CN111269258A - Sulfur-containing organic silicon compound and preparation method and application thereof - Google Patents
Sulfur-containing organic silicon compound and preparation method and application thereof Download PDFInfo
- Publication number
- CN111269258A CN111269258A CN202010194320.0A CN202010194320A CN111269258A CN 111269258 A CN111269258 A CN 111269258A CN 202010194320 A CN202010194320 A CN 202010194320A CN 111269258 A CN111269258 A CN 111269258A
- Authority
- CN
- China
- Prior art keywords
- sulfur
- containing organosilicon
- organosilicon compound
- compound
- carbon atoms
- 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.)
- Granted
Links
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 46
- 239000011593 sulfur Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 150000003377 silicon compounds Chemical class 0.000 title abstract description 5
- 150000003961 organosilicon compounds Chemical class 0.000 claims abstract description 40
- 238000000576 coating method Methods 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 12
- 239000000853 adhesive Substances 0.000 claims abstract description 5
- 230000001070 adhesive effect Effects 0.000 claims abstract description 5
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000012948 isocyanate Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000007259 addition reaction Methods 0.000 claims description 10
- 229940125904 compound 1 Drugs 0.000 claims description 10
- 229940125782 compound 2 Drugs 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- UJTGYJODGVUOGO-UHFFFAOYSA-N diethoxy-methyl-propylsilane Chemical compound CCC[Si](C)(OCC)OCC UJTGYJODGVUOGO-UHFFFAOYSA-N 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- BUZRAOJSFRKWPD-UHFFFAOYSA-N isocyanatosilane Chemical compound [SiH3]N=C=O BUZRAOJSFRKWPD-UHFFFAOYSA-N 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- WPNRZVONKRBZDU-UHFFFAOYSA-L [dodecanoyloxy(diethyl)stannyl] dodecanoate Chemical compound CC[Sn+2]CC.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O WPNRZVONKRBZDU-UHFFFAOYSA-L 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000000565 sealant Substances 0.000 claims description 2
- 239000012974 tin catalyst Substances 0.000 claims description 2
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000002318 adhesion promoter Substances 0.000 claims 1
- DRRZZMBHJXLZRS-UHFFFAOYSA-N n-[3-[dimethoxy(methyl)silyl]propyl]cyclohexanamine Chemical compound CO[Si](C)(OC)CCCNC1CCCCC1 DRRZZMBHJXLZRS-UHFFFAOYSA-N 0.000 claims 1
- 239000003973 paint Substances 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007789 sealing Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 9
- 239000000758 substrate Substances 0.000 description 7
- 239000008199 coating composition Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229940126062 Compound A Drugs 0.000 description 4
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 description 3
- NNTRMVRTACZZIO-UHFFFAOYSA-N 3-isocyanatopropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCN=C=O NNTRMVRTACZZIO-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical compound [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- PJIFJEUHCQYNHO-UHFFFAOYSA-N diethoxy-(3-isocyanatopropyl)-methylsilane Chemical compound CCO[Si](C)(OCC)CCCN=C=O PJIFJEUHCQYNHO-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a sulfur-containing organic silicon compound and a preparation method thereof, wherein the sulfur-containing organic silicon compound has the following general formula:
wherein R is1Independently represents an alkyl group having 1 to 4 carbon atoms; r2Independently represents an alkyl group having 1 to 3 carbon atoms; x is independently 1, 2 or 3; n is an integer selected from 2 to 6. The sulfur-containing organosilicon compound has a multifunctional structure with four or more functionality, can be used as a refractive index regulator, can also be used as a tackifier of a sealing agent, an adhesive and a coating, and can improve the performances of the product such as bonding strength, water resistance, weather resistance and the like.
Description
Technical Field
The invention relates to an organic silicon synthesis technology, in particular to a sulfur-containing organic silicon compound and a preparation method and application thereof.
Background
Transparent resin plastic materials such as polycarbonate plastic have the characteristics of light weight, easiness in processing, impact resistance and the like, and lenses made of resin are rapidly and widely applied to the aspects of replacing glass lenses and the like as materials of optical base materials such as sunglass lenses, helmet lenses, labor protection lenses and the like. However, the surface of the plastic lens is soft and is easily scratched by scratching, so a hard coating needs to be provided for protection. The material for forming the hard coat layer is generally a silicone type material.
The common organosilicon material has a low refractive index, and when a hard coating is formed, the common organosilicon material forms a light interference phenomenon, namely rainbow lines appear on the surface of a lens and influence the appearance due to the mismatch of the refractive index (1.586) of the common organosilicon material and a polycarbonate substrate.
The sulfur element has the characteristic of high refractive index, and the sulfur-containing compound is introduced into the organic silicon material, so that the refractive index of the organic silicon material can be improved, the polycarbonate substrate can be well matched, and the light interference phenomenon is reduced.
Disclosure of Invention
The invention aims to overcome the defect that the refractive index of the existing organosilicon material is lower, and provides a novel sulfur-containing organosilicon compound, which has the following general formula:
the sulfur-containing organosilicon compounds obtained by the present invention also have the characteristic of high functionality, and the compounds with four or six functionalities are obtained from two or three functionalities. The high-functionality compound (such as tetrafunctional compound and hexafunctional compound) can improve the crosslinking density of the cured coating, thereby improving the hardness and wear resistance of the hard coating.
The invention also provides a preparation method of the sulfur-containing organosilicon compound, which is characterized in that the compound 1 and the compound 2 are subjected to addition reaction of amino and isocyanate groups, and the reaction formula is shown in figure 1.
Compound 1 is an isocyanatosilane and can be represented by the formula:
an isocyanate group-containing siloxane represented by the formula (2) wherein R1Represents an alkyl group having 1 to 4 carbon atoms; r2Represents an alkyl group having 1 to 3 carbon atoms; r1And R2May be the same or different; x is an integer of 1, 2 or 3; n is an integer selected from 2 to 6.
In some preferred embodiments, R is1Represents a hydrocarbon group having 1 to 3 carbon atoms; further preferably, R is1Represents methyl or ethyl.
In some preferred embodiments, R is2Represents methyl or ethyl.
In some embodiments, when x is 3, the isocyanate group-containing siloxane is an isocyanate group-containing trifunctional alkoxysilane, and examples of compounds satisfying the conditions include 3-Isocyanatopropyltrimethoxysilane (IPTMS), 3-Isocyanatopropyltriethoxysilane (IPTES), and the like.
In some embodiments, when x is 2, the isocyanate group-containing siloxane is an isocyanate group-containing difunctional alkoxysilane, and examples of compounds satisfying the conditions include 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, and the like.
The experimental research of the inventor finds that the activity of isocyanate groups in the difunctional isocyanate silane is basically consistent with that of the trifunctional isocyanate silane, and the reaction conditions are basically consistent with the process.
The invention also protects the application of the sulfur-containing organosilicon compound, can improve the refractive index of organosilicon materials, and can reduce the refractive index difference between a hard coating and a substrate when the compound is used in organosilicon hardening liquid, thereby reducing the interference phenomenon of light. And the crosslinking density of the hard coating can be improved by applying the high-functionality organosilicon compound, so that the hardness and the wear resistance of the hard coating can be improved.
The specific scheme is as follows:
a sulfur containing organosilicon compound having the general formula:
wherein R is1Independently represents an alkyl group having 1 to 4 carbon atoms; r2Independently represents an alkyl group having 1 to 3 carbon atoms; x is independently 1, 2 or 3; n is an integer selected from 2 to 6.
Further, R1Represents a hydrocarbon group having 1 to 3 carbon atoms; preferably, R1Represents methyl or ethyl;
optionally, R2Represents methyl or ethyl;
optionally, n is 3, 4 or 5.
Further, the structural formula of the sulfur-containing organosilicon compound is as follows:
the invention also provides a preparation method of the sulfur-containing organosilicon compound, which comprises the step of carrying out addition reaction of amino and isocyanate on the compound 1 and the compound 2, wherein the reaction formula is as follows:
wherein the compound 1 is isocyanatosilane and the compound 2 is thiourea, and in the reaction formula: r1Independently represents an alkyl group having 1 to 4 carbon atoms; r2Independently represents an alkyl group having 1 to 3 carbon atoms; x is independently 1, 2 or 3; n is an integer selected from 2 to 6.
Further, the compound 1 is any one of 3-isocyanatopropyl trimethoxy silane, 3-isocyanatopropyl triethoxy silane, 3-isocyanatopropyl methyl dimethoxy silane and 3-isocyanatopropyl methyl diethoxy silane;
optionally, the molar ratio between-NCO groups contained in the siloxane in said compound 1 and amino groups contained in said compound 2 is 1: (1-1.1).
Further, the addition reaction is carried out under the action of a catalyst, and the catalyst is an organic tin catalyst, preferably at least one of tin octoate, dibutyltin diacetate, dibutyltin dilaurate or diethyltin dilaurate;
optionally, the amount of the catalyst is 0.01-0.1% of the total feeding mass.
Further, the addition reaction is carried out under the protection of inert gas, preferably nitrogen;
optionally, the temperature of the reaction of the addition reaction is 20 ℃ to 100 ℃, preferably 50 ℃ to 90 ℃; the reaction time is 1h-100h, preferably 24h-72 h.
The invention also protects the application of the sulfur-containing organosilicon compound, can be used as a refractive index regulator, can also be used as a tackifier of a sealing agent, an adhesive and a coating, and can improve the adhesive strength, water resistance, weather resistance and other properties of a product.
The invention also protects a coating comprising the sulfur-containing organosilicon compound, or comprising the product of the polymerization of the sulfur-containing organosilicon compound as monomer.
Finally, the invention also protects a coating formed by drying and curing a film layer containing the coating.
Has the advantages that:
the invention provides a novel sulfur-containing organosilicon compound, which can improve the refractive index of organosilicon materials, and can reduce the refractive index difference between a hard coating and a base material by using the compound in organosilicon hardening liquid, thereby reducing the interference phenomenon of light.
The present invention provides a novel sulfur-containing organosilicon compound useful as a refractive index modifier and also as a tackifier for sealants, adhesives and coatings.
The invention also provides a preparation method of the sulfur-containing organosilicon compound, which is characterized by mild reaction conditions, high reproducibility and high conversion rate through the addition reaction of amino and isocyanate groups, and can realize industrial production.
Drawings
In order to illustrate the technical solution of the present invention more clearly, the drawings will be briefly described below, and it is apparent that the drawings in the following description relate only to some embodiments of the present invention and are not intended to limit the present invention.
FIG. 1 is a schematic diagram of the reaction equation provided by the present invention;
FIG. 2 is a NMR spectrum of the product provided in example 1 of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. In the following examples, "%" means weight percent, unless otherwise specified.
The performance evaluation method comprises the following steps:
a polycarbonate plastic straight plate with the size of 15cm multiplied by 5cm multiplied by 1mm is adopted, a dip coating mode is adopted, the pulling speed is 2mm/s, and then the substrate is dried for 2 hours at the temperature of 120 ℃ to solidify the hardening liquid coating composition, so that the substrate with the hard coating transparent coating is obtained. The rainbow patterns of the obtained substrate having a transparent coating film were evaluated by the following methods.
Measurement of rainbow texture Properties:
a 36W three-primary-color fluorescent lamp (philips) having a color temperature of 4000K was mounted in a box having a black inner wall, and the light of the fluorescent lamp was reflected on the surface of the hard coat film formed on the sample substrate, and the occurrence of a rainbow pattern (interference fringe) due to light interference was visually observed and evaluated according to the following criteria.
Evaluation criteria:
almost no interference fringes: superior food
Interference fringes are not obvious: good wine
Interference fringes exist, but within the allowed range: in
Interference fringes are significant, exceeding the allowable range: and (4) poor.
Example 1
Adding 76.12g of thiourea, 543g of 3-isocyanate propyltriethoxysilane and 0.3g of dibutyltin dilaurate into a reactor protected by nitrogen, heating to 50 ℃, and stirring at constant temperature for 72 hours to obtain a sulfur-containing organosilicon compound A, wherein the structural formula of the sulfur-containing organosilicon compound A is as follows:
the chemical structure of the sulfur containing organosilicon compound was confirmed by NMR as shown in FIG. 2.
The residual isocyanate content in the compound was determined by measuring the isocyanate group content in the standard HG/T2409-1992 polyurethane prepolymer, whereby the conversion was calculated to be 91%.
Example 2
Adding 38.06g of thiourea, 205g of 3-isocyanate propyl trimethoxy silane and 0.024g of dibutyltin dilaurate into a reactor protected by nitrogen, heating to 90 ℃, and stirring at constant temperature for 24 hours to obtain a sulfur-containing organosilicon compound B, wherein the structural formula of the sulfur-containing organosilicon compound B is as follows:
the chemical structure of the sulfur containing organosilicon compound was confirmed by NMR and the conversion was calculated to be 94%.
Example 3
38.06g of thiourea, 189.3g of 3-isocyanatopropylmethyldimethoxysilane and 0.13g of dibutyltin dilaurate were added to a reactor protected with nitrogen, and the mixture was heated to 70 ℃ and stirred at a constant temperature for 48 hours to obtain a sulfur-containing organosilicon compound C having the formula:
the chemical structure of the sulfur containing organosilicon compound was confirmed by NMR and the conversion was calculated to be 92%.
Example 4
Adding thiourea, 3-isocyanate propyl methyl diethoxy silane and a catalyst tin octoate into a reactor protected by nitrogen, wherein the molar ratio of-NCO groups contained in the 3-isocyanate propyl methyl diethoxy silane to amino groups contained in the thiourea is 1: 1, the dosage of the catalyst is 0.05 percent of the total feeding mass, then the temperature is raised to 60 ℃, and the mixture is stirred for 36 hours at constant temperature, thus obtaining the sulfur-containing organosilicon compound.
Example 5
Adding thiourea, 3-isocyanate propyl methyl diethoxysilane and a catalyst dibutyltin diacetate into a reactor protected by nitrogen, wherein the molar ratio of-NCO groups contained in the 3-isocyanate propyl methyl diethoxysilane to amino groups contained in the thiourea is 1: 1, the dosage of the catalyst is 0.1 percent of the total feeding mass, then the temperature is raised to 20 ℃, and the mixture is stirred for 48 hours at constant temperature, thus obtaining the sulfur-containing organosilicon compound.
Example 6
Adding thiourea, 3-isocyanate propyl methyl diethoxysilane and a catalyst dibutyltin dilaurate into a reactor protected by nitrogen, wherein the molar ratio of-NCO groups contained in the 3-isocyanate propyl methyl diethoxysilane to amino groups contained in the thiourea is 1: 1.1, the dosage of the catalyst is 0.01 percent of the total feeding mass, then the temperature is raised to 100 ℃, and the mixture is stirred for 24 hours at constant temperature, thus obtaining the sulfur-containing organosilicon compound.
Example 7
30g of gamma-glycidoxypropyltrimethoxysilane, 20g of a sulfur-containing organosilicon compound A (the product prepared in example 1), 20g of propylene glycol monomethyl ether, 20g of deionized water, 2g of acetic acid and 38g of isopropanol were mixed, and then hydrolyzed at room temperature for 24 hours, and then 3g of aluminum acetylacetonate and 0.2g of a leveling agent (BYK 346) were added thereto, and the mixture was sufficiently stirred and mixed to prepare a hardening liquid coating composition.
The results of the rainbow texture evaluation of the hardbanding coating composition were excellent: there are almost no interference fringes.
Comparative example 1
A hardening liquid coating composition was prepared by replacing the sulfur-containing organosilicon compound A of example 7 with methyltrimethoxysilane and leaving the remaining components unchanged.
The results of the rainbow-streak evaluation on the hardbanding coating composition were poor: the interference fringes are obvious and exceed the allowable range.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A sulfur-containing organosilicon compound characterized by: the sulfur containing organosilicon compounds have the general formula:
wherein R is1Independently represents an alkyl group having 1 to 4 carbon atoms; r2Independently represents an alkyl group having 1 to 3 carbon atoms; x is independently 1, 2 or 3; n is an integer selected from 2 to 6.
2. The sulfur-containing organosilicon compound of claim 1, wherein: r1Represents a hydrocarbon group having 1 to 3 carbon atoms; preferably, R1Represents methylOr an ethyl group;
optionally, R2Represents methyl or ethyl;
optionally, n is 3, 4 or 5.
3. The sulfur-containing organosilicon compound according to claim 1 or 2, characterized in that: the structural formula of the sulfur-containing organosilicon compound is as follows:
4. a process for producing the sulfur-containing organosilicon compound according to any one of claims 1 to 3, characterized by: comprises the step of carrying out addition reaction of amino and isocyanate on a compound 1 and a compound 2, wherein the reaction formula is as follows:
wherein the compound 1 is isocyanatosilane and the compound 2 is thiourea, and in the reaction formula: r1Independently represents an alkyl group having 1 to 4 carbon atoms; r2Independently represents an alkyl group having 1 to 3 carbon atoms; x is independently 1, 2 or 3; n is an integer selected from 2 to 6.
5. The method for producing the sulfur-containing organosilicon compound according to claim 4, wherein: the compound 1 is any one of 3-isocyanate propyl trimethoxy silane, 3-isocyanate propyl triethoxy silane, 3-isocyanate propyl methyl dimethoxy silane and 3-isocyanate propyl methyl diethoxy silane; optionally, the molar ratio between-NCO groups contained in the siloxane in said compound 1 and amino groups contained in said compound 2 is 1: (1-1.1).
6. The method for producing the sulfur-containing organosilicon compound according to claim 4 or 5, wherein: the addition reaction is carried out under the action of a catalyst, and the catalyst is an organic tin catalyst, preferably at least one of tin octoate, dibutyltin diacetate, dibutyltin dilaurate or diethyltin dilaurate;
optionally, the amount of the catalyst is 0.01-0.1% of the total feeding mass.
7. The method for producing the sulfur-containing organosilicon compound according to claim 4 or 5, wherein: the addition reaction is carried out under the protection of inert gas, preferably nitrogen;
optionally, the temperature of the reaction of the addition reaction is 20 ℃ to 100 ℃, preferably 50 ℃ to 90 ℃; the reaction time is 1h-100h, preferably 24h-72 h.
8. Use of the sulfur-containing organosilicon compound of any of claims 1-3, characterized by: used as refractive index regulator or adhesion promoter for sealant, adhesive and paint.
9. A coating comprising the sulfur-containing organosilicon compound of any of claims 1 to 3, or the product of polymerization of the sulfur-containing organosilicon compound of any of claims 1 to 3 as monomers.
10. A coating formed by the dry curing of a film layer comprising the coating of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010194320.0A CN111269258B (en) | 2020-03-19 | 2020-03-19 | Sulfur-containing organic silicon compound and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010194320.0A CN111269258B (en) | 2020-03-19 | 2020-03-19 | Sulfur-containing organic silicon compound and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111269258A true CN111269258A (en) | 2020-06-12 |
| CN111269258B CN111269258B (en) | 2022-08-19 |
Family
ID=70996332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010194320.0A Active CN111269258B (en) | 2020-03-19 | 2020-03-19 | Sulfur-containing organic silicon compound and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111269258B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005505512A (en) * | 2001-06-29 | 2005-02-24 | ダウ・コーニング・コーポレイション | Method for producing sulfur-containing organosilicon compound using buffer phase transfer catalyst method |
| CN101381443A (en) * | 2007-07-13 | 2009-03-11 | 拜尔材料科学股份公司 | Polyisocyanates containing allophanate and silane groups |
| CN103572298A (en) * | 2012-08-06 | 2014-02-12 | 信越化学工业株式会社 | Metal surface treatment agent, surface treated steel and surface treatment method thereof, and coated steel and making method thereof |
| CN104230976A (en) * | 2013-06-12 | 2014-12-24 | 信越化学工业株式会社 | Novel organosilicon compounds, making methods, and adhesion improver |
| CN110382510A (en) * | 2017-03-09 | 2019-10-25 | 信越化学工业株式会社 | Organo-silicon compound and its manufacturing method |
-
2020
- 2020-03-19 CN CN202010194320.0A patent/CN111269258B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005505512A (en) * | 2001-06-29 | 2005-02-24 | ダウ・コーニング・コーポレイション | Method for producing sulfur-containing organosilicon compound using buffer phase transfer catalyst method |
| CN101381443A (en) * | 2007-07-13 | 2009-03-11 | 拜尔材料科学股份公司 | Polyisocyanates containing allophanate and silane groups |
| CN103572298A (en) * | 2012-08-06 | 2014-02-12 | 信越化学工业株式会社 | Metal surface treatment agent, surface treated steel and surface treatment method thereof, and coated steel and making method thereof |
| CN104230976A (en) * | 2013-06-12 | 2014-12-24 | 信越化学工业株式会社 | Novel organosilicon compounds, making methods, and adhesion improver |
| CN110382510A (en) * | 2017-03-09 | 2019-10-25 | 信越化学工业株式会社 | Organo-silicon compound and its manufacturing method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111269258B (en) | 2022-08-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2258780B1 (en) | Primer composition | |
| EP0759457B2 (en) | Weather and soiling-resistant silicone-containing coating composition | |
| JP3389338B2 (en) | Method for producing hydrolyzable functional group-containing organopolysiloxane and curable resin composition | |
| CN109369880A (en) | A kind of photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylate and its preparation method and application | |
| CN116656240B (en) | Photo-curing coating and coating prepared based on epoxy acrylate condensed alkenyl silicone resin | |
| MXPA02003532A (en) | Coating materials. | |
| AU2014242111A1 (en) | Single-component moisture-curable coatings based on N-substituted urea polymers with extended chains and terminal alkoxysilanes | |
| JP6994562B2 (en) | A coating film containing a coating resin composition and a cured product thereof as a coating layer. | |
| JPS6312671A (en) | Inorganic coating agent | |
| CN111269258B (en) | Sulfur-containing organic silicon compound and preparation method and application thereof | |
| EP4059991A1 (en) | Organopolysiloxane and coating composition containing same | |
| CN116655921A (en) | Photo-curing epoxy acrylate condensed alkenyl silicone resin, preparation method and application | |
| CN116535653A (en) | Organic polysilazane, preparation method thereof and coating material | |
| US11236251B2 (en) | Resin composition for coating, and coating film comprising cured product thereof as coating layer | |
| CN111621016B (en) | Organic silicon polymer and preparation method thereof, adhesive and application thereof | |
| JPH09165450A (en) | Curabale composition, its production, and its cured item | |
| JPH09110984A (en) | Cured silicate product and its production | |
| KR102703471B1 (en) | An organic/inorganic hybrid coating resin composition, a method for preparing the same, and a coating film with high hardness and transparency prepared using the same | |
| KR20160081848A (en) | Composition For Hard Coating and Hard Coating Film Including Cured Product Of The Same As The Coating Layer | |
| JP2750881B2 (en) | Room temperature curable resin composition | |
| KR100518623B1 (en) | Coating-Composition and Manufacturing Method Thereof | |
| KR20190105914A (en) | Room temperature curing coating materials containing silan oligomer | |
| CN112851943B (en) | Polysiloxane with high phenyl content, curable organic silicon composition, preparation method and application | |
| US20230203341A1 (en) | Coating resin composition and coating film comprising cured article thereof as coating layer | |
| KR101967147B1 (en) | Composition For Hard Coating and Hard Coating film Including Cured Product Of The Same As The Coating Layer |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |