CN107987254B - A kind of adjustable silicon substrate thiazole epoxy curing agent of structure and preparation method thereof - Google Patents
A kind of adjustable silicon substrate thiazole epoxy curing agent of structure and preparation method thereof Download PDFInfo
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- CN107987254B CN107987254B CN201711070003.2A CN201711070003A CN107987254B CN 107987254 B CN107987254 B CN 107987254B CN 201711070003 A CN201711070003 A CN 201711070003A CN 107987254 B CN107987254 B CN 107987254B
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- thiazole
- curing agent
- silicon substrate
- epoxy curing
- adjustable silicon
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 82
- 239000004593 Epoxy Substances 0.000 title claims abstract description 71
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 63
- 239000010703 silicon Substances 0.000 title claims abstract description 63
- 239000000758 substrate Substances 0.000 title claims abstract description 63
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 aminothiazole class compound Chemical class 0.000 claims abstract description 19
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 18
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 9
- 238000006467 substitution reaction Methods 0.000 claims abstract description 9
- 125000005605 benzo group Chemical group 0.000 claims abstract description 6
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims abstract 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical compound NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 claims 1
- 229950003476 aminothiazole Drugs 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 229920000647 polyepoxide Polymers 0.000 abstract description 29
- 239000003822 epoxy resin Substances 0.000 abstract description 28
- 125000003118 aryl group Chemical group 0.000 abstract description 14
- 239000000047 product Substances 0.000 description 28
- 238000010521 absorption reaction Methods 0.000 description 20
- 239000000126 substance Substances 0.000 description 12
- BUMGIEFFCMBQDG-UHFFFAOYSA-N dichlorosilicon Chemical compound Cl[Si]Cl BUMGIEFFCMBQDG-UHFFFAOYSA-N 0.000 description 11
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 9
- 238000001757 thermogravimetry curve Methods 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- 229910018540 Si C Inorganic materials 0.000 description 5
- 125000002723 alicyclic group Chemical group 0.000 description 5
- 229910010271 silicon carbide Inorganic materials 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 229910007991 Si-N Inorganic materials 0.000 description 4
- 229910006294 Si—N Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 235000013399 edible fruits Nutrition 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000805 composite resin Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 2
- HBGPNLPABVUVKZ-POTXQNELSA-N (1r,3as,4s,5ar,5br,7r,7ar,11ar,11br,13as,13br)-4,7-dihydroxy-3a,5a,5b,8,8,11a-hexamethyl-1-prop-1-en-2-yl-2,3,4,5,6,7,7a,10,11,11b,12,13,13a,13b-tetradecahydro-1h-cyclopenta[a]chrysen-9-one Chemical compound C([C@@]12C)CC(=O)C(C)(C)[C@@H]1[C@H](O)C[C@]([C@]1(C)C[C@@H]3O)(C)[C@@H]2CC[C@H]1[C@@H]1[C@]3(C)CC[C@H]1C(=C)C HBGPNLPABVUVKZ-POTXQNELSA-N 0.000 description 1
- PFRGGOIBYLYVKM-UHFFFAOYSA-N 15alpha-hydroxylup-20(29)-en-3-one Natural products CC(=C)C1CCC2(C)CC(O)C3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 PFRGGOIBYLYVKM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SOKRNBGSNZXYIO-UHFFFAOYSA-N Resinone Natural products CC(=C)C1CCC2(C)C(O)CC3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 SOKRNBGSNZXYIO-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GLQWRXYOTXRDNH-UHFFFAOYSA-N thiophen-2-amine Chemical compound NC1=CC=CS1 GLQWRXYOTXRDNH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
Abstract
The present invention provides a kind of adjustable silicon substrate thiazole epoxy curing agent of structure and preparation method thereof, the structural formula of the adjustable silicon substrate thiazole epoxy curing agent of structure are as follows:Wherein, R1For the alkyl or phenyl or benzo base of hydrogen or C atomicity 1~5；R2For the alkylene of the alkyl or C atomicity 2~4 of hydrogen or C atomicity 1~5 or the aryl of C atomicity 6~10；R3For the alkylene of the alkyl or C atomicity 2~4 of hydrogen or C atomicity 1~5 or the aryl of C atomicity 6~10；The preparation method of the adjustable silicon substrate thiazole epoxy curing agent of structure includes the steps that substitution reaction, which occurs, by aminothiazole class compound and dichlorosilane is made the adjustable silicon substrate thiazole epoxy curing agent of the structure.The adjustable silicon substrate thiazole epoxy curing agent of structure provided by the invention is reacted with epoxy resin is capable of forming high heat epoxy cured product.
Description
Technical field
The present invention relates to epoxy curing agent synthesis technical field more particularly to a kind of adjustable silicon substrate thiazole epoxies of structure
Resin curing agent and preparation method thereof.
Background technique
Epoxy resin is in a class formation containing two or more epoxy groups, with aliphatic, alicyclic and fragrant
Fragrant race etc. is the organic matter of skeleton, and shrinking percentage is small, easy to process and cured product has corrosion resistance, chemistry when because of its solidification
The features such as stability, electrical insulating property, is widely used in the fields such as coating, adhesive, building and water conservancy traffic.With composite material
The continuous development of application, especially in the high-end sciemtifec and technical sphere such as electric, national defence, aerospace, since service condition is harsh,
To the thermal stability of material, more stringent requirements are proposed.Therefore, exploitation high heat epoxy is always that researcher is ground
Study carefully one of the hot spot of epoxy resin.
The thermal stability of epoxy resin-cured product depends primarily on the molecular structure of epoxy resin itself, solidification
The structure and curing process of agent.So improving the thermal stability of epoxy resin can be realized by following four method:
One, change the molecular structure of epoxy resin itself, synthesis contains the epoxy resin of heat-resisting group；Two, epoxy resin is improved
The degree of cross linking of cured product；Three, the curing agent of synthesizing new introduces heat-resisting group, and the heat for improving epoxy resin-cured product is steady
Qualitative energy；Four, the material good with thermal stability is blended or is modified.
Just there is practical value since epoxy resin must react generation tridimensional network with curing agent.Therefore curing agent
Structure and quality will directly affect the application effect of epoxy resin.Domestic and foreign scholars are to the research and development of curing agent more than ring
Oxygen resin is active, and compared with epoxy resin kind, curing agent kind is more, and confidentiality is stronger.It is every to develop a kind of new solidification
Agent can solve the problems, such as one aspect, be equivalent in some sense and develop the new epoxy resin of one kind or open asphalt mixtures modified by epoxy resin
One new purposes of rouge.As it can be seen that exploitation Novel curing agent is even more important more than exploitation neo-epoxy resin.
Summary of the invention
The technical problems to be solved by the present invention are: provide a kind of adjustable silicon substrate thiazole epoxy curing agent of structure and its
Preparation method, the structure is adjustable silicon substrate thiazole epoxy curing agent crosslinks with epoxy resin react after can obtain it is high resistance to
Hot epoxy resin cured product.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention are as follows:
A kind of adjustable silicon substrate thiazole epoxy curing agent of structure, the adjustable silicon substrate thiazole epoxy curing agent of structure
Structural formula are as follows:
Wherein, R1The alkyl or phenyl or benzo base for being 1~5 for hydrogen or C atomicity；
R2For hydrogen or C atomicity be 1~5 alkyl or C atomicity be 2~4 alkylene or C atomicity be 6~10
Aryl；
R3For hydrogen or C atomicity be 1~5 alkyl or C atomicity be 2~4 alkylene or C atomicity be 6~10
Aryl.
A kind of preparation method of the adjustable silicon substrate thiazole epoxy curing agent of structure, including by aminothiazole class compound with
The step of structure adjustable silicon substrate thiazole epoxy curing agent is made in substitution reaction, occurs for dichlorosilane.
The beneficial effects of the present invention are:
The preparation method of the adjustable silicon substrate thiazole epoxy curing agent of structure provided by the invention, by being protected in inert gas
Under shield, substitution reaction occurs for aminothiazole class compound and dichlorosilane, and the siliceous of Good Heat-resistance is prepared in one-step method
The structure of nitrogen sulphur is adjustable silicon substrate thiazole epoxy curing agent；Raw material used by this method is simple and easy to get, reaction condition is mild,
Reaction process is simply easily implemented, at low cost.The adjustable silicon substrate thiazole epoxy curing agent of structure provided by the invention is solid for amine
Agent, the openable epoxy group of active hydrogen in the curing agent structure on-NH-Si-NH- segment on secondary amine nitrogen atom, makes epoxy
Resin crosslinking curing；Meanwhile introduced in the curing agent structure five-ring heterocycles in thiazole compound structure and further
Pass through the controllable unit R of structure1Or R2Or R3The heat-resisting rigid radicals such as aromatic ring, alicyclic ring are introduced, to improve epoxy resin cure production
It is contour can to meet electric, heat-resisting composite resin matrix, national defence and aerospace for the thermal decomposition temperature of object
Hold the application demand of sciemtifec and technical sphere.
Detailed description of the invention
Fig. 1 is the structural characterization figure of the adjustable silicon substrate thiazole epoxy curing agent of structure prepared in the embodiment of the present invention two
Spectrum, respectively Fourier transform infrared spectroscopy figure (a), hydrogen nuclear magnetic resonance spectrogram (b) and carbon-13 nmr spectra figure (c)；
Fig. 2 is that the adjustable silicon substrate thiazole epoxy curing agent of structure prepared in the embodiment of the present invention one or embodiment two is consolidated
Change cured product obtained by triglycidyl group p aminophenol epoxy resin (TGPAP) in N2In atmosphere (a) and air (b)
Thermal gravimetric analysis curve (TGA) figure；
Fig. 3 is the structural characterization figure of the adjustable silicon substrate thiazole epoxy curing agent of structure prepared in the embodiment of the present invention four
Spectrum, respectively Fourier transform infrared spectroscopy figure (a), hydrogen nuclear magnetic resonance spectrogram (b) and carbon-13 nmr spectra figure (c)；
Fig. 4 is that the adjustable silicon substrate thiazole epoxy curing agent of structure prepared in the embodiment of the present invention three or example IV is consolidated
Change cured product obtained by triglycidyl group p aminophenol epoxy resin (TGPAP) in N2In atmosphere (a) and air (b)
Thermal gravimetric analysis curve (TGA) figure；
Fig. 5 is the structural formula of the adjustable silicon substrate thiazole epoxy curing agent of structure obtained in the embodiment of the present invention five.
Specific embodiment
To explain the technical content, the achieved purpose and the effect of the present invention in detail, below in conjunction with embodiment and cooperate attached
Figure is explained.
The most critical design of the present invention is: by under inert gas protection, aminothiazole class compound and dichloro silicon
The adjustable silicon substrate thiazole epoxy curing agent of structure of Good Heat-resistance is prepared in the substitution reaction of alkane, one-step method；Pass through
The five-ring heterocycles that are introduced into curing agent structure in thiazole compound structure and further by the controllable unit R of structure1、
R2、R3The heat-resisting rigid radicals such as aromatic ring, alicyclic ring are introduced, the heat resistance of epoxy resin-cured product is improved.
The present invention provides a kind of adjustable silicon substrate thiazole epoxy curing agent of structure, the adjustable silicon substrate thiazole epoxy of structure
The structural formula of resin curing agent are as follows:
Wherein, R1The alkyl or phenyl or benzo base for being 1~5 for hydrogen or C atomicity；
R2For hydrogen or C atomicity be 1~5 alkyl or C atomicity be 2~4 alkylene or C atomicity be 6~10
Aryl；
R3For hydrogen or C atomicity be 1~5 alkyl or C atomicity be 2~4 alkylene or C atomicity be 6~10
Aryl.
As can be seen from the above description, the beneficial effects of the present invention are:
The adjustable silicon substrate thiazole epoxy curing agent of structure provided by the invention is amine curing agent, the curing agent structure
In the openable epoxy group of active hydrogen on-NH-Si-NH- segment on secondary amine nitrogen atom, solidify cross linking of epoxy resin；Meanwhile
The five-ring heterocycles in thiazole compound structure are introduced in the curing agent structure and further pass through the controllable unit of structure
R1Or R2Or R3Introduce the heat-resisting rigid radicals such as aromatic ring, alicyclic ring makes to improve the thermal decomposition temperature of epoxy resin-cured product
Its application that can satisfy the high-end sciemtifec and technical spheres such as electric, heat-resisting composite resin matrix, national defence and aerospace
Demand.
The present invention also provides a kind of preparation methods of the adjustable silicon substrate thiazole epoxy curing agent of structure, including by amino thiophene
The step of structure adjustable silicon substrate thiazole epoxy curing agent is made in substitution reaction, occurs for azole compounds and dichlorosilane.
Wherein, the equation that aminothiazole class compound is reacted with dichlorosilane are as follows:
Wherein, R1The alkyl or phenyl or benzo base for being 1~5 for hydrogen or C atomicity；
R2For hydrogen or C atomicity be 1~5 alkyl or C atomicity be 2~4 alkylene or C atomicity be 6~10
Aryl；
R3For hydrogen or C atomicity be 1~5 alkyl or C atomicity be 2~4 alkylene or C atomicity be 6~10
Aryl.
Further, the preparation method of the adjustable silicon substrate thiazole epoxy curing agent of the structure, specifically includes following step
It is rapid:
Step 1: aminothiazole class compound, acid binding agent and the first stirring solvent are dissolved；
Step 2: under inert gas protection, the mixed solution of dichlorosilane and the second solvent being added to obtained by step 1
It is reacted in solution；
Step 3: the solution filtering after above-mentioned steps are reacted collects filtrate and removes the solvent in filtrate, then vacuum is dry
It is dry to obtain the adjustable silicon substrate thiazole epoxy curing agent of structure.
As can be seen from the above description, the beneficial effects of the present invention are:
The preparation method of the adjustable silicon substrate thiazole epoxy curing agent of structure provided by the invention, by being protected in inert gas
Under shield, substitution reaction occurs for aminothiazole class compound and dichlorosilane, and the siliceous of Good Heat-resistance is prepared in one-step method
The structure of nitrogen sulphur is adjustable silicon substrate thiazole epoxy curing agent；Raw material used by this method is simple and easy to get, reaction condition is mild,
Reaction process is simply easily implemented, at low cost.
Further, the molar ratio of the aminothiazole class compound and dichlorosilane is (2~3.5): 1.
Further, the condition reacted in the step 2 are as follows: reaction temperature is -30 DEG C~+50 DEG C, reaction time 2h
~12h.
Further, vacuum drying condition in the step 3 are as follows: drying temperature is 50~80 DEG C, drying time 2h
~6h.
Further, the acid binding agent is triethylamine.
Further, first solvent is tetrahydrofuran.
Further, second solvent is tetrahydrofuran.
Further, the inert gas is one or more of nitrogen, argon gas and helium.
The embodiment of the present invention one are as follows:
A kind of adjustable silicon substrate thiazole epoxy curing agent of structure, the adjustable silicon substrate thiazole epoxy curing agent of structure
Structural formula are as follows:
The embodiment of the present invention two are as follows:
A kind of preparation method of the adjustable silicon substrate thiazole epoxy curing agent of structure, comprising the following steps:
Under high pure nitrogen protection, 2- ammonia is sequentially added into the 150mL three-necked flask equipped with 50mL constant pressure funnel
Base benzothiazole (1.50g, 10mmol), tetrahydrofuran (20mL) and triethylamine (1.5mL, 10mmol) after stirring and dissolving, pass through
The mixed solution of methyl hydrogen dichlorosilane (0.54mL, 5mmol) and tetrahydrofuran (20mL) is added in constant pressure funnel, drips
6h is reacted at -10 DEG C after finishing, after reaction, standing sedimentation removes triethylamine hydrochloride through filtering, and collects filtrate, washes
Wash purification, rotary evaporation removes solvent, finally vacuum drying obtains target product.
It please refers to shown in Fig. 1 (a), table is carried out using structure of the Fourier transform infrared spectroscopy (FT-IR) to target product
Sign is as a result as follows: 3396cm-1、3271cm-1There is the characteristic absorption peak of N-H key, 2167cm in place-1There is Si -- H bond in place
Characteristic absorption peak, 1123cm-1There is the characteristic absorption peak of Si-C key, 917cm in place-1There is the characteristic absorption of Si-N key in place
Peak；This shows to contain N-H key, Si -- H bond, Si-C key and Si-N key in target product.
Please refer to shown in Fig. 1 (b), using nuclear magnetic resonance spectroscopy (1H-NMR) structure of target product is characterized, is tied
Fruit is as follows: CH occurs at chemical shift 0.22ppm3Absorption peak, there is the absorption of Si-NH at chemical shift 3.50ppm
There is the absorption peak of Si-H at chemical shift 4.74ppm, occurs Ph-H (phenyl ring at 7.02~8.04ppm of chemical shift in peak
On hydrogen) absorption peak；
Please refer to shown in Fig. 1 (c), using carbon-13 nmr spectra (13C-NMR) structure of target product is characterized, is tied
Fruit is as follows: occur the absorption peak of Si-C at chemical shift 0.72ppm, chemical shift 119ppm, 120ppm, 122ppm,
Occur at 126ppm, 130ppm, 151ppmAbsorption peak, chemical shift 166ppm occurs S-C-N's
Absorption peak.
From the analysis above, we can see that the structure of the target product are as follows:
It is shunk with the adjustable silicon substrate thiazole epoxy curing agent solidification three of the structure prepared in embodiment one or embodiment two
Glyceryl p aminophenol epoxy resin (TGPAP), cured product is in N2In atmosphere TGA curve (heating rate be 10 DEG C/
Min) as shown in Fig. 2 (a), 5% (T of weightlessnessd5) and 10% (T of weightlessnessd10) corresponding to temperature be respectively 318 DEG C and 340 DEG C, most
Big weightless corresponding temperature (Tdmax) it is 374 DEG C, 600 DEG C of quality retention rate is 26.9%.
Solidify three-glycidyl with the adjustable silicon substrate thiazole epoxy curing agent of structure in embodiment one or embodiment two
Base p aminophenol epoxy resin (TGPAP), the aerial TGA curve of cured product (heating rate is 10 DEG C/min) is such as
Shown in Fig. 2 (b), Td5And Td10Corresponding temperature is respectively 284 DEG C and 310 DEG C, TdmaxIt is 366 DEG C, 600 DEG C of quality retains
Rate is 19.6%.
From the analysis above, we can see that the adjustable silicon substrate thiazole epoxy curing agent of the structure prepared in embodiment one or embodiment two
It is reacted with TGPAP and forms high heat epoxy cured product.
The embodiment of the present invention three are as follows:
A kind of adjustable silicon substrate thiazole epoxy curing agent of structure, the adjustable silicon substrate thiazole epoxy curing agent of structure
Structural formula are as follows:
The embodiment of the present invention four are as follows:
A kind of preparation method of the adjustable silicon substrate thiazole epoxy curing agent of structure, comprising the following steps:
Under high pure nitrogen protection, 2- ammonia is sequentially added into the 150mL three-necked flask equipped with 50mL constant pressure funnel
Base benzothiazole (1.50g, 10mmol), tetrahydrofuran (20mL) and triethylamine (1.5mL, 10mmol) after stirring and dissolving, pass through
The mixed solution of diphenyl dichlorosilane (1mL, 5mmol) and tetrahydrofuran (20mL) is added in constant pressure funnel, is added dropwise
6h is reacted at -10 DEG C afterwards, after reaction, standing sedimentation removes triethylamine hydrochloride through filtering, and collects filtrate, washing
Purification, rotary evaporation remove solvent, and finally vacuum drying obtains target product.
Referring to figure 3. shown in (a), table is carried out using structure of the Fourier transform infrared spectroscopy (FT-IR) to target product
Sign is as a result as follows: 3394cm-1、3270cm-1There is the characteristic absorption peak of N-H key, 1642cm in place-1There is Ph-H (benzene in place
Hydrogen on ring) characteristic absorption peak, 1123cm-1There is the characteristic absorption peak of Si-C key, 992cm in place-1There is Si-N key in place
Characteristic absorption peak；This shows to contain N-H key, Ph-H key, Si-C key and Si-N key in target product.
Referring to figure 3. shown in (b), using nuclear magnetic resonance spectroscopy (1H-NMR) structure of target product is characterized, is tied
Fruit is as follows: occurring the absorption peak of N-H at chemical shift 3.53ppm, Ph-H occurs at 7.05~8.11ppm of chemical shift
The absorption peak of (hydrogen on phenyl ring)；
Referring to figure 3. shown in (c), using carbon-13 nmr spectra (13C-NMR) structure of target product is characterized, is tied
Fruit is as follows: occurring at chemical shift 118ppm, 120ppm, 122ppm, 125ppm, 130ppm, 152ppm
Absorption peak, there is the absorption peak of Ph-C (carbon on phenyl ring) at chemical shift 129ppm, 130ppm, 134ppm, 139ppm,
There is the absorption peak of S-C-N in chemical shift 166ppm.
From the analysis above, we can see that the structure of the target product are as follows:
It is shunk with the adjustable silicon substrate thiazole epoxy curing agent solidification three of the structure prepared in embodiment three or example IV
Glyceryl p aminophenol epoxy resin (TGPAP), cured product is in N2In atmosphere TGA curve (heating rate be 10 DEG C/
Min) as shown in Fig. 4 (a), Td5And Td10Corresponding temperature is respectively 317 DEG C and 338 DEG C, TdmaxIt is 368 DEG C, 600 DEG C of matter
Measuring retention rate is 25.1%.
It is shunk with the adjustable silicon substrate thiazole epoxy curing agent solidification three of the structure prepared in embodiment three or example IV
Glyceryl p aminophenol epoxy resin (TGPAP), the aerial TGA curve of cured product (heating rate be 10 DEG C/
Min) as shown in Fig. 4 (b), Td5And Td10Corresponding temperature is respectively 276 DEG C and 294 DEG C, TdmaxIt is 336 DEG C, 600 DEG C of matter
Measuring retention rate is 10.0%.
From the analysis above, we can see that the adjustable silicon substrate thiazole epoxy curing agent of the structure prepared in embodiment three or example IV
It is reacted with TGPAP and forms high heat epoxy cured product.
The embodiment of the present invention five are as follows:
A kind of preparation method of the adjustable silicon substrate thiazole epoxy curing agent of structure, including by aminothiazole class compound with
The step of structure adjustable silicon substrate thiazole epoxy curing agent is made in substitution reaction, the knot obtained occur for dichlorosilane
The structural formula of structure is adjustable silicon substrate thiazole epoxy curing agent is as shown in Figure 5, wherein R1The alkane for being 1~5 for hydrogen or C atomicity
Alkyl or phenyl or benzo base；R2For hydrogen or C atomicity be 1~5 alkyl or C atomicity be 2~4 alkylene or C it is former
The aryl that subnumber is 6~10；R3For hydrogen or C atomicity be 1~5 alkyl or C atomicity be 2~4 alkylene or C atom
The aryl that number is 6~10.
In conclusion the preparation method of the adjustable silicon substrate thiazole epoxy curing agent of structure provided by the invention, by
Under inert gas shielding, substitution reaction occurs for aminothiazole class compound and dichlorosilane, and heat resistance is prepared in one-step method
The adjustable silicon substrate thiazole epoxy curing agent of structure of excellent siliceous nitrogen sulphur；Raw material used by this method is simple and easy to get, anti-
Mild condition is answered, reaction process is simply easily implemented, at low cost.The adjustable silicon substrate thiazole epoxy resin cure of structure provided by the invention
Agent is amine curing agent, the openable epoxy group of active hydrogen in the curing agent structure on-NH-Si-NH- segment on secondary amine nitrogen atom
Group, solidifies cross linking of epoxy resin；Meanwhile introduced in the curing agent structure five-ring heterocycles in thiazole compound structure with
And further pass through the controllable unit R of structure1Or R2Or R3The heat-resisting rigid radicals such as aromatic ring, alicyclic ring are introduced, to improve asphalt mixtures modified by epoxy resin
The thermal decomposition temperature of rouge cured product can meet electric, heat-resisting composite resin matrix, national defence and aviation
The application demand of the high-end sciemtifec and technical sphere such as space flight.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalents made by bright specification and accompanying drawing content are applied directly or indirectly in relevant technical field, similarly include
In scope of patent protection of the invention.
Claims (10)
1. a kind of adjustable silicon substrate thiazole epoxy curing agent of structure, which is characterized in that the adjustable silicon substrate thiazole epoxy of structure
The structural formula of resin curing agent are as follows:
Wherein, R1The alkyl or phenyl or benzo base for being 1~5 for hydrogen or C atomicity；
R2For hydrogen or C atomicity be 1~5 alkyl or C atomicity be 2~4 alkylene or C atomicity be 6~10 virtue
Base；
R3For hydrogen or C atomicity be 1~5 alkyl or C atomicity be 2~4 alkylene or C atomicity be 6~10 virtue
Base.
2. a kind of preparation method of the adjustable silicon substrate thiazole epoxy curing agent of structure, which is characterized in that including by aminothiazole
The step of structure adjustable silicon substrate thiazole epoxy curing agent is made in substitution reaction, occurs for class compound and dichlorosilane.
3. the preparation method of the adjustable silicon substrate thiazole epoxy curing agent of structure according to claim 2, which is characterized in that
Specifically includes the following steps:
Step 1: aminothiazole class compound, acid binding agent and the first stirring solvent are dissolved；
Step 2: under inert gas protection, the mixed solution of dichlorosilane and the second solvent being added to step 1 acquired solution
Middle reaction；
Step 3: the solution filtering after above-mentioned steps are reacted collects filtrate and removes the solvent in filtrate, then is dried in vacuo
To the adjustable silicon substrate thiazole epoxy curing agent of structure.
4. the preparation method of the adjustable silicon substrate thiazole epoxy curing agent of structure according to claim 3, which is characterized in that
The molar ratio of the aminothiazole class compound and dichlorosilane is (2~3.5): 1.
5. the preparation method of the adjustable silicon substrate thiazole epoxy curing agent of structure according to claim 3, which is characterized in that
The condition reacted in the step 2 are as follows: reaction temperature is -30 DEG C~+50 DEG C, and the reaction time is 2h~12h.
6. the preparation method of the adjustable silicon substrate thiazole epoxy curing agent of structure according to claim 3, which is characterized in that
Vacuum drying condition in the step 3 are as follows: drying temperature is 50~80 DEG C, and drying time is 2h~6h.
7. the preparation method of the adjustable silicon substrate thiazole epoxy curing agent of structure according to claim 3, which is characterized in that
The acid binding agent is triethylamine.
8. the preparation method of the adjustable silicon substrate thiazole epoxy curing agent of structure according to claim 3, which is characterized in that
First solvent is tetrahydrofuran.
9. the preparation method of the adjustable silicon substrate thiazole epoxy curing agent of structure according to claim 3, which is characterized in that
Second solvent is tetrahydrofuran.
10. the preparation side of the structure according to any one of claim 3~9 is adjustable silicon substrate thiazole epoxy curing agent
Method, which is characterized in that the inert gas is one or more of nitrogen, argon gas and helium.
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| CN111423562B (en) * | 2020-05-08 | 2022-10-21 | 福建云森科技有限公司 | High-temperature-resistant epoxy resin curing agent containing amino-containing azole, preparation method of curing agent, epoxy resin composition, cured product and application of curing agent |
| CN112459526B (en) * | 2020-12-03 | 2021-12-14 | 安徽墨砂工程修缮技术有限公司 | Method for repairing external wall thermal insulation hollowing and dropping |
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| CN1350026A (en) * | 2000-10-20 | 2002-05-22 | 株式会社日矿材料 | Phenol curing agent for epoxy resin and epoxy resin composition using said curing agent |
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| EP0526847A1 (en) * | 1991-08-01 | 1993-02-10 | Japan Energy Corporation | Novel imidazole-silane compounds, process for producing the same, and metal surface finishing agent containing the same |
| CN1350026A (en) * | 2000-10-20 | 2002-05-22 | 株式会社日矿材料 | Phenol curing agent for epoxy resin and epoxy resin composition using said curing agent |
| CN102286261A (en) * | 2011-07-14 | 2011-12-21 | 上海景涵实业有限公司 | Epoxy functional organic silicon conductive adhesive for amino curing system for light emitting diode (LED) |
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