CN107868610A - A kind of siliceous coating of normal temperature cure - Google Patents
A kind of siliceous coating of normal temperature cure Download PDFInfo
- Publication number
- CN107868610A CN107868610A CN201711108979.4A CN201711108979A CN107868610A CN 107868610 A CN107868610 A CN 107868610A CN 201711108979 A CN201711108979 A CN 201711108979A CN 107868610 A CN107868610 A CN 107868610A
- Authority
- CN
- China
- Prior art keywords
- silane
- degree
- functionality
- siliceous coating
- normal temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011248 coating agent Substances 0.000 title claims abstract description 53
- 238000000576 coating method Methods 0.000 title claims abstract description 53
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910000077 silane Inorganic materials 0.000 claims abstract description 34
- 125000000962 organic group Chemical group 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 26
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 23
- 230000007062 hydrolysis Effects 0.000 claims abstract description 21
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 21
- -1 siloxanes Chemical class 0.000 claims abstract description 16
- 229920001709 polysilazane Polymers 0.000 claims abstract description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000062 azane Inorganic materials 0.000 claims abstract description 7
- 229920005591 polysilicon Polymers 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000413 hydrolysate Substances 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 4
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- YBHBEZSZXFLQMW-UHFFFAOYSA-N [dimethoxy(phenyl)silyl]methanamine Chemical compound CO[Si](CN)(OC)C1=CC=CC=C1 YBHBEZSZXFLQMW-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 239000005055 methyl trichlorosilane Substances 0.000 claims description 3
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical group C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 claims description 2
- 229920001002 functional polymer Polymers 0.000 claims description 2
- 239000005054 phenyltrichlorosilane Substances 0.000 claims description 2
- 239000002952 polymeric resin Substances 0.000 claims description 2
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 claims description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- 229920006009 resin backbone Polymers 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 235000011167 hydrochloric acid Nutrition 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical compound [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 1
- RBIILJCATVGHHI-UHFFFAOYSA-N [diethoxy(phenyl)silyl]methanamine Chemical compound NC[Si](OCC)(OCC)C1=CC=CC=C1 RBIILJCATVGHHI-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002454 metastable transfer emission spectrometry Methods 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000005028 tinplate Substances 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a kind of siliceous coating of normal temperature cure; hydrolysis performed polymer and polysilazane the hybrid resin mixing that it is mainly added in solvent by two degree of functionality silane, three-functionality-degree silane and tetra functional silane mixture form; the polysilazane hybrid resin is mixed by methyl polysilicon azane resin and Perhydropolysilazane in the flask that nitrogen is protected, and the hydrolysis performed polymer is the siloxanes hydrolysis performed polymer that the ratio of organic group R and Si in organic group degree are 1.2~1.6, phenyl content is 20~60wt% in organic group degree.Superior performance of the present invention, can at normal temperatures the short time solidify, without extra catalyst or baking, in the organic group degree ratio of methyl and phenyl base degree to siliceous coating property also can normal temperature cure, and can takes into account the siliceous coating of the performances such as siliceous coating hardness, thermoplasticity, adhesion.
Description
Technical field
The present invention relates to the synthetic method of the siliceous coating of the normal temperature cure of good weatherability, particularly a kind of energy normal temperature cure,
The siliceous coating that various performances are taken into account.
Background technology
It is silica structure organic siliconresin that siliceous coating, which refers to a kind of main chain, is the poly-organosilicon of highly cross-linked network structure
Oxygen alkane, typically with methyl trichlorosilane, dimethyldichlorosilane, phenyl trichlorosilane, diphenyl dichlorosilane or methylbenzene
The various mixtures of base dichlorosilane, in the presence of organic solvent such as toluene, hydrolytic condensation, initial product is ring-type, line style
And cross-linked polymer mixture, generally also contain considerable hydroxyl.Hydrolysate removes acid, neutral first polycondensation through washing
Body thermal oxide or further polycondensation in the presence of a catalyst in air, eventually form highly cross-linked dimensional network structure.Gu
Change and form silica chain link typically by silanol condensation to realize.When condensation reaction is being carried out, because silanol concentration is gradual
Reduce, add steric hindrance, poor fluidity, cause reaction rate to decline.Therefore, resin is fully cured, must be by adding
Heat and addition catalyst are carried out to accelerate to react.The performance of the siliceous final fabricated product of coating depends on the number of contained organic group degree
Amount, i.e. organic group（The organic groups such as methyl, ethyl, phenyl）R and Si ratio.General siliceous coating with practical value,
R and Si ratio is between 1.2~1.6 in its molecular composition.Universal law is R：Si value is smaller, resulting siliceous painting
Material more can just solidify at a lower temperature；R：Si value is bigger, and thermoelasticity is more much better than the former, and solidification temperature is also higher, very
To make it solidify just needs to the siliceous coating having to toast for a long time at a high temperature of 200 ~ 250 DEG C.
In addition, the ratio of methyl and phenyl base degree also has a great impact to siliceous coating property in organic group degree.It is organic
Phenyl content is lower in base degree, and the paint film of generation is softer, and condensation is faster, and phenyl content is higher, and the paint film of generation is harder, more has
Thermoplasticity.For phenyl content between 20~60%, the bending resistance and heat resistance of paint film are best.In addition, introducing phenyl can also change
Enter the compatibility of siliceous coating and pigment, can also improve the compatibility of siliceous coating and other organic siliceous coating and siliceous painting
Expect the adhesion to various base materials.
Want solve siliceous coating both superior performances, and can is current urgent problem in normal temperature cure, to be siliceous
Coating application, open up broader space.
The content of the invention：
The present invention is for existing siliceous coating deficiency, there is provided a kind of energy normal temperature cure, and can take into account siliceous coating hardness, thermoplastic
The siliceous coating of the performances such as property, adhesion.
The technical problem to be solved in the present invention takes technical scheme as follows：The siliceous coating of normal temperature cure is mainly by two
Degree of functionality silane, three-functionality-degree silane and tetra functional silane mixture are added to hydrolysis performed polymer and polysilazane in solvent
Hybrid resin mixing composition, the polysilazane hybrid resin is by methyl polysilicon azane resin and Perhydropolysilazane resin in nitrogen
Mixed in the flask of gas shielded, it is described hydrolysis performed polymer be organic group degree in organic group R and Si ratio production 1.2~
1.6th, the siloxanes that phenyl content is 20~60wt% in organic group degree hydrolyzes performed polymer.
Normal temperature cure siliceous the degree of functionality silane of coating two, three-functionality-degree silane and tetra functional silane mixture of the present invention
The hydrolysis performed polymer solid content and polysilazane hybrid resin ratio that thing is added in solvent are 10:1~2, preferably 10:1.
The siliceous coating of normal temperature cure methyl polysilicon azane resin described further of the present invention, the master of Perhydropolysilazane resin
Chain structure is the three of silazine link structure, tetra functional polymer resin.There is extremely strong reactivity, the siliceous coating of the present invention can be made to exist
Silicone hydroxyl, silicon nitrogen base condensation cross-linking under the conditions of normal temperature or lower temperature, it can just solidify in the short time.In solidification process, silazine link
In the presence of, can the hydrolysis of absorption air moisture and with substrate surface hydroxyl condensation, coating and base material adhesive force, improvement coating can be promoted
Physical property.
Methyl polysilicon azane resin in the siliceous coating of normal temperature cure of the present invention, Perhydropolysilazane resin mixed proportion can shadows
Ring siliceous paint solidification speed, mixed proportion preferably 1：1 mixing.
The siliceous coating of normal temperature cure of the present invention can be with auxiliary agents such as additional pigment, levelling agents.
The two degrees of functionality silane is dimethyldichlorosilane, diphenyl dichlorosilane, dichloromethyl phenylsilane, diformazan
Base dimethoxysilane, dimethyldiethoxysilane, dimethoxydiphenylsilane, aminomethyl phenyl dimethoxysilane, two
Diethylamino phenyl TMOS aminomethyl phenyl diethoxy silane etc.；The three-functionality-degree silane is methyl trichlorosilane, phenyl three
Chlorosilane, MTMS, MTES, phenyltrimethoxysila,e, phenyl triethoxysilane etc.；
The tetra functional silane is tetrachloro silicane, methyl silicate, tetraethyl orthosilicate etc..
The two degrees of functionality silane, three-functionality-degree silane, the preferred alkoxy silane of tetra functional silane, further preferred first
TMOS.
Two degrees of functionality silane of the present invention, three-functionality-degree silane, tetra functional siloxanes hydrolysis performed polymer are two functions
Degree silane, three-functionality-degree silane, tetra functional siloxanes leave a part of silicone hydroxyl when being blended in hydrolytic condensation in solvent and not contracted
The hydrolysate of conjunction（Hydrolyze performed polymer）.
The quantity that the performance of the final fabricated product of the siliceous coating of the present invention of the present invention depends on contained organic group degree is
Organic group（The organic groups such as methyl, ethyl, phenyl）R and Si ratio.General siliceous coating with practical value, its group of molecules
Into middle R and Si mass fraction ratio preferably between 1.2~1.6.Even if R：Si value is larger, resulting siliceous coating
Can at normal temperatures the short time solidify, without extra catalyst or baking.
Also there is very big the ratio of methyl and phenyl base degree to siliceous coating property in present invention organic group degree described further
Influence.Phenyl content is lower in organic group degree, and the paint film of generation is softer, and condensation is faster, and phenyl content is higher, the paint film of generation
It is harder, more with thermoplasticity.For phenyl content between 20~60%, the bending resistance and heat resistance of paint film are best.In addition, introduce
Phenyl can improve the compatibility of siliceous coating and pigment, can also improve the compatibility of siliceous coating and other organic siliceous coating
And siliceous coating is to the adhesion of various base materials.It can consolidate at normal temperatures between phenyl content 20~60% in organic group degree
Change.
Solvent of the present invention of the present invention selects atent solvent, such as benzene, hexamethylene, dimethylbenzene, ethyl acetate, solvent naphtha
One or more kinds of mixed solvents.
Embodiment
In order that those skilled in the art more fully understand technical scheme, enter below by specific embodiment
The present invention is described in detail in one step, and the degree of functionality silane of embodiment two, three-functionality-degree silane, tetra functional silane methoxy silane are
Example.The quantity of organic group degree is the organic group of silicone product（The organic groups such as methyl, ethyl, phenyl）R and Si quality point
Number ratio.
1st, dimethyldimethoxysil,ne 120g, MTMS 136g, phenyltrimethoxysila,e are taken
148.7g, methyl silicate 57g, dimethylbenzene（Solvent）500g is added to stirring in 5000ml glass reaction kettles, is started, and drips 2
~ 3 drop concentrated hydrochloric acids, normal temperature are added dropwise deionized water 54g, rear normal-temperature reaction are added dropwise 1 hour, are warming up to 65 DEG C, use vacuum rapidly
Extract by-product methanol out, remaining hydrolysate is that organic group degree is 1.2, the siloxanes that phenyl content is 20% in organic group degree
Performed polymer is hydrolyzed, hydrolysis performed polymer solid content about 42% or so, is recorded as No. 1 hydrolysis performed polymer.
2nd, dimethoxydiphenylsilane 244.3g, MTMS 136g, phenyltrimethoxysila,e are taken
99g, methyl silicate 63.9g, hexamethylene（Solvent）500g is added to stirring in 5000ml glass reaction kettles, is started, and drips 2 ~ 3
Concentrated hydrochloric acid is dripped, normal temperature is added dropwise deionized water 50g, rear normal-temperature reaction is added dropwise 1 hour, is warming up to 65 DEG C, is taken out with vacuum rapidly
Go out by-product carbinol, remaining hydrolysate is that organic group degree is 1.2, the siloxanes water that phenyl content is 60% in organic group degree
Performed polymer is solved, hydrolysis performed polymer solid content about 47% or so, is recorded as No. 2 hydrolysis performed polymers.
3rd, aminomethyl phenyl dimethoxysilane 244.3g, dimethyldimethoxysil,ne 120g, phenyl trimethoxy silicon are taken
Alkane 136g, tetraethyl orthosilicate 19g, ethyl acetate（Solvent）500g is added to in 5000ml glass reaction kettles, starts stirring,
The drop concentrated hydrochloric acid of drop 2 ~ 3, normal temperature are added dropwise deionized water 45g, rear normal-temperature reaction are added dropwise 1 hour, are warming up to 65 DEG C, rapid with true
Sky extracts by-product carbinol out, and remaining product is that organic group degree is 1.6, the siloxanes water that phenyl content is 20% in organic group degree
Performed polymer is solved, hydrolysis performed polymer solid content about 46% or so, is recorded as No. 3 hydrolysis performed polymers.
4th, dimethoxydiphenylsilane 244.3, phenyl-trimethylsilicane 198.3g, MTMS are taken
272g, methyl silicate 19g, dimethylbenzene（Solvent）500g is added to stirring in 5000ml glass reaction kettles, is started, and drips 2 ~ 3
Concentrated hydrochloric acid is dripped, normal temperature is added dropwise deionized water 51g, rear normal-temperature reaction is added dropwise 1 hour, is warming up to 65 DEG C, is taken out with vacuum rapidly
Go out by-product carbinol, remaining product is that organic group degree is 1.6, and the siloxanes hydrolysis that phenyl content is 60% in organic group degree is pre-
Aggressiveness, hydrolysis performed polymer solid content about 56% or so, it is recorded as No. 4 hydrolysis performed polymers.
5th, take methyl polysilicon azane resin 500g and Perhydropolysilazane 500g to add in the flask for thering is nitrogen to protect to mix
Uniformly, as polysilazane hybrid resin.
Embodiment 1：Weigh No. 1 and hydrolyze performed polymer 100g, polysilazane hybrid resin 4.2g is well mixed, and is recorded as No. 1
Siliceous coating.
Embodiment 2：Weigh No. 2 and hydrolyze performed polymer 100g, polysilazane hybrid resin 4.7g is well mixed, and is recorded as No. 2
Siliceous coating.
Embodiment 3：Weigh No. 3 and hydrolyze performed polymer 100g, polysilazane hybrid resin 4.6g is well mixed, and is recorded as No. 3
Siliceous coating.
Embodiment 4：Weigh No. 4 and hydrolyze performed polymer 100g, polysilazane hybrid resin 5.6g is well mixed, and is recorded as No. 4
Siliceous coating.
Embodiment 5：Weigh No. 1 hydrolysis performed polymer 100g, levelling agent 0.2g, titanium white powder pigment 1, polysilazane hybrid resin
4.2g is well mixed, and is recorded as No. 5 siliceous coating 5.
1~5 siliceous coating of above-described embodiment, metrics evaluation are as follows：
Base material selects tinplate, is rubbed using small cloth, 25 DEG C of normal temperature cures.Surface drying time is detected using cotton pellet method is blown, when doing solid work
Between using pressure cotton pellet method detection, hardness using pencil method detection, pliability using mandrel rod analyzer determine, as a result such as following table：
| Finish code | Surface drying time | Do solid work the time | Pencil hardness | Pliability |
| No. 1 siliceous coating | 1 hour 20 points | 5 hours 20 points | 2H | 3mm |
| No. 2 siliceous coating | 2 hours 20 points | 7 hours 30 points | 3H | 3mm |
| No. 3 siliceous coating | 2 hours 20 points | 8 hours 30 points | 3H | 4mm |
| No. 4 siliceous coating | 3 hours 20 points | 12 hours 20 points | 3H | 4mm |
| No. 5 siliceous coating | 1 hour 20 points | 1 hour 20 points | 2H | 3mm |
It is described above to contribute to skilled artisan understands that the invention, but not limit the protection model of the invention
Enclose.It is any equal replacement described above, modification are improved without departing from the invention substantive content or delete numerous conform to the principle of simplicity and
The implementation of progress, each fall within the scope of the present patent application request patent protection.
Claims (4)
- A kind of 1. siliceous coating of normal temperature cure, it is characterised in that：It is mainly by two degree of functionality silane, three-functionality-degree silane and four officials Energy degree silane mixture is added to hydrolysis performed polymer and polysilazane hybrid resin mixing composition in solvent, the polysilazane Hybrid resin is mixed by methyl polysilicon azane resin and Perhydropolysilazane in the flask that nitrogen is protected, and the hydrolysis is pre- Aggressiveness be the ratio of organic group R and Si in organic group degree be 1.2~1.6, phenyl content is 20~60wt%'s in organic group degree Siloxanes hydrolyzes performed polymer.
- 2. the siliceous coating of a kind of normal temperature cure according to claim 1, it is characterised in that the two degrees of functionality silane is two Dimethyl dichlorosilane (DMCS), diphenyl dichlorosilane, dichloromethyl phenylsilane, dimethyldimethoxysil,ne, dimethyl diethoxy Base silane, dimethoxydiphenylsilane, aminomethyl phenyl dimethoxysilane, diphenyl diethoxy silane aminomethyl phenyl diethyl TMOS；The three-functionality-degree silane is methyl trichlorosilane, phenyl trichlorosilane, MTMS, methyl three Ethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane；The tetra functional silane is tetrachloro silicane, positive silicon Sour methyl esters, tetraethyl orthosilicate.
- A kind of 3. siliceous coating of normal temperature cure according to claim 1, it is characterised in that：The two degrees of functionality silane, three officials Energy degree silane, tetra functional siloxanes hydrolysis performed polymer are two degree of functionality silane, three-functionality-degree silane, tetra functional siloxanes water The hydrolysate that a part of silicone hydroxyl is not condensed is left during solution condensation.
- 4. the siliceous coating of a kind of normal temperature cure according to claim 1, it is characterized in that：Polysilazane hybrid resin high activity, Promote siliceous coating can be in normal temperature cure, the polysilazane hybrid resin is by methyl polysilicon azane resin, the poly- silicon nitrogen of perhydro Alkane resin backbone structure is the three of silazine link structure, tetra functional polymer resin composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711108979.4A CN107868610A (en) | 2017-11-11 | 2017-11-11 | A kind of siliceous coating of normal temperature cure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711108979.4A CN107868610A (en) | 2017-11-11 | 2017-11-11 | A kind of siliceous coating of normal temperature cure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107868610A true CN107868610A (en) | 2018-04-03 |
Family
ID=61753872
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711108979.4A Pending CN107868610A (en) | 2017-11-11 | 2017-11-11 | A kind of siliceous coating of normal temperature cure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107868610A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109517522A (en) * | 2018-11-20 | 2019-03-26 | 萍乡亨厚新材科技有限公司 | A kind of super-hydrophobic self-cleaning coating for building |
| CN111116921A (en) * | 2019-12-31 | 2020-05-08 | 广东省稀有金属研究所 | Self-flame-retardant high-hardness organic silicon resin and preparation method and application thereof |
| CN111334189A (en) * | 2020-04-26 | 2020-06-26 | 广东四方威凯新材料有限公司 | A kind of antifouling self-cleaning paint post-treating agent and preparation method thereof |
| JP2021014514A (en) * | 2019-07-11 | 2021-02-12 | ヤマモトホールディングス株式会社 | Coating liquid and coating method |
| CN112831271A (en) * | 2021-01-05 | 2021-05-25 | 北京动力机械研究所 | Hole sealing agent for plasma spraying gradient thermal barrier coating and use method thereof |
| CN113728044A (en) * | 2019-04-23 | 2021-11-30 | 住友化学株式会社 | Mixed composition |
| CN114262567A (en) * | 2021-11-23 | 2022-04-01 | 航天科工武汉磁电有限责任公司 | Low-temperature-cured high-temperature-resistant wave-absorbing coating and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0992556A1 (en) * | 1998-04-24 | 2000-04-12 | Catalysts & Chemicals Industries Co., Ltd. | Coating liquid for forming silica-based film having low dielectric constant and substrate having film of low dielectric constant coated thereon |
| CN1587299A (en) * | 2004-07-29 | 2005-03-02 | 复旦大学 | Process for preparing organic-inorganic hybridized resin and its coating material |
| CN101044219A (en) * | 2004-10-19 | 2007-09-26 | 瓦尔斯帕供应公司 | Heat-resistant coating compositions, coated articles, and methods |
| CN101857674A (en) * | 2010-05-27 | 2010-10-13 | 大连交通大学 | A kind of synthetic method of high temperature resistant silicone resin |
| CN104812543A (en) * | 2012-07-03 | 2015-07-29 | 伯宁布什集团有限公司 | High performance silicon based coating compositions |
-
2017
- 2017-11-11 CN CN201711108979.4A patent/CN107868610A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0992556A1 (en) * | 1998-04-24 | 2000-04-12 | Catalysts & Chemicals Industries Co., Ltd. | Coating liquid for forming silica-based film having low dielectric constant and substrate having film of low dielectric constant coated thereon |
| CN1587299A (en) * | 2004-07-29 | 2005-03-02 | 复旦大学 | Process for preparing organic-inorganic hybridized resin and its coating material |
| CN101044219A (en) * | 2004-10-19 | 2007-09-26 | 瓦尔斯帕供应公司 | Heat-resistant coating compositions, coated articles, and methods |
| CN101857674A (en) * | 2010-05-27 | 2010-10-13 | 大连交通大学 | A kind of synthetic method of high temperature resistant silicone resin |
| CN104812543A (en) * | 2012-07-03 | 2015-07-29 | 伯宁布什集团有限公司 | High performance silicon based coating compositions |
Non-Patent Citations (2)
| Title |
|---|
| P•科隆博（P.COLOMBO）等著；楚增勇 等译: "《先驱体陶瓷-从纳米结构到应用》", 29 February 2016, 国防工业出版社 * |
| 贾梦秋 等: "耐高温有机硅树脂的合成", 《化工新型材料》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109517522A (en) * | 2018-11-20 | 2019-03-26 | 萍乡亨厚新材科技有限公司 | A kind of super-hydrophobic self-cleaning coating for building |
| CN113728044A (en) * | 2019-04-23 | 2021-11-30 | 住友化学株式会社 | Mixed composition |
| JP2021014514A (en) * | 2019-07-11 | 2021-02-12 | ヤマモトホールディングス株式会社 | Coating liquid and coating method |
| CN111116921A (en) * | 2019-12-31 | 2020-05-08 | 广东省稀有金属研究所 | Self-flame-retardant high-hardness organic silicon resin and preparation method and application thereof |
| CN111334189A (en) * | 2020-04-26 | 2020-06-26 | 广东四方威凯新材料有限公司 | A kind of antifouling self-cleaning paint post-treating agent and preparation method thereof |
| CN111334189B (en) * | 2020-04-26 | 2021-10-15 | 广东四方威凯新材料有限公司 | A kind of antifouling self-cleaning paint post-treating agent and preparation method thereof |
| CN112831271A (en) * | 2021-01-05 | 2021-05-25 | 北京动力机械研究所 | Hole sealing agent for plasma spraying gradient thermal barrier coating and use method thereof |
| CN114262567A (en) * | 2021-11-23 | 2022-04-01 | 航天科工武汉磁电有限责任公司 | Low-temperature-cured high-temperature-resistant wave-absorbing coating and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107868610A (en) | A kind of siliceous coating of normal temperature cure | |
| JP4336767B2 (en) | Elastomer-modified epoxy siloxane composition | |
| CN103228736B (en) | Curable composition | |
| CA2310283C (en) | Addition-crosslinkable epoxy-functional organopolysiloxane polymer and coating compositions | |
| CN102432862B (en) | There is the modified alkoxylated product of at least one non-end alkoxysilyl, the polymkeric substance prepared with them | |
| CN100482761C (en) | Single-component room-temperature fast sulfidization dealcoholization type sealing rubber with silicone structure and preparing method thereof | |
| CN101802114B (en) | Coating compositions comprising organofunctional polysiloxane polymers, and use thereof | |
| CN104152104B (en) | A kind of autohension organic silicon pressure-sensitive adhesive and preparation method thereof | |
| CN101341216B (en) | Room temperature curable silicon group-containing polymer composition | |
| CN104387546A (en) | Phenyl organic silicon modified polyurethane resin, preparation method and application thereof | |
| CN102712814A (en) | Curable composition | |
| CN103044920B (en) | One-component room temperature vulcanized and methyl alcohol-removed silicon rubber of starting-resistant engine oil and preparation method of rubber | |
| JPH0812761A (en) | Silicone resin composition | |
| CN105602426B (en) | A kind of water-fast aqueous polyurethane coating | |
| CN105368378B (en) | Paintability silicone adhesive and preparation method thereof | |
| CN105218825A (en) | A kind of organosilicon solvent-free solvent impregnated resin and synthetic method thereof | |
| CN103788916A (en) | Organic silicon sealant with fast-curing property and high heat and humidity resistance and preparation method thereof | |
| CN110591557B (en) | Organic silicon coating adhesive and preparation method thereof | |
| CN106146850A (en) | A kind of additional organosilicon impregnating resin viscosifier and preparation method thereof | |
| CN110156997A (en) | It is a kind of can moisture solidification organic silicon block copolymer and preparation method thereof | |
| CN1914290B (en) | Adhesive composition | |
| KR101049269B1 (en) | Room temperature curing type surface coating agent, non-slip surface coating agent and construction method using the same | |
| CN107641466B (en) | Organic silicon solvent-free impregnating varnish and preparation method thereof | |
| CN104558611A (en) | MDTQ silicon resin, as well as preparation method and application thereof | |
| KR101521643B1 (en) | Organosilicon compositions and methods for making same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180403 |