochromic material, liquid crystal material, sensor, organic effect film crystal
Pipe field can be applied, and preparation has the light responsive material of various premium properties.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the diphenyl diimide monomer of the 2-in-1 one-tenth of embodiment.
It can be seen that in the infrared spectrum of methacrylic acid, 1636cm-1Absworption peak represent C=C double bond
Stretching vibration D.M.Garc í a et al., " Synthesis and Characterization of Poly (methacrylic
Acid)Hydrogels for Metoclopramide Delivery,”European Polymer Journal 40,no.8
(2004): 1,637 43, doi:10.1016/j.eurpolymj.2004.03.011., 1700cm-1And 1203cm-1Represent respectively
The absworption peak S.Ramesh et al. of C=O and C-O stretching vibration, " FTIR Studies of PVC/PMMA Blend
Based Polymer Electrolytes,”Spectrochimica Acta-Part A:Molecular and
Biomolecular Spectroscopy 66,no.4–5(2007):1237–42,doi:10.1016/
j.saa.2006.06.012..Diphenyl diimide raw material 4-(4-nitrophenylazo)-1-naphthols and methacrylic acid pass through esterification
Preparing azo product, the infrared spectrum of product is similar to 4-(4-nitrophenylazo)-1-naphthols, simply product infrared spectrum
O-H stretching vibration peak in figure disappears, and at 1701cm-1Occur in that the absworption peak of new representative C=O stretching vibration, illustrate even
The success of pyridine Product formation.
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of the diphenyl diimide product prepared by embodiment 2；
Its concrete peak position:1H NMR (500MHz, DMSO-d6): δ=8.49 (d, 2H, Ar-H), 8.26 (d, 2H, Ar-
H), 8.00 (t, 2H, Ar-H), 7.85 (t, 1H, Ar-H), 7.77 (t, 1H, Ar-H), 7.60 (m, 2H, Ar-H), 6.50 (d, 1H,
Ar-H), 6.07 (s, 1H, C=C-H), 5.75 (s, 1H, C=C-H), 2.13 (s, 3H, C-H).
Azo raw material 4-(4-nitrophenylazo)-1-naphthols that Fig. 3 is used by embodiment 2 and the scanning electron microscope of product
(SEM) photo.
It can be seen that 4-(4-nitrophenylazo)-1-naphthols has undefined structure from Fig. 3 (a), sample is by unformed
Granule composition random block.Product shown in Fig. 3 (b), then by being self-assembly of banding Micro-sheet Structure, arranges
Neatly.
Fig. 4 is the photoresponse photo of the azobenzene polymer of embodiment 2 preparation.
Fig. 4 (a) is non-irradiated Azo Liquid Crystal Polymer Films, there it can be seen that Azo Liquid Crystal Polymer Films is smooth, does not occurs
Deformation.Fig. 4 (b) is the Azo Liquid Crystal Polymer Films after ultra-vioket radiation 5s, it can be seen that thin film occurs significantly in 5s
Texturized, illustrate that this Azo Liquid Crystal Polymer Films has the most significantly optical drive phenomenon.
Detailed description of the invention
Preferred scope that the present invention further illustrate rather than limit the present invention is presented herein below.Its course of reaction and saying
Bright step is as follows:
(1) synthesis of azo monomer: under the conditions of 0 DEG C, with dichloromethane as solvent, by 0.01-1mol/L 4-(4-nitre
Base benzeneazo)-1-naphthols or 4-[(4-ethoxyl phenenyl) azo] naphthol solution be added drop-wise in methacrylic acid, 4-(4-nitro
Benzeneazo) molal weight of-1-naphthols or 4-[(4-ethoxyl phenenyl) azo] naphthols and methacrylic acid is than for 2:1-1:5.
Adding DMAP (DMAP) and dicyclohexylcarbodiimide (DCC) in system, the molal weight ratio of DMAP and DCC is
1:5-1:20；First reaction is carried out 2-5 hour at 0 DEG C, after being warming up to 25 DEG C, continues reaction 12-24 hour, obtains azo and produces
Thing；
Course of reaction is:
(2) synthesis of Tri-n-butyltin methacrylate azobenzene polymer: by azo monomer and the methyl methacrylate of synthesis
Carrying out polycondensation reaction in a mole ratio of mass ratio 1:10-1:100, the addition of initiator A IBN is that methyl methacrylate adds
The 1-5% of dosage；First methyl methacrylate and AIBN are added in container, oxygen in logical nitrogen eliminating system at 25 DEG C
Gas.With backward system is slowly added dropwise in step 1 azo monomer prepared, after being added dropwise to complete, it is warming up to 60-90 DEG C and carries out anti-
Should, react end in 3-8 hour, obtain Tri-n-butyltin methacrylate azobenzene polymer.
Its reaction equation is:
R1:OCH2CH3
NO2
Embodiment 1:
(1) synthesis of azo monomer: under the conditions of 0 DEG C, with dichloromethane as solvent, by 0.01mol/L 4-(4-nitro
Benzeneazo)-1-naphthol solution is slowly dropped in methacrylic acid, 4-(4-nitrophenylazo)-1-naphthols and methacrylic acid
Molal weight than for 2:1；System adds DMAP (DMAP) and dicyclohexylcarbodiimide (DCC), DMAP
With the molal weight of DCC than for 1:5.First react 2 hours at 0 DEG C, then be warming up to 25 DEG C, continue reaction 12 hours, obtain
Azo monomer.Structural formula is:
(2) synthesis of Tri-n-butyltin methacrylate azobenzene polymer: by the azo monomer of methyl methacrylate Yu synthesis
Carrying out polycondensation reaction in a mole ratio of mass ratio 1:10, the addition of initiator A IBN is methyl methacrylate addition
1%.First methyl methacrylate and AIBN are added in container, oxygen in logical nitrogen eliminating system at 25 DEG C；With backward
System is slowly added dropwise in step 1 azo monomer of preparation, after being added dropwise to complete, is warming up to 60 DEG C and reacts, react 3 hours knots
Bundle, obtains Tri-n-butyltin methacrylate azobenzene polymer.
Embodiment 2:
(1) synthesis of azo monomer: under the conditions of 0 DEG C, with dichloromethane as solvent, by 0.1mol/L 4-(4-Nitrobenzol
Azo)-1-naphthol solution is slowly dropped in methacrylic acid, 4-(4-nitrophenylazo)-1-naphthols and methacrylic acid
Molal weight is than for 1:1.System adds DMAP (DMAP) and dicyclohexylcarbodiimide (DCC), DMAP with
The molal weight of DCC is than for 1:10；First react 2 hours at 0 DEG C, then be warming up to 25 DEG C, continue reaction 12 hours, obtain idol
Nitrogen monomer.Structural formula is:
(2) synthesis of Tri-n-butyltin methacrylate azobenzene polymer: the azo that methyl methacrylate and step 1 are synthesized
Monomer carries out polycondensation reaction in a mole ratio of mass ratio 1:15, and the addition of initiator A IBN is that methyl methacrylate adds
The 3% of amount.First methyl methacrylate and AIBN are added in container, oxygen in logical nitrogen eliminating system at 25 DEG C；With
Being slowly added dropwise in step 1 azo monomer of preparation in backward system, after being added dropwise to complete, be warming up to 75 DEG C and react, reaction 5 is little
Time terminate, obtain Tri-n-butyltin methacrylate azobenzene polymer.
Fig. 1 is 4-(4-nitrophenylazo)-1-naphthols, azo product and the infrared spectrogram of methacrylic acid.From figure
It can be seen that in the infrared spectrum of methacrylic acid, 1636cm-1Absworption peak represent C=C double bond stretching vibration absorb
Peak, 1700cm-1And 1203cm-1Represent the absworption peak of C=O and C-O stretching vibration respectively.4-(4-nitrophenylazo)-1-naphthols
Azo product is prepared by esterification, the infrared spectrum of product and 4-(4-nitrophenylazo)-1-with methacrylic acid
Naphthols is similar, and simply the O-H stretching vibration peak in azo product infrared spectrogram disappears, and at 1701cm-1Occur in that new generation
The absworption peak of table C=O stretching vibration, illustrates the synthesis success of azo product.
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of azo product, and its concrete peak position is as follows:
1H NMR (500MHz, DMSO-d6): δ=8.49 (d, 2H, Ar-H), 8.26 (d, 2H, Ar-H), 8.00 (t, 2H,
Ar-H), 7.85 (t, 1H, Ar-H), 7.77 (t, 1H, Ar-H), 7.60 (m, 2H, Ar-H), 6.50 (d, 1H, Ar-H), 6.07 (s,
1H, C=C-H), 5.75 (s, 1H, C=C-H), 2.13 (s, 3H, C-H).
Fig. 3 is scanning electron microscope (SEM) photo of 4-(4-nitrophenylazo)-1-naphthols and azo product.From figure permissible
Finding out, 4-(4-nitrophenylazo)-1-naphthols has undefined structure, and sample is random by form in unformed granule
Block.Product is then by being self-assembly of banding Micro-sheet Structure, marshalling.
Fig. 4 is the photoresponse photo of the azobenzene polymer of preparation, it can be seen that azobenzene polymer has quickly from photo
Response characteristic, and degree of crook is the biggest.
Embodiment 3:
(1) synthesis of azo monomer: under the conditions of 0 DEG C, with dichloromethane as solvent, by 1mol/L 4-, (4-Nitrobenzol is even
Nitrogen)-1-naphthol solution is slowly dropped in methacrylic acid, and 4-(4-nitrophenylazo)-1-naphthols rubs with methacrylic acid
Your mass ratio is 1:5.System adds DMAP (DMAP) and dicyclohexylcarbodiimide (DCC), DMAP and DCC
Molal weight than for 1:20；First react 5 hours at 0 DEG C, then be warming up to 25 DEG C, continue reaction 24 hours, obtain azo
Monomer.Structural formula is:
(2) synthesis of Tri-n-butyltin methacrylate azobenzene polymer: the azo that methyl methacrylate and step 1 are synthesized
Monomer carries out polycondensation reaction in a mole ratio of mass ratio 1:100, and the addition of initiator A IBN is that methyl methacrylate adds
The 5% of dosage.First methyl methacrylate and AIBN are added in container, oxygen in logical nitrogen eliminating system at 25 DEG C；
With backward system is slowly added dropwise in step 1 azo monomer prepared, after being added dropwise to complete, it is warming up to 90 DEG C and reacts, react 8
Hour terminate, obtain Tri-n-butyltin methacrylate azobenzene polymer.
Embodiment 4:
(1) synthesis of azo monomer: under the conditions of 0 DEG C, with dichloromethane as solvent, by 0.01mol/L 4-[(4-ethoxy
Base phenyl) azo] naphthol solution is slowly dropped in methacrylic acid, 4-[(4-ethoxyl phenenyl) azo] naphthols and methyl-prop
The molal weight of olefin(e) acid is than for 2:1；System adds DMAP (DMAP) and dicyclohexylcarbodiimide (DCC),
The molal weight of DMAP and DCC is than for 1:5.First react 2 hours at 0 DEG C, then be warming up to 25 DEG C, continue reaction 12 hours,
Obtain azo monomer.Structural formula is:
(2) synthesis of Tri-n-butyltin methacrylate azobenzene polymer: the azo that methyl methacrylate and step 1 are synthesized
Monomer carries out polycondensation reaction in a mole ratio of mass ratio 1:10, and the addition of initiator A IBN is that methyl methacrylate adds
The 1% of amount；First methyl methacrylate and AIBN are added in container, oxygen in logical nitrogen eliminating system at 25 DEG C.With
Being slowly added dropwise in step 1 azo monomer of preparation in backward system, after being added dropwise to complete, be warming up to 60 DEG C and react, reaction 3 is little
Time terminate, obtain Tri-n-butyltin methacrylate azobenzene polymer.
Embodiment 5:
(1) synthesis of azo monomer: under the conditions of 0 DEG C, with dichloromethane as solvent, by 0.2mol/L 4-[(4-ethoxy
Base phenyl) azo] naphthol solution is slowly dropped in methacrylic acid, 4-[(4-ethoxyl phenenyl) azo] naphthols and methyl-prop
The molal weight of olefin(e) acid is than for 1:2；System adds DMAP (DMAP) and dicyclohexylcarbodiimide (DCC),
The molal weight of DMAP and DCC is than for 1:15.First react 3 hours at 0 DEG C, then be warming up to 25 DEG C, continue reaction 17 hours,
Obtain azo monomer.Structural formula is:
(2) synthesis of Tri-n-butyltin methacrylate azobenzene polymer: the azo that methyl methacrylate and step 1 are synthesized
Monomer carries out polycondensation reaction in a mole ratio of mass ratio 1:30, and the addition of initiator A IBN is that methyl methacrylate adds
The 2.5% of amount；First methyl methacrylate and AIBN are added in container, oxygen in logical nitrogen eliminating system at 25 DEG C.
With backward system is slowly added dropwise in step 1 azo monomer prepared, after being added dropwise to complete, it is warming up to 70 DEG C and reacts, react 4
Hour terminate, obtain Tri-n-butyltin methacrylate azobenzene polymer.
Embodiment 6:
(1) synthesis of azo monomer: under the conditions of 0 DEG C, with dichloromethane as solvent, by 1mol/L 4-[(4-ethyoxyl
Phenyl) azo] naphthol solution is slowly dropped in methacrylic acid, 4-[(4-ethoxyl phenenyl) azo] naphthols and metering system
The molal weight of acid ratio is for 1:5；System adds DMAP (DMAP) and dicyclohexylcarbodiimide (DCC),
The molal weight of DMAP and DCC is than for 1:20.First react 5 hours at 0 DEG C, then be warming up to 25 DEG C, continue reaction 24 hours,
Obtain azo monomer.Structural formula is:
(2) synthesis of Tri-n-butyltin methacrylate azobenzene polymer: the azo that methyl methacrylate and step 1 are synthesized
Monomer carries out polycondensation reaction in a mole ratio of mass ratio 1:100, and the addition of initiator A IBN is that methyl methacrylate adds
The 5% of dosage；First methyl methacrylate and AIBN are added in container, oxygen in logical nitrogen eliminating system at 25 DEG C.
With backward system is slowly added dropwise in step 1 azo monomer prepared, after being added dropwise to complete, it is warming up to 90 DEG C and reacts, react 8
Hour terminate, obtain Tri-n-butyltin methacrylate azobenzene polymer.
Claims (9)
1. there is a Tri-n-butyltin methacrylate azobenzene polymer for optical Response, it is characterized in that its structure is as follows:
2. the synthetic method of the Tri-n-butyltin methacrylate azobenzene polymer with optical Response of claim 1；It is characterized in that
Step is as follows:
(1) synthesis of azo monomer: be dissolved in dichloromethane by diphenyl diimide, under the conditions of 0 DEG C, is added drop-wise to containing metering system
Acid, in the system of catalyst DMAP, is passed through air in nitrogen eliminating system；Subsequently by dehydrant dicyclohexyl carbon
Diimine drips in system, and 0 DEG C is reacted 2-5 hour, is warming up to 25 DEG C, reacts 12-24 hour, obtain one end and contain alkylene
The azo monomer of group；
(2) by methyl methacrylate, initiator A IBN adds in container, and oxygen in logical nitrogen eliminating system drips in system
Add the azo monomer of preparation in step 1, react at 60-90 DEG C, react end in 3-8 hour, obtain methyl methacrylate
Class azobenzene polymer.
3. method as claimed in claim 2, is characterized in that described diphenyl diimide is 4-(4-nitrophenylazo)-1-naphthols or 4-
[(4-ethoxyl phenenyl) azo] naphthols.
4. method as claimed in claim 2, is characterized in that the mol ratio of described diphenyl diimide monomer and methacrylic acid is 2:1
～1:5.
5. method as claimed in claim 4, is characterized in that the mol ratio of described diphenyl diimide monomer and methacrylic acid is 1:
1。
6. method as claimed in claim 2, is characterized in that described DMAP and dicyclohexylcarbodiimide
Molal weight is than for 1:5～20.
7. method as claimed in claim 2, is characterized in that the azo monomer of described synthesis is massaged with methyl methacrylate
You are mass ratio 1:10-1:100.
8. method as claimed in claim 7, is characterized in that azo monomer and the methyl methacrylate quality of described synthesis
Ratio is 1:15.
9. method as claimed in claim 2, is characterized in that the addition of initiator A IBN is that methyl methacrylate adds matter
The 1～5% of amount percentage composition.
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| CN107098995A (en) * | 2017-04-29 | 2017-08-29 | 天津大学 | A kind of heterocycle azo benzene macromolecule energy storage material and preparation method |
| CN107099006A (en) * | 2017-05-18 | 2017-08-29 | 常州大学 | A kind of preparation method with liquid crystal and light memory storage type Comblike polymers material |
| CN108767313A (en) * | 2018-04-20 | 2018-11-06 | 中山大学 | A kind of full solid state polymer electrolyte and its preparation method and application with spectrum plasticization effect |
| CN110498884A (en) * | 2019-08-28 | 2019-11-26 | 河北大学 | A kind of pH responsive polymer and preparation method thereof |
| CN111349200A (en) * | 2020-04-20 | 2020-06-30 | 广东花果山环保科技有限公司 | Aqueous high-hardness low-film-forming-temperature single-component acrylic resin and preparation method thereof |
| CN114335894A (en) * | 2021-12-21 | 2022-04-12 | 惠州锂威新能源科技有限公司 | Diaphragm with photochromic coating, preparation method thereof and secondary battery |
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| CN107098995A (en) * | 2017-04-29 | 2017-08-29 | 天津大学 | A kind of heterocycle azo benzene macromolecule energy storage material and preparation method |
| CN107098995B (en) * | 2017-04-29 | 2019-05-24 | 天津大学 | A kind of heterocycle azo benzene macromolecule energy storage material and preparation method |
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| CN110498884B (en) * | 2019-08-28 | 2021-06-15 | 河北大学 | PH response polymer and preparation method thereof |
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