CN104804124B - The polymer insulation layer material of heat cross-linking functionalization and preparation method and purposes - Google Patents
The polymer insulation layer material of heat cross-linking functionalization and preparation method and purposes Download PDFInfo
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- CN104804124B CN104804124B CN201510179443.6A CN201510179443A CN104804124B CN 104804124 B CN104804124 B CN 104804124B CN 201510179443 A CN201510179443 A CN 201510179443A CN 104804124 B CN104804124 B CN 104804124B
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- 238000007306 functionalization reaction Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000000463 material Substances 0.000 title abstract description 42
- 238000004132 cross linking Methods 0.000 title abstract description 33
- 229920000642 polymer Polymers 0.000 title abstract description 10
- 238000009413 insulation Methods 0.000 title abstract description 9
- 125000000852 azido group Chemical group *N=[N+]=[N-] 0.000 claims abstract description 23
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Chemical group C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000005669 field effect Effects 0.000 claims abstract description 15
- -1 nitrine alkynes Chemical class 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 40
- 229920001577 copolymer Polymers 0.000 claims description 40
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 23
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- WPGNHXPIVDREIR-UHFFFAOYSA-N but-3-ynyl prop-2-enoate Chemical compound C=CC(=O)OCCC#C WPGNHXPIVDREIR-UHFFFAOYSA-N 0.000 claims description 15
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 claims description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- 230000004888 barrier function Effects 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- WHVSIWLMCCGHFW-UHFFFAOYSA-N 3-azidopropan-1-ol Chemical compound OCCCN=[N+]=[N-] WHVSIWLMCCGHFW-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 claims description 5
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001345 alkine derivatives Chemical class 0.000 claims description 3
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 claims description 3
- 229940094989 trimethylsilane Drugs 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 239000012212 insulator Substances 0.000 abstract description 10
- 238000010719 annulation reaction Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000003431 cross linking reagent Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 229910052755 nonmetal Inorganic materials 0.000 abstract description 2
- 239000004793 Polystyrene Substances 0.000 description 44
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 34
- 229920002223 polystyrene Polymers 0.000 description 24
- 238000005160 1H NMR spectroscopy Methods 0.000 description 18
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- TURAMGVWNUTQKH-UHFFFAOYSA-N propa-1,2-dien-1-one Chemical group C=C=C=O TURAMGVWNUTQKH-UHFFFAOYSA-N 0.000 description 10
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 238000002329 infrared spectrum Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- FPWICHDFVFGNQT-UHFFFAOYSA-N 1-azido-4-prop-1-enylbenzene Chemical compound CC=CC1=CC=C(N=[N+]=[N-])C=C1 FPWICHDFVFGNQT-UHFFFAOYSA-N 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000010511 deprotection reaction Methods 0.000 description 4
- 239000002027 dichloromethane extract Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- CSQAOYKOFQMUMV-UHFFFAOYSA-N 2-pentacen-1-ylethynyl-tri(propan-2-yl)silane Chemical compound C1=CC=C2C=C(C=C3C(C=C4C=CC=C(C4=C3)C#C[Si](C(C)C)(C(C)C)C(C)C)=C3)C3=CC2=C1 CSQAOYKOFQMUMV-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001665 Poly-4-vinylphenol Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ONJMNXFNTYIEEA-UHFFFAOYSA-N benzene ethene Chemical compound C1=CC=CC=C1.C=C.C=C.C=C ONJMNXFNTYIEEA-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- BQFCCCIRTOLPEF-UHFFFAOYSA-N chembl1976978 Chemical compound CC1=CC=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 BQFCCCIRTOLPEF-UHFFFAOYSA-N 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000007416 differential thermogravimetric analysis Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
Abstract
The present invention relates to polymer insulation layer material, the Preparation method and use of two kinds of heat cross-linking difunctional functionalization.The polymer formulae of described heat cross-linking difunctional functionalization is as follows respectively:The invention still further relates to the preparation method of the polymer insulation layer material of described heat cross-linking difunctional functionalization and it is as purposes in organic field effect tube for the gate insulator.The polymer insulation layer material of the heat cross-linking difunctional functionalization of the present invention is incorporated into azido group and acetylene bond on main polymer chain and realizes crosslinking by the annulation of nitrine alkynes in a heated condition, thus lower temperature, non-metal catalyst and without add crosslinking agent under conditions of obtained crosslinking polymer insulation layer material, preparation technology is simple, resulting materials has good solvent orthogonality and excellent performance, fitting through solwution method and preparing various OFETs device, application prospect is quite varied.
Description
Technical field
The present invention relates to the polymer insulation layer material of the difunctional functionalization of two kinds of heat cross-linkings, especially two kinds heat cross-linkings
The polymeric material of difunctional functionalization and preparation method thereof, purposes.
Background technology
Organic field effect tube (organic field-effect transistor, OFETs) is with organic semiconductor material
The transistor device that material is active layer, is one of important organic semiconductor device.Organic field effect tube with without airport
Effect transistor is compared has lot of advantages: 1. have mechanical flexibility, can be compatible with plastic supporting base, and can be applicable to can
In the product folding；2. manufacture craft is simple, it is not necessary to the lithographic printing of high temperature, high vacuum and complexity；3. make
Standby technique is simple, and cost is relatively low；4. organic matter is easy to get, by adjusting the chemical modification of organic molecule easily
The performance of joint field-effect transistor；5. can realize large area, can large scale bending etc..These inorganic devices do not have
Feature so that it is large area, low cost and flexibility organic electronic product (as flexible display device drive circuit,
RFID tag and sensor) aspect has potential application prospect.
In organic field effect tube, insulating layer material is an important part, and this is mainly due to organic field
The mainly transmission in the organic semiconductor layer (2-6 molecular layer) closing on insulating barrier side of the electric charge of effect transistor.Absolutely
The impact on device for the edge layer mainly has following several respects: 1. the pattern of insulating barrier, orientation and surface roughness are half-and-half led
Body thin film form, the size of semiconductor grain, molecules align and electric charge transmission all have large effect；2. insulating barrier
Stability, carrier transport on organic field effect tube for the interfacial property have very big impact；3. insulating barrier
Dielectric constant has close ties with the threshold voltage of device with operation voltage.Therefore, study and prepare and organic semiconductor
The insulating barrier of excellent performance thinking coupling is also the important directions that organic field effect tube only has development.
The organic insulation layer material being applied to OTFT research at present mainly has following a few class: polymethylacrylic acid
Methyl esters, polyimides, polyvinyl phenol, polystyrene, polyvinyl alcohol etc..Simple polymer is bigger owing to having
Free volume causes being easy to leak electricity and breakdown.Crosslinked solvent orthogonality and the heat endurance that can strengthen thin polymer film
And electricity intensity.Crosslinking can be realized by illumination and heating, the crosslinked temperature of the insulating layer material of some current heat cross-linkings
Spending higher (150 DEG C), high processing temperature can be limited in the application of flexible field-effect transistor.Other heat cross-linking is anti-
Need during Ying to add catalyst or in course of reaction, generate new material and remain in a insulating layer, thus affecting device
The performance of part.
Content of the invention
For defect of the prior art, it is an object of the invention to provide the polymerization of two kinds of heat cross-linking difunctional functionalization
Thing insulating layer material and preparation method and purposes.
The present invention is achieved by the following technical solutions:
First aspect, the invention provides the polymethyl methacrylate copolymer of a kind of difunctional functionalization, its structure
It is shown below:
Wherein: x:y:z=(30～6): 3:3.
Second aspect, a kind of method of polymethyl methacrylate copolymer preparing above-mentioned difunctional functionalization, its bag
Include following steps:
A) by methyl methacrylate, trimethyl silica-based propargylmethyl acrylate, 3-nitrine propyl methacrylate
Adding in organic solvent A with initiator, under anaerobic, at 60～80 DEG C, preferably 70 DEG C issue raw free radical
Copolyreaction, it is thus achieved that the acetylene bond containing trimethyl silicane protection and the polymethyl methacrylate copolymer of azido group
(TMS-PMMA)；
B) polymethyl methacrylate copolymer of the described acetylene bond containing trimethyl silicane protection and azido group is dissolved in organic
In solvent B, add deprotecting regent, under room temperature, slough trimethyl silane, it is thus achieved that contain the difunctionality of acetylene bond and azido group
The polymethyl methacrylate copolymer (Di-PMMA) of group's functionalization.
Reaction scheme is as follows:
Preferably, in step a), described methyl methacrylate, trimethyl silica-based propargylmethyl acrylate
Mol ratio with 3-nitrine propyl methacrylate is (30～6): 3:3, preferably 14:3:3.
Described initiator is azodiisobutyronitrile, and the mol ratio of methyl methacrylate and initiator is 1:
(0.01～0.02), preferably 1:0.02；
Described organic solvent A is toluene；
In step b), described deprotecting regent is the tetrahydrofuran solution of tetrabutyl ammonium fluoride；
The mol ratio of described copolymer and deprotecting regent is 1:(100～200), preferably 1:200；
Described organic solvent B is oxolane.
Preferably, the preparation method of described trimethyl silica-based propargylmethyl acrylate is: described trimethyl silicane
The preparation method of base propargylmethyl acrylate is: use methacrylic chloride and propargyl alcohol in the presence of pyridine, in room temperature
React 8～12 hours, generate propargylmethyl acrylate；By described propargylmethyl acrylate at silver chlorate and 1,8-
Under the catalysis of diazabicylo 11 carbon-7-alkene, carry out back flow reaction 24～36 hours with trim,ethylchlorosilane, obtain front three
Base silica-based propargylmethyl acrylate；
Wherein, the mol ratio of described methacrylic chloride and propargyl alcohol is 1:(1～1.5)；Described propargylmethyl acrylic acid
The mol ratio of ester and trim,ethylchlorosilane is 1:(1～1.5).
The preparation method of described 3-nitrine propyl methacrylate is: by 3-chloropropyl alcohol and sodium azide at 60 DEG C anti-
Answer 36～48 hours, obtain 3-Azidopropanol；By described 3-Azidopropanol and methacrylic chloride in the presence of pyridine,
Carry out reacting 8～12 hours in room temperature, obtain 3-nitrine propyl methacrylate；
Wherein, the mol ratio of described 3-chloropropyl alcohol and sodium azide is 1:(2～4)；Described methacrylic chloride and 3-fold
The mol ratio of nitrogen base propyl alcohol is 1:(1～1.5).
The third aspect, present invention also offers a kind of polymethyl methacrylate materials such as above-mentioned difunctional functionalization and makees
For purposes in organic field effect tube for the gate insulator.
Fourth aspect, the invention provides the polystyrene copolymer of a kind of difunctional functionalization, its structure such as following formula institute
Show:
Wherein: x:y:z=(30～6): 3:3.
5th aspect, a kind of method of polystyrene copolymer preparing described difunctional functionalization, it includes as follows
Step:
C) styrene, 4-trimethyl silica-based propynyloxy base styrene, 4-azido-methyl styrene and initiator are added organic
In solvent orange 2 A, under anaerobic, at 60～80 DEG C, preferably 70 DEG C issue raw free radicals copolymerization reaction, it is thus achieved that contain
The acetylene bond of trimethyl silicane protection and the polystyrene copolymer (TMS-PS) of azido group；
D) will be dissolved in organic solvent B, and add deprotecting regent, at room temperature slough trimethyl silane, it is thus achieved that contain alkynes
The polystyrene copolymer (Di-PS) of the difunctional functionalization of key and azido group.
Reaction scheme is as follows:
In step c), described styrene, 4-trimethyl silica-based propynyloxy base styrene, cinnamic mole of 4-azido-methyl
Ratio is (30～6): 3:3, preferably 18:3:3.
Described initiator is azodiisobutyronitrile, and the mol ratio of monomer and initiator is 1:(0.01～0.02), it is preferably
1:0.02.
Described organic solvent C is toluene；
In step d), described deprotecting regent is the tetrahydrofuran solution of tetrabutyl ammonium fluoride；
The mol ratio of described copolymer and deprotecting regent is 1:(100～200), preferably 1:200.
Described organic solvent D is oxolane.
Preferably, the cinnamic preparation method of the silica-based propynyloxy base of described 4-trimethyl is: described 4-trimethyl
The cinnamic preparation method of silica-based propynyloxy base is: by 4-Vinyl phenol at Anhydrous potassium carbonate and be TBAB
Act on the back flow reaction carrying out in a solvent with propine bromine down under nitrogen protection 18～30 hours, obtain 4-propynyloxy base benzene second
Alkene；By described 4-propynyloxy base styrene under the catalysis of silver chlorate and 1,8-diazabicylo 11 carbon-7-alkene with trimethyl
Chlorosilane carries out the back flow reaction 18～24 hours under nitrogen protection in a solvent, obtains 4-trimethyl silica-based propynyloxy base benzene
Ethene；
Wherein, 4-Vinyl phenol and the mol ratio of propine bromine and Anhydrous potassium carbonate are 1:(2～3): (2～3)；Described 4-alkynes third
The mol ratio of epoxide styrene and trim,ethylchlorosilane is 1:(1～3)；
The cinnamic preparation method of described 4-azido-methyl is: by 4-1-chloro-4-methyl-benzene with sodium azide according to 1:(4～6)
Mol ratio, in DMF, 60 DEG C react 36～48 hours, obtain 4-azido-methyl styrene.
6th aspect, present invention also offers the polystyrene material of the difunctional functionalization of a kind of heat cross-linking described above
As purposes in organic field effect tube for the gate insulator.
Compared with prior art, the present invention has a following beneficial effect:
(1) the inventive method simply effectively, raw material be readily synthesized preparation, low cost, the target product purity obtaining is high；
(2) present invention uses the polymeric material of difunctional functionalization in a heated condition, introduces the cyclization of nitrine-alkynes
Reaction is as crosslinking method, it is to avoid what blending type insulating layer material caused is separated, it is achieved that at lower temperature, without gold
Metal catalyst and the cross-linked polymer insulating layer material without preparation densification under conditions of interpolation crosslinking agent；
(3) polymeric material of the heat cross-linking of gained of the present invention fits through solwution method and prepares various OFETs device, is
A kind of organic field effect tube gate insulating layer material of excellent performance.
Brief description
By reading the detailed description made non-limiting example with reference to the following drawings, other of the present invention are special
Levy, objects and advantages will become more apparent upon:
Fig. 1 is the proton nmr spectra of the polymethyl methacrylate copolymer (Di-PMMA) of difunctional functionalization
(1H-NMR)；
Fig. 2 be the polystyrene copolymer (Di-PS) of difunctional functionalization proton nmr spectra (1H-NMR)；
Fig. 3 is the infrared absorption spectroscopy (FT-IR) of difunctional functionalized copolymer material；
Fig. 4 is the differential scanning calorimetry curve of difunctional functionalized copolymer material；
Fig. 5 is the thermal gravimetric analysis curve of difunctional functionalized copolymer material；
Fig. 6 is the structural representation of the OFET device with the difunctional functionalized copolymer of heat cross-linking as gate insulator
Figure；
Fig. 7 is the leakage current density of the OFET device with the difunctional functionalized copolymer of heat cross-linking as gate insulator
Curve；
The curve of output of the OFET device with the difunctional functionalized copolymer of heat cross-linking as gate insulator for the Fig. 8；
The transfer curve of the OFET device with the difunctional functionalized copolymer of heat cross-linking as gate insulator for the Fig. 9.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.Following example will assist in those skilled in the art
Member is further appreciated by the present invention, but does not limit the present invention in any form.It should be pointed out that, the common skill to this area
For art personnel, without departing from the inventive concept of the premise, some deformation can also be made and improve.These broadly fall into
Protection scope of the present invention.
The 1st, embodiment prepares the polymethyl methacrylate copolymer insulating layer material of difunctional functionalization of heat cross-linking
Present embodiments provide polymethyl methacrylate copolymer (Di-PMMA) the insulating barrier material of difunctional functionalization
Material, is by after free-radical polymerized by the monomer of two kinds of functionalization and methyl methacrylate, then is obtained by deprotection steps
Arriving, its structure is shown below.
Wherein x=17, y=3, z=3.
1.1st, preparation contains the acetylene bond of trimethyl silicane protection and the polymethyl methacrylate copolymer of azido group
(TMS-PMMA)
The structural formula of described copolymer TMS-PMMA is as follows:
Wherein x=17, y=3, z=3.Fig. 2 be copolymer TMS-PMMA proton nmr spectra (1H-NMR), it is prepared
Method is as follows:
By methyl methacrylate (1.4g, 14.0mmol), trimethyl silica-based propargylmethyl acrylate (0.61g, 3.0
Mmol), the acid of 3-nitrine propyl methyl (0.51g, 3.0mmol) and azodiisobutyronitrile (0.066g, 0.40mmol)
It is dissolved in 20mL toluene, nitrogen bubble 0.5h, 70 DEG C of reaction 14h.Reactant liquor is cooled to room temperature, after concentration
Absolute methanol precipitates three times.Suction filtration final vacuum is dried to obtain white solid 2.0g (Mn=13,390g/mol, PDI=
4.6)。
Wherein, the preparation method of trimethyl silica-based propargylmethyl acrylate is as follows:
With methacrylic chloride and propargyl alcohol in the presence of pyridine, with the mol ratio of 1:1 in room temperature reaction 8～12 hours,
Generate propargylmethyl acrylate；By described propargylmethyl acrylate at silver chlorate and 1,8-diazabicylo 11
Under the catalysis of carbon-7-alkene, carry out back flow reaction 24～36 hours with trim,ethylchlorosilane with the mol ratio of 1:1.5, obtain three
Methylsilyl propargylmethyl acrylate；
The preparation method of 3-nitrine propyl methacrylate is: exist 3-chloropropyl alcohol and sodium azide with the mol ratio of 1:2
React 36～48 hours at 60 DEG C, obtain 3-Azidopropanol；By 3-Azidopropanol with methacrylic chloride with 1:1's
Mol ratio, in the presence of pyridine, carries out reacting 8～12 hours in room temperature, obtains 3-nitrine propyl methacrylate；
Nucleus magnetic hydrogen spectrum is as shown in Figure 1:1H NMR(δ,CDCl3):4.70-4.48(m,2H),4.12-3.94(m,2H),
3.72-3.50(m,19H),3.48-3.33(m,2H),2.12-0.70(m,52H),0.30-0.10(m,9H)；Infrared spectrum is such as
Shown in Fig. 3 a: FTIR2998,2944,2091,1727,1487,1440,1247,1146,983cm-1。
1.2nd, preparation contains the polymethyl methacrylate copolymer (Di-PMMA) of acetylene bond and azido group
The structural formula of described copolymer Di-PMMA is as follows:
Wherein x=17, y=3, z=3.Fig. 3 be copolymer Di-PMMA proton nmr spectra (1H-NMR), its system
Preparation Method is as follows:
It is dissolved in copolymer TMS-PMMA (0.60g, 0.045mmol) in 10mL oxolane, then drip four fourths
The tetrahydrofuran solution (1.0M, 0.010mol) of base ammonium fluoride, after dropping finishes, is stirred at room temperature 12 hours, adds after concentration
Entering 10mL distilled water, dichloromethane extracts three times, and anhydrous sodium sulfate is dried, and solution is loaded bag filter after concentrating by suction filtration
(MwCutoff3500), dialysed two days by acetone.Concentrating the solution in bag filter, vacuum drying obtains white solid 0.51
g(Mn=10,202g/mol, PDI=3.3).
Nucleus magnetic hydrogen spectrum is as shown in Figure 1:1H NMR(δ,CDCl3):4.72-4.46(m,2H),4.15-3.93(m,2H),
3.75-3.50(m,19H),3.50-3.35(m,2H),2.58-2.40(m,1H),2.15-0.53(m,51H)；Infrared spectrum is such as
Fig. 3 a:FTIR 3277,2998,2952,2091,1720,1487,1440,1239,1139,975cm-1。
The 2nd, embodiment prepares the polystyrene copolymer insulating layer material of difunctional functionalization of heat cross-linking
Present embodiments provide polystyrene copolymer (Di-PS) insulating layer material of difunctional functionalization, be by two kinds of work(
The monomer of energyization and styrene are by after free-radical polymerized, then are obtained by deprotection steps, and its structure is shown below,
Wherein x=18, y=3, z=3.
2.1st, preparation contains the acetylene bond of trimethyl silicane protection and the polystyrene copolymer (TMS-PS) of azido group
The structural formula of described copolymer TMS-PS is as follows:
Wherein x=18, y=3, z=3.Fig. 1 be copolymer TMS-PS proton nmr spectra (1H-NMR), it is prepared
Method is as follows:
By styrene (1.46g, 14.0mmol), 4-trimethyl silica-based propynyloxy base styrene (0.69g, 3.0mmol), 4-
Azido-methyl styrene (0.48g, 3.0mmol) and azodiisobutyronitrile (0.066g, 0.40mmol) are dissolved in 20mL first
In benzene, reactant liquor is cooled to room temperature, precipitates after concentration in absolute methanol by nitrogen bubble 0.5h, 70 DEG C of reaction 14h.
Three times.Suction filtration final vacuum is dried to obtain faint yellow solid 1.2g (Mn=16,905g/mol, PDI=1.6).
Wherein, the cinnamic preparation method of 4-trimethyl silica-based propynyloxy base is: by the 4-hydroxy benzenes second of 1 molfraction
Alkene under the effect of the Anhydrous potassium carbonate of 2 molfractions and the TBAB of 3 molfractions with propine bromine in a solvent
Carry out the back flow reaction 18～30 hours under nitrogen protection, obtain 4-propynyloxy base styrene；Again by 4-propynyloxy base benzene second
Alkene presses the mol ratio of 1:1 molten under the catalysis of silver chlorate and 1,8-diazabicylo 11 carbon-7-alkene with trim,ethylchlorosilane
Agent carries out the back flow reaction 18～24 hours under nitrogen protection, obtains 4-trimethyl silica-based propynyloxy base styrene；
The cinnamic preparation method of 4-azido-methyl is: by 4-1-chloro-4-methyl-benzene and sodium azide rubbing according to 1:4～6
That ratio, in DMF, 60 DEG C are reacted 36～48 hours, obtain 4-azido-methyl styrene.
Nucleus magnetic hydrogen spectrum is as shown in Figure 2:1HNMR(δ,CDCl3):7.24-6.16(m,34H),4.72-4.45(m,2H),
4.35-4.07(m,2H),2.28-0.74(m,27H),0.28-0.09(m,9H)；Infrared spectrum is as shown in Figure 3 b: FTIR
3068,3029,2921,2843,2091,1596,1503,1449,1239,1030cm-1。
2.2nd, preparation contains the polystyrene copolymer (Di-PS) of acetylene bond and azido group
The structural formula of described copolymer Di-PS is as follows:
Wherein x=18, y=3, z=3.Fig. 3 be copolymer Di-PS proton nmr spectra (1H-NMR), its preparation side
Method is as follows:
It is dissolved in copolymer TMS-PS (0.90g, 0.053mmol) in 10mL oxolane, then drip tetrabutyl fluorine
Change the tetrahydrofuran solution (1.0M, 0.020mol) of ammonium, after dropping finishes, be stirred at room temperature 12 hours, add after concentration
10mL distilled water, dichloromethane extracts three times, and anhydrous sodium sulfate is dried, and solution loads after suction filtration concentration bag filter (Mw
Cutoff3500), dialysed two days by acetone.Concentrating the solution in bag filter, vacuum drying obtains faint yellow solid 0.53
g(Mn=11,534g/mol, PDI=1.4).
Nucleus magnetic hydrogen spectrum is as shown in Figure 2:1H NMR(δ,CDCl3):7.26-6.16(m,38H),4.76-4.50(m,2H),
4.36-4.08(m,2H),2.60-2.37(m,1H),2.15-0.70(m,30H)；Infrared spectrum is as shown in Figure 3 b: FTIR
3292,3060,3022,2921,2851,2091,1603,1503,1449,1216,1107,1015cm-1。
The infrared absorption spectroscopy of embodiment the 3rd, difunctional functionalized copolymer, differential scanning calorimetry analysis and thermogravimetric analysis
Double officials that difunctional functionalized copolymer used by the present embodiment is respectively embodiment 1 and embodiment 2 prepares
The polymethyl methacrylate copolymer (Di-PMMA) of functionalization and the polystyrene copolymerization of difunctional functionalization can be rolled into a ball
Thing (Di-PS).
Fig. 3 give Di-PMMA and Di-PS spin-coating film after infrared absorption spectroscopy, 2100cm in collection of illustrative plates-1With
3290cm-1Absworption peak be respectively the characteristic absorption peak of azido group and acetylene bond, show prepared Di-PMMA and
Di-PS film (SM) contains azido and acetylene bond.After sample is heated 0.5h at 100 DEG C, it can be seen that azido
The absorption intensity of the characteristic peak of group and acetylene bond substantially weakens, and shows to there occurs nitrine-alkynes annulation.After heating 1h, folded
The absorption intensity of the characteristic peak of nitrogen groups and acetylene bond weakens inconspicuous, shows that reaction reaches balance.In device fabrication process,
Cross linking conditions is set to 100 DEG C of heating 0.5h.Fig. 4 shows gathering of the simple function group functionalization only modified by azido group
Methyl methacrylate and polystyrene copolymer only have an exothermic peak 200～280 DEG C of scopes, are dividing of azido group
Solution causes.And Di-PMMA and Di-PS copolymer has an obvious exothermic peak 90～210 DEG C of scopes, show
There occurs nitrine-alkynes annulation.Fig. 5 shows Di-PMMA and Di-PS copolymer owing to occurring in temperature-rise period
Cross-linking reaction, thus have preferably thermally-stabilised than a copolymer for the simple function group functionalization only modified by azido group
Property.
The difunctional functionalized copolymer insulating layer material of embodiment the 4th, heat cross-linking is imitated at organic field as gate insulator
Answer the purposes in transistor
Double officials that difunctional functionalized copolymer used by the present embodiment is respectively embodiment 1 and embodiment 2 prepares
The polymethyl methacrylate copolymer (Di-PMMA) of functionalization and the polystyrene copolymerization of difunctional functionalization can be rolled into a ball
Thing (Di-PS).
Fig. 6 gives with the polymethyl methacrylate copolymer of heat cross-linking (C-PMMA) and polystyrene copolymer
(C-PS) material as gate insulator at organic field effect tube (OFET) structural representation.As shown in Figure 6, OFET
The preparation method of device is: in glass matrix, the aluminum metal layer of evaporation last layer 40nm thickness is as grid, by double officials
The copolymer that can roll into a ball functionalization is dissolved in chlorobenzene (40mg/mL) and is spin-coated in matrix, subsequently 100 DEG C of heating in an oven
0.5h carries out crosslinking.Then the silver of the upper 40nm thickness of evaporation passes through as source electrode and drain electrode, electrode on the insulating layer
Phenyl-pentafluoride thiophenol is modified.The semiconductor layer of device is by double (triisopropylsilyl acetenyl) pentacene of 6,13-and polyphenyl
The chloroformic solution of ethene drips casting and forms, the semiconductor channel length of device 60 μm, and width is 1200 μm.Fig. 7～9 are respectively
Give polymethyl methacrylate copolymer (C-PMMA) and polystyrene copolymer (C-PS) the material material of heat cross-linking
Expect leakage current curve, curve of output and the transfer curve of the OFET device as gate insulator.It can be seen that
Under the grid voltage of 1.5MV/cm, leakage current density is 10-7A/cm2.Mobility reaches 0.59cm respectively2V-1S-1
And 0.15cm2V-1S-1, on-off ratio is respectively～105With～103, threshold voltage is respectively 0.5V and-0.6V.
The 5th, embodiment prepares the polystyrene copolymer insulating layer material of difunctional functionalization of heat cross-linking
Present embodiments provide polystyrene copolymer (Di-PS) insulating layer material of difunctional functionalization, be by two kinds of work(
The monomer of energyization and styrene are by after free-radical polymerized, then are obtained by deprotection steps, and its structure is shown below,
Wherein x=93, y=5, z=5.
5.1st, preparation contains the acetylene bond of trimethyl silicane protection and the polystyrene copolymer (TMS-PS) of azido group
The structural formula of described copolymer TMS-PS is as follows:
Wherein x=93, y=5, z=5.Fig. 2 be copolymer TMS-PS proton nmr spectra (1H-NMR), it is prepared
Method is as follows:
By styrene (1.87g, 18.0mmol), 4-trimethyl silica-based propynyloxy base styrene (0.23g, 1.0mmol), 4-
Azido-methyl styrene (0.16g, 1.0mmol) and azodiisobutyronitrile (0.066g, 0.40mmol) are dissolved in 20mL first
In benzene, reactant liquor is cooled to room temperature, precipitates after concentration in absolute methanol by nitrogen bubble 0.5h, 65 DEG C of reaction 12h.
Three times.Suction filtration final vacuum is dried to obtain faint yellow solid 1.6g (Mn=16,314g/mol, PDI=1.3).
Nucleus magnetic hydrogen spectrum:1H NMR(δ,CDCl3):7.20-6.17(m,100H),4.68-4.46(m,2H),4.27-4.07(m,
2H),2.22-0.72(m,71H),0.26-0.07(m,9H)；Infrared spectrum: FTIR 3069,3030,2923,2845,2093,
1599,1506,1447,1236,1034cm-1。
5.2nd, preparation contains the polystyrene copolymer (Di-PS) of acetylene bond and azido group
The structural formula of described copolymer Di-PS is as follows:
Wherein x=93, y=5, z=5.Fig. 2 be copolymer Di-PS proton nmr spectra (1H-NMR), its preparation side
Method is as follows:
It is dissolved in copolymer TMS-PS (0.90g, 0.053mmol) in 10mL oxolane, then drip tetrabutyl fluorine
Change the tetrahydrofuran solution (1.0M, 0.020mol) of ammonium, after dropping finishes, be stirred at room temperature 12 hours, add after concentration
10mL distilled water, dichloromethane extracts three times, and anhydrous sodium sulfate is dried, and solution loads after suction filtration concentration bag filter (Mw
Cutoff3500), dialysed two days by acetone.Concentrating the solution in bag filter, vacuum drying obtains faint yellow solid 0.53
g(Mn=10,177g/mol, PDI=1.6).
Nucleus magnetic hydrogen spectrum:1H NMR(δ,CDCl3):7.21-6.24(m,101H),4.72-4.50(m,2H),4.33-4.10(m,
2H),2.55-2.39(m,1H),2.10-0.75(m,80H)；Infrared spectrum: FTIR 3295,3062,3020,2918,2847,
2094,1605,1501,1451,1218,1110,1013cm-1。
The 6th, embodiment prepares the polystyrene copolymer insulating layer material of difunctional functionalization of heat cross-linking
Present embodiments provide polystyrene copolymer (Di-PS) insulating layer material of difunctional functionalization, be by two kinds of work(
The monomer of energyization and styrene are by after free-radical polymerized, then are obtained by deprotection steps, and its structure is shown below,
Wherein x=20, y=5, z=5.
6.1st, preparation contains the acetylene bond of trimethyl silicane protection and the polystyrene copolymer (TMS-PS) of azido group
The structural formula of described copolymer TMS-PS is as follows:
Wherein x=20, y=5, z=5.Fig. 2 be copolymer TMS-PS proton nmr spectra (1H-NMR), it is prepared
Method is as follows:
By styrene (0.63g, 6.0mmol), 4-trimethyl silica-based propynyloxy base styrene (0.69g, 3.0mmol), 4-
Azido-methyl styrene (0.48g, 3.0mmol) and azodiisobutyronitrile (0.066g, 0.40mmol) are dissolved in 20mL first
In benzene, reactant liquor is cooled to room temperature, precipitates after concentration in absolute methanol by nitrogen bubble 0.5h, 70 DEG C of reaction 14h.
Three times.Suction filtration final vacuum is dried to obtain faint yellow solid 0.7g (Mn=17,029g/mol, PDI=1.6).
Nucleus magnetic hydrogen spectrum:1H NMR(δ,CDCl3):7.22-6.14(m,26H),4.70-4.45(m,2H),4.32-4.05(m,
2H),2.08-0.74(m,27H),0.30-0.07(m,9H)；Infrared spectrum: FTIR 3068,3035,2923,2844,2093,
1599,1504,1447,1236,1035cm-1。
6.2nd, preparation contains the polystyrene copolymer (Di-PS) of acetylene bond and azido group
The structural formula of described copolymer Di-PS is as follows:
Wherein x=20, y=5, z=5.Fig. 2 be copolymer Di-PS proton nmr spectra (1H-NMR), its preparation side
Method is as follows:
It is dissolved in copolymer TMS-PS (0.90g, 0.053mmol) in 10mL oxolane, then drip tetrabutyl fluorine
Change the tetrahydrofuran solution (1.0M, 0.020mol) of ammonium, after dropping finishes, be stirred at room temperature 12 hours, add after concentration
10mL distilled water, dichloromethane extracts three times, and anhydrous sodium sulfate is dried, and solution loads after suction filtration concentration bag filter (Mw
Cutoff3500), dialysed two days by acetone.Concentrating the solution in bag filter, vacuum drying obtains faint yellow solid 0.53
g(Mn=11,785g/mol, PDI=1.8).
Nucleus magnetic hydrogen spectrum:1H NMR(δ,CDCl3):7.20-6.10(m,28H),4.71-4.44(m,2H),4.33-4.07(m,
2H),2.57-2.27(m,1H),2.02-0.65(m,32H)；Infrared spectrum: FTIR 3293,3063,3024,2922,2850,
2093,1605,1504,1452,1214,1109,1016cm-1。
In sum, the heat cross-linking difunctional functionalized copolymer insulating materials of the present invention introduce nitrine under heating condition-
The annulation of alkynes is as crosslinking method, it is achieved that in lower temperature, non-metal catalyst and the condition without interpolation crosslinking agent
The crosslinked polymer insulation layer material of lower preparation, resulting materials is applicable to solwution method and prepares various OFETs device, is one
Planting the organic field effect tube gate insulating layer material of excellent performance, application prospect is quite varied.
Above the specific embodiment of the present invention is described.It is to be appreciated that the invention is not limited in
Stating particular implementation, those skilled in the art can make various deformation or modification within the scope of the claims,
This has no effect on the flesh and blood of the present invention.
Claims (5)
1. the polymethyl methacrylate copolymer of a difunctional functionalization, it is characterised in that described copolymer
Structure is shown below:
Wherein, x:y:z=(30～6): 3:3.
2. a preparation method for the polymethyl methacrylate copolymer of difunctional functionalization as claimed in claim 1,
It is characterized in that, comprise the steps:
A) by methyl methacrylate, trimethyl silica-based propargylmethyl acrylate, 3-nitrine propyl methacrylate
Add in organic solvent A with initiator, under anaerobic, issue raw free radicals copolymerization reaction in 60～80 DEG C, it is thus achieved that
Acetylene bond containing trimethyl silicane protection and the polymethyl methacrylate copolymer of azido group；
B) polymethyl methacrylate copolymer of the described acetylene bond containing trimethyl silicane protection and azido group is dissolved in organic
In solvent B, add deprotecting regent, under room temperature, slough trimethyl silane, it is thus achieved that contain the difunctionality of acetylene bond and azido group
The polymethyl methacrylate copolymer of group's functionalization.
3. preparation method as claimed in claim 2, it is characterised in that in step a), described methyl methacrylate,
The mol ratio of trimethyl silica-based propargylmethyl acrylate and 3-nitrine propyl methacrylate is (30～6): 3:3；
Described initiator is azodiisobutyronitrile, and the mol ratio of methyl methacrylate and initiator is 1:
(0.01～0.02)；
Described organic solvent A is toluene；
In step b): described deprotecting regent is the tetrahydrofuran solution of tetrabutyl ammonium fluoride；
The mol ratio of described copolymer and deprotecting regent is 1:(100～200)；
Described organic solvent B is oxolane.
4. preparation method as claimed in claim 2 or claim 3, it is characterised in that the silica-based propargylmethyl of described trimethyl
The preparation method of acrylate is: use methacrylic chloride and propargyl alcohol in the presence of pyridine, little in room temperature reaction 8～12
When, generate propargylmethyl acrylate；By described propargylmethyl acrylate at silver chlorate and 1,8-diazabicylo
Under the catalysis of 11 carbon-7-alkene, carry out back flow reaction 24～36 hours with trim,ethylchlorosilane, obtain the silica-based alkynes of trimethyl third
Methyl acrylate；
Wherein, the mol ratio of described methacrylic chloride and propargyl alcohol is 1:(1～1.5)；Described propargylmethyl acrylic acid
The mol ratio of ester and trim,ethylchlorosilane is 1:(1～1.5)；
The preparation method of described 3-nitrine propyl methacrylate is: by 3-chloropropyl alcohol and sodium azide at 60 DEG C anti-
Answer 36～48 hours, obtain 3-Azidopropanol；By described 3-Azidopropanol and methacrylic chloride in the presence of pyridine,
Carry out reacting 8～12 hours in room temperature, obtain 3-nitrine propyl methacrylate；
Wherein, the mol ratio of described 3-chloropropyl alcohol and sodium azide is 1:(2～4)；Described methacrylic chloride and 3-fold
The mol ratio of nitrogen base propyl alcohol is 1:(1～1.5).
5. the polymethyl methacrylate copolymer of a difunctional functionalization as claimed in claim 1 is as grid
Purposes in organic field effect tube for the insulating barrier.
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| CN103819684A (en) * | 2014-02-17 | 2014-05-28 | 上海交通大学 | Thermo-crosslinked polystyrene polymer, preparation method and applications thereof |
| CN104371206A (en) * | 2014-11-07 | 2015-02-25 | 上海交通大学 | Crosslinked polystyrene material as well as preparation method and use |
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| CN103819684A (en) * | 2014-02-17 | 2014-05-28 | 上海交通大学 | Thermo-crosslinked polystyrene polymer, preparation method and applications thereof |
| CN104371206A (en) * | 2014-11-07 | 2015-02-25 | 上海交通大学 | Crosslinked polystyrene material as well as preparation method and use |
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