CN107698768A - A kind of preparation method of high-performance anti-fingerprint agent - Google Patents
A kind of preparation method of high-performance anti-fingerprint agent Download PDFInfo
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- CN107698768A CN107698768A CN201710796436.XA CN201710796436A CN107698768A CN 107698768 A CN107698768 A CN 107698768A CN 201710796436 A CN201710796436 A CN 201710796436A CN 107698768 A CN107698768 A CN 107698768A
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- 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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- 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
- C09D183/10—Block or graft copolymers containing polysiloxane sequences
- C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1675—Polyorganosiloxane-containing compositions
Abstract
The invention discloses a kind of preparation method of high-performance anti-fingerprint agent, comprise the following steps：The silicone compounds reaction for first passing through end-allyl group PFPE and silicon-hydrogen bond containing obtains the Perfluoropolyether silanes compound containing si-h bond, it is the Perfluoropolyether silanes that dichlorosilane is modified that products therefrom and methylvinyldichlorosilane reaction are obtained into end group, products therefrom and allylic bromination reactive magnesium are obtained into polyfunctional group end-allyl group and are modified Perfluoropolyether silanes, products therefrom and dimethyl dichlorosilane (DMCS) reaction are obtained to the Perfluoropolyether silanes of dichlorosilane modification, dendroid end-allyl group modification Perfluoropolyether silanes are obtained by repeating to react, silicone compounds reaction of the products therefrom again with si-h bond is obtained into dendroid polyfunctional group novel perfluoropolyether alkoxysilane compound.Anti-fingerprint agent hydro-oleophobicity produced by the present invention is good, and antifouling property is excellent, has fabulous binding strength with glass baseplate, anti-wear performance and endurance quality increase substantially.
Description
Technical field
The invention belongs to anti-fingerprint agent preparing technical field, more particularly to a kind of preparation method of high-performance anti-fingerprint agent.
Background technology
In recent years, using the display of mobile phone as representative, the touch panelization of screen is accelerated.But touch panel is naked
The state of dew makes it easily be polluted in use by finger mark, skin oil and fat, sweat, cosmetics etc., influences outward appearance and use.Therefore
In order to improve outward appearance and identity, for being not easy fingerprint to be attached to the technology of display surface or easily removing the technology of dirt
It is required that more and more higher, will not only assign touch panel surface good waterproof and oilproof stain-proofing layer, and its surface is not when wiping
Damage is easily caused, there is good anti-wear performance.Thus generally require to spray anti-fingerprint agent in touch screen surface.
Currently used anti-fingerprint agent all contains perfluoropolyether group, and main component is the perfluor with alkoxysilane group
Polyethers.Being primarily due to the compound containing perfluoropolyether group has heat endurance, chemical inertness, nontoxic, low glass
Change the set of physicochemical characteristic such as temperature and good dielectric properties, hydro-oleophobicity.Just because of these characteristics, it extensively should
Led for the waterproof and oilproof anti-fouling agent of glass surface, the lubricant of magnetic recording media, the oil-proofing agent of precision instrument, diaphragm etc.
Domain.However, organic material is combined with inorganic material such as glass, often using silane coupled technology, alkoxyl silicone is utilized
Groups react with the moisture in air, formed silicone hydroxyl, and silicone hydroxyl under conditions of catalyst or high temperature with glass
The silicone hydroxyl condensation on surface, forms firm chemical bond, firm PFPE coating is formed in glass surface.
For example, patent CN102666759A, 3M house journal of Corning Incorporated CN101501046A, CN1902249A etc. are reported
Road with double bond compound by using PFPE acyl fluorides or end carboxyl PFPE as initiation material, reacting and obtaining PFPE alkene
Hydrolyzable alkoxy is introduced with alkoxy hydrogen silane Si―H addition reaction again after key compound, single-ended PFPE alkane is prepared
TMOS.But because the hydrolization group of such compound exists only in one end of molecule, thus exist in terms of durability
Problem, performance is decreased obviously after long-term use.Therefore, it is necessary to develop with excellent antifouling property and excellent endurance quality
Anti-fingerprint agent product.
The content of the invention
Present invention aims at solve above-mentioned technical problem present in prior art, there is provided a kind of high-performance anti-fingerprint agent
Preparation method, obtained compound forms the excellent low surface energy coat with highly durable property, and it can effectively be prevented
The dirt such as water droplet or finger mark, skin oil and fat, sweat, cosmetics is attached to various materials, especially touch-screen, optical glass and built
Build the surface of glass, and cause water droplet and dirt even if also easily wiping in the post-attachment, while and base material there is fabulous combination
Fastness, anti-wear performance and endurance quality are improved largely.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme that：
A kind of preparation method of high-performance anti-fingerprint agent, it is characterised in that comprise the following steps：
(1)：Under nitrogen protection, to end-allyl group PFPE (PFPE-CH2- CH=CH2) fluorine ethereal solution in add
Pt catalyst, the rear silicone compounds for adding silicon-hydrogen bond containing, back flow reaction 6~8 hours, is washed with methanol, then is steamed through decompression
Fluorine ether solvents are removed in distillation, obtain the Perfluoropolyether silanes compound (A) containing si-h bond；
(2)：Using the three-neck flask device for having reflux condensing tube, the perfluor containing si-h bond that (1) step obtains is added
Polyether silane compound (A), methylvinyldichlorosilane and Pt catalyst, are uniformly mixed, and controlling reaction temperature 60~
100 DEG C, 6~10h is reacted, is washed with tetrahydrofuran and removes unreacted methylvinyldichlorosilane, then removed through being evaporated under reduced pressure
The fluorine ether solvents gone in remaining reactant mixture, it is PFPE-silane (B) that dichlorosilane is modified to obtain end group；
(3)：Using the three-neck flask device for having reflux condensing tube and constant pressure funnel, (2) step is added into three-neck flask
The end group of acquisition is the PFPE-silane (B) and fluorine ether solvents that dichlorosilane is modified, and is uniformly mixed, control reaction temperature
0~10 DEG C of degree, the diethyl ether solution of allylic bromination magnesium is added into constant pressure funnel, is progressively added dropwise, controlling reaction temperature 20~30
DEG C, 8~12h is reacted, methanol is added dropwise after terminating in reaction, is filtered to remove insoluble matter, then obtain polyfunctional group through solvent is distilled off
End-allyl group is modified PFPE-silane (C)；
(4)：The polyfunctional group end-allyl group that (3) step obtains is added into autoclave and is modified PFPE-silane
(C), dimethyl dichlorosilane (DMCS) and Pt catalyst, are uniformly mixed, 60~120 DEG C of controlling reaction temperature, react 6~10h, decompression
Unreacted dimethyl dichlorosilane (DMCS) in reactant mixture is distilled off, washs extraction removing Pt with tetrahydrofuran and fluorine ether solvents and urges
Agent, it is PFPE-silane (D) that dichlorosilane is modified to obtain end group；
(5)：Repeat test procedure (3)-(4) 2~3 times, obtain dendroid end-allyl group and be modified PFPE-silane；
(6)：Under nitrogen protection, the fluorine ether of PFPE-silane is modified to the dendroid end-allyl group that (5) step obtains
Pt catalyst is added in solution, the rear silicone compounds for adding silicon-hydrogen bond containing, back flow reaction 6~8 hours, is washed with methanol,
It is evaporated under reduced pressure and removes fluorine ether solvents, obtains dendroid polyfunctional group novel perfluoropolyether alkoxysilane compound.
Further, end-allyl group PFPE (PFPE-CH in (1) step2- CH=CH2) molecular weight for 2000~
8000, structural formula such as following formula represents：
Wherein m is at least 1 integer, and n and l are respectively at least 0 integer, the random combination of each repeat unit.
Further, the silicone compounds of silicon-hydrogen bond containing are the one or more in following structural formula in (1) step：
Further, Perfluoropolyether silanes compound (A) and methylvinyldichlorosilane containing si-h bond in (2) step
Mol ratio be 1:1~1:5.
Further, end group is the PFPE-silane (B) and allylic bromination magnesium that dichlorosilane is modified in (3) step
Mol ratio is 1:2~1:5.
Further, polyfunctional group end-allyl group is modified PFPE-silane (C) and dimethyl dichlorosilane (DMCS) in (4) step
Mol ratio is 1:1~1:5, reaction temperature is 60~100 DEG C.
Further, the silicone compounds of silicon-hydrogen bond containing are trimethoxy hydrogen silane, triethoxy hydrogen silane in (6) step
One or both of mixture.
The present invention is by adopting the above-described technical solution, have the advantages that：
Dendroid polyfunctional group PFPE-siloxanes is configured to anti-fingerprint agent, during applied to glass surface, dendroid
The a large amount of alkoxysilane groups contained in polyfunctional group PFPE-siloxane molecule chain occur anti-with the moisture in air
Should, silicone hydroxyl is formed, and silicone hydroxyl of the silicone hydroxyl with glass surface under conditions of catalyst or high temperature is condensed, and is formed firm
Chemical bond, compared with common single-ended PFPE siloxanes or common polyfunctional group siloxanes, it contains more curable bases
Group, and the combination of glass substrate surface is more firm, and can reactive group be distributed on strand side chain, with glass baseplate table
The silicone hydroxyl in face is more easy to react, and can greatly improve its adhesive fastness with glass baseplate, while molecule interchain can also occur
Cross-linking reaction, the hardness of coating is improved, further enhance the anti-wear performance and endurance quality of coating；Perfluoropolyether segment is due to table
The effect of face energy migrates to coating surface to be assembled, and assigns coating excellent Waterproofing/oilproofing anti-pollution characteristic, therefore the tree in the present invention
Dendritic polyfunctional group PFPE-siloxanes can assign the more excellent Waterproofing/oilproofing anti-pollution characteristic of coating, anti-wear performance, durable
Performance.
The present invention uses special synthetic route, obtains dendroid polyfunctional group PFPE-siloxanes, has following spy
Point：(1) there are perfluoropolyether structures, assemble in the curing process because the effect of surface energy migrates to coating surface, formed
Coating there is excellent waterproof and oilproof performance, excellent antifouling property and splendid lubrication feel；(2) in strand contain compared with
More hydrolization groups, it can effectively be formed and be chemically bonded with base material, improve endurance quality；(3) hydrolization group in strand
Intermolecular cross-linked structure is easily formed, assigns coating higher hardness, improves its scratch resistant performance.
Embodiment
A kind of preparation method of high-performance anti-fingerprint agent of the present invention, comprises the following steps：
(1)：Under nitrogen protection, to end-allyl group PFPE (PFPE-CH2- CH=CH2) fluorine ethereal solution in add
Pt catalyst, the rear silicone compounds for adding silicon-hydrogen bond containing, back flow reaction 6~8 hours, is washed with methanol, then is steamed through decompression
Fluorine ether solvents are removed in distillation, obtain the Perfluoropolyether silanes compound (A) containing si-h bond, and structural formula such as following formula represents：
End-allyl group PFPE (PFPE-CH2- CH=CH2) molecular weight be 2000~8000, structural formula such as following formula table
Show：
Wherein m is at least 1 integer, and n and l are respectively at least 0 integer, the combination that each repeat unit can be random.
The silicone compounds of silicon-hydrogen bond containing are the one or more in following structural formula：
(2)：Using the three-neck flask device for having reflux condensing tube, the perfluor containing si-h bond that (1) step obtains is added
Polyether silane compound (A), methylvinyldichlorosilane and Pt catalyst, the Perfluoropolyether silanes compound containing si-h bond
(A) mol ratio with methylvinyldichlorosilane is 1:1~1:5, it is uniformly mixed, 60~100 DEG C of controlling reaction temperature,
6~10h is reacted, is washed with tetrahydrofuran and removes unreacted methylvinyldichlorosilane, then residue is removed through being evaporated under reduced pressure
Fluorine ether solvents in reactant mixture, obtain PFPE-silane (B) that end group is dichlorosilane modification, structural formula such as following formula
Represent：
(3)：Using the three-neck flask device for having reflux condensing tube and constant pressure funnel, (2) step is added into three-neck flask
The end group of acquisition is the PFPE-silane (B) and fluorine ether solvents that dichlorosilane is modified, and is uniformly mixed, control reaction temperature
0~10 DEG C of degree, the diethyl ether solution of allylic bromination magnesium is added into constant pressure funnel, and end group is that the perfluor that dichlorosilane is modified gathers
The mol ratio of ether-silane (B) and allylic bromination magnesium is 1:2~1:5, progressively it is added dropwise, 20~30 DEG C of controlling reaction temperature, reacts
Methanol is added dropwise after terminating in 8~12h, reaction, is filtered to remove insoluble matter, then obtain polyfunctional group end-allyl group through solvent is distilled off
Modified PFPE-silane (C), structural formula such as following formula represent：
(4)：The polyfunctional group end-allyl group that (3) step obtains is added into autoclave and is modified PFPE-silane
(C), dimethyl dichlorosilane (DMCS) and Pt catalyst, polyfunctional group end-allyl group are modified PFPE-silane (C) and dimethyl dichlorosilane (DMCS)
Mol ratio be 1:1~1:5, it is uniformly mixed, 60~100 DEG C of controlling reaction temperature, reacts 6~10h, is evaporated under reduced pressure and removes
Unreacted dimethyl dichlorosilane (DMCS) in reactant mixture, wash extraction with tetrahydrofuran and fluorine ether solvents and remove Pt catalyst, obtain
It is PFPE-silane (D) that dichlorosilane is modified to obtain end group, and structural formula such as following formula represents：
(5)：Repeat test procedure (3)-(4) 2~3 times, obtain dendroid end-allyl group and be modified PFPE-silane.
(6)：Under nitrogen protection, the fluorine ether of PFPE-silane is modified to the dendroid end-allyl group that (5) step obtains
Pt catalyst is added in solution, the rear silicone compounds for adding silicon-hydrogen bond containing, the silicone compounds of silicon-hydrogen bond containing are front three
One or both of epoxide hydrogen silane, triethoxy hydrogen silane mixture, back flow reaction 6~8 hours, is washed with methanol, subtracted
Fluorine ether solvents are distilled off in pressure, obtain dendroid polyfunctional group novel perfluoropolyether alkoxysilane compound, structural formula such as following formula table
Show：
Fluorine ether solvents in (1), (2), (3), (4), (5), (6) step can be 7100,7200, the 7300, Su Wei of 3M
HT70, HT110, HT130 in one or more.
Dendroid polyfunctional group PFPE-siloxanes is configured to anti-fingerprint agent, during applied to glass surface, dendroid
The a large amount of alkoxysilane groups contained in polyfunctional group PFPE-siloxane molecule chain occur anti-with the moisture in air
Should, silicone hydroxyl is formed, and silicone hydroxyl of the silicone hydroxyl with glass surface under conditions of catalyst or high temperature is condensed, and is formed firm
Chemical bond, compared with common single-ended PFPE siloxanes or common polyfunctional group siloxanes, it contains more curable bases
Group, and the combination of glass substrate surface is more firm, and can reactive group be distributed on strand side chain, with glass baseplate table
The silicone hydroxyl in face is more easy to react, and can greatly improve its adhesive fastness with glass baseplate, while molecule interchain can also occur
Cross-linking reaction, the hardness of coating is improved, further enhance the anti-wear performance and endurance quality of coating；Perfluoropolyether segment is due to table
The effect of face energy migrates to coating surface to be assembled, and assigns coating excellent Waterproofing/oilproofing anti-pollution characteristic, therefore the tree in the present invention
Dendritic polyfunctional group PFPE-siloxanes can assign the more excellent Waterproofing/oilproofing anti-pollution characteristic of coating, anti-wear performance, durable
Performance.
The present invention uses special synthetic route, obtains dendroid polyfunctional group PFPE-siloxanes, has following spy
Point：(1) there are perfluoropolyether structures, assemble in the curing process because the effect of surface energy migrates to coating surface, formed
Coating there is excellent waterproof and oilproof performance, excellent antifouling property and splendid lubrication feel；(2) in strand contain compared with
More hydrolization groups, it can effectively be formed and be chemically bonded with base material, improve endurance quality；(3) hydrolization group in strand
Intermolecular cross-linked structure is easily formed, assigns coating higher hardness, improves its scratch resistant performance.
Embodiment 1
(1)：Under nitrogen protection, to 20g end-allyl group PFPEs (PFPE-CH2- CH=CH2, molecular weight 2000)
Fluorine ethereal solution (3M 7200) in add Pt catalyst, the rear silicone compounds for adding 4.92g silicon-hydrogen bond containings, back flow reaction 6
Hour, washed with methanol, be evaporated under reduced pressure and remove fluorine ether solvents, obtain the Perfluoropolyether silanes compound that 22g contains si-h bond
(A), the structural formula of the silicone compounds of silicon-hydrogen bond containing such as following formula represents：
(2)：Using the three-neck flask device for having reflux condensing tube, add the 20g that (1) step obtains and contain the complete of si-h bond
Perfluoroalkyl polyether silane compound (A), 2.82g methylvinyldichlorosilanes, Pt catalyst and 100ml fluorine ethereal solution (3M 7200),
It is uniformly mixed, 70 DEG C of temperature control, adds Pt catalyst, react 8h, is washed with tetrahydrofuran and remove unreacted ethylene methacrylic
Base dichlorosilane, then through being evaporated under reduced pressure the fluorine ether solvents removed in remaining reactant mixture, obtain 21g end groups and change for dichlorosilane
PFPE-silane (B) of property；
(3)：Using the three-neck flask device for having reflux condensing tube and constant pressure funnel, 20g (2) is added into three-neck flask
The end group that step obtains is the PFPE-silane (B) and fluorine ether solvents (3M7200) that dichlorosilane is modified, and is uniformly mixed,
0 DEG C of temperature control；The diethyl ether solution (wherein allylic bromination magnesium is 2.9g) of allylic bromination magnesium is added into constant pressure funnel, slowly drop
Add, 20 DEG C of temperature control, react 10h, reaction is added dropwise methanol after terminating, is filtered to remove insoluble matter, and solvent is distilled off and obtains the more officials of 22g
End-allyl group can be rolled into a ball and be modified PFPE-silane (C)；
(4)：The polyfunctional group end-allyl group that 20g (3) step obtains is added in autoclave and is modified PFPE-silicon
Alkane (C), 4g dimethyl dichlorosilane (DMCS)s and Pt catalyst, are uniformly mixed, 80 DEG C of temperature control, react 6h, and vacuum distillation removes dereaction
Unreacted dimethyl dichlorosilane (DMCS) in mixture, wash extraction with tetrahydrofuran and fluorine ether solvents and remove Pt catalyst, obtain
21.6g end groups are PFPE-silane (D) that dichlorosilane is modified；
(5)：Repeat test procedure (3)-(4) 2 times, obtain dendroid end-allyl group and be modified PFPE-silane；
(6)：Under nitrogen protection, it is modified PFPE-silane to the dendroid end-allyl group that 20g (5) step obtains
Add Pt catalyst in 100ml fluorine ethereal solution (3M 7200), it is rear to add 5g trimethoxy hydrogen silanes, back flow reaction 6 hours, use first
Alcohol washs, and is evaporated under reduced pressure and removes fluorine ether solvents, obtains 20g dendroid polyfunctional group novel perfluoropolyether alkoxysilane compounds.
Embodiment 2
(1)：Under nitrogen protection, to 20g end-allyl group PFPEs (PFPE-CH2- CH=CH2, molecular weight 4000)
Fluorine ethereal solution (3M 7100) in add Pt catalyst, the rear silicone compounds for adding 2.4g silicon-hydrogen bond containings, back flow reaction 7
Hour, washed with methanol, be evaporated under reduced pressure and remove fluorine ether solvents, obtain the Perfluoropolyether silanes compound that 21g contains si-h bond
(A), the structural formula of the silicone compounds of silicon-hydrogen bond containing such as following formula represents：
(2)：Using the three-neck flask device for having reflux condensing tube, add the 20g that (1) step obtains and contain the complete of si-h bond
Perfluoroalkyl polyether silane compound (A), 4.26g methylvinyldichlorosilanes, Pt catalyst and 100ml fluorine ethereal solutions (Su Wei
HT110), it is uniformly mixed, 70 DEG C of temperature control, adds Pt catalyst, react 7h, is washed with tetrahydrofuran and remove unreacted first
Base hydridovinyldichlorosilane, then through being evaporated under reduced pressure the fluorine ether solvents removed in remaining reactant mixture, it is dichloro to obtain 21g end groups
Silane-modified PFPE-silane (B)；
(3)：Using the three-neck flask device for having reflux condensing tube and constant pressure funnel, 20g (2) is added into three-neck flask
The end group that step obtains is the PFPE-silane (B) and fluorine ether solvents (3M7100) that dichlorosilane is modified, and is uniformly mixed,
0 DEG C of temperature control；The diethyl ether solution (wherein allylic bromination magnesium is 2.16g) of allylic bromination magnesium is added into constant pressure funnel, slowly
It is added dropwise, 30 DEG C of temperature control, reacts 10h, reaction is added dropwise methanol after terminating, is filtered to remove insoluble matter, and it is more that solvent acquisition 20g is distilled off
Functional group's end-allyl group is modified PFPE-silane (C)；
(4)：The polyfunctional group end-allyl group that 20g (3) step obtains is added in autoclave and is modified PFPE-silicon
Alkane (C), 3g dimethyl dichlorosilane (DMCS)s and Pt catalyst, are uniformly mixed, 80 DEG C of temperature control, react 6h, and vacuum distillation removes dereaction
Unreacted dimethyl dichlorosilane (DMCS) in mixture, wash extraction with tetrahydrofuran and fluorine ether solvents and remove Pt catalyst, obtain
20.4g end groups are PFPE-silane (D) that dichlorosilane is modified；
(5)：Repeat test procedure (3)-(4) 3 times, obtain dendroid end-allyl group and be modified PFPE-silane；
(6)：Under nitrogen protection, it is modified PFPE-silane to the dendroid end-allyl group that 20g (5) step obtains
Add Pt catalyst in 100ml fluorine ethereal solution (3M 7200), it is rear to add 5g trimethoxy hydrogen silanes, back flow reaction 6 hours, use first
Alcohol washs, and is evaporated under reduced pressure and removes fluorine ether solvents, obtains 19.3g dendroid polyfunctional group novel perfluoropolyether alkoxysilane compounds.
Embodiment 3
(1)：Under nitrogen protection, to 20g end-allyl group PFPEs (PFPE-CH2- CH=CH2, molecular weight 4000)
Fluorine ethereal solution (3M 7100) in add Pt catalyst, the rear silicone compounds for adding 5.6g silicon-hydrogen bond containings, back flow reaction 7
Hour, washed with methanol, be evaporated under reduced pressure and remove fluorine ether solvents, obtain the Perfluoropolyether silanes compound that 21g contains si-h bond
(A), the structural formula of the silicone compounds of silicon-hydrogen bond containing such as following formula represents：
(2)：Using the three-neck flask device for having reflux condensing tube, add the 20g that (1) step obtains and contain the complete of si-h bond
Perfluoroalkyl polyether silane compound (A), 8.52g methylvinyldichlorosilanes, Pt catalyst and 100ml fluorine ethereal solutions (Su Wei
HT110), it is uniformly mixed, 70 DEG C of temperature control, adds Pt catalyst, react 7h, is washed with tetrahydrofuran and remove unreacted first
Base hydridovinyldichlorosilane, then through being evaporated under reduced pressure the fluorine ether solvents removed in remaining reactant mixture, it is dichloro to obtain 22g end groups
Silane-modified PFPE-silane (B)；
(3)：Using the three-neck flask device for having reflux condensing tube and constant pressure funnel, 20g (2) is added into three-neck flask
The end group that step obtains is the PFPE-silane (B) and fluorine ether solvents (3M7100) that dichlorosilane is modified, and is uniformly mixed,
0 DEG C of temperature control；The diethyl ether solution (wherein allylic bromination magnesium is 8.42g) of allylic bromination magnesium is added into constant pressure funnel, slowly
It is added dropwise, 30 DEG C of temperature control, reacts 10h, reaction is added dropwise methanol after terminating, is filtered to remove insoluble matter, and solvent is distilled off and obtains 22.5g
Polyfunctional group end-allyl group is modified PFPE-silane (C)；
(4)：The polyfunctional group end-allyl group that 20g (3) step obtains is added in autoclave and is modified PFPE-silicon
Alkane (C), 8g dimethyl dichlorosilane (DMCS)s and Pt catalyst, are uniformly mixed, 80 DEG C of temperature control, react 6h, and vacuum distillation removes dereaction
Unreacted dimethyl dichlorosilane (DMCS) in mixture, wash extraction with tetrahydrofuran and fluorine ether solvents and remove Pt catalyst, obtain 22g
End group is PFPE-silane (D) that dichlorosilane is modified；
(5)：Repeat test procedure (3)-(4) 2 times, obtain dendroid end-allyl group and be modified PFPE-silane；
(6)：Under nitrogen protection, it is modified PFPE-silane to the dendroid end-allyl group that 20g (5) step obtains
Add Pt catalyst in 100ml fluorine ethereal solution (3M 7200), it is rear to add 15g trimethoxy hydrogen silanes, back flow reaction 6 hours, use first
Alcohol washs, and is evaporated under reduced pressure and removes fluorine ether solvents, obtains 23g dendroid polyfunctional group novel perfluoropolyether alkoxysilane compounds.
Embodiment 4
(1)：Under nitrogen protection, to 20g end-allyl group PFPEs (PFPE-CH2- CH=CH2, molecular weight 8000)
Fluorine ethereal solution (3M 7100) in add Pt catalyst, the rear silicone compounds for adding 5.6g silicon-hydrogen bond containings, back flow reaction 7
Hour, washed with methanol, be evaporated under reduced pressure and remove fluorine ether solvents, obtain the Perfluoropolyether silanes compound that 20g contains si-h bond
(A), the structural formula of the silicone compounds of silicon-hydrogen bond containing such as following formula represents：
(2)：Using the three-neck flask device for having reflux condensing tube, add the 20g that (1) step obtains and contain the complete of si-h bond
Perfluoroalkyl polyether silane compound (A), 6.4g methylvinyldichlorosilanes, Pt catalyst and 100ml fluorine ethereal solutions (Su Wei
HT110), it is uniformly mixed, 70 DEG C of temperature control, adds Pt catalyst, react 7h, is washed with tetrahydrofuran and remove unreacted first
Base hydridovinyldichlorosilane, then through being evaporated under reduced pressure the fluorine ether solvents removed in remaining reactant mixture, it is two to obtain 21.6g end groups
PFPE-silane (B) that chlorosilane is modified；
(3)：Using the three-neck flask device for having reflux condensing tube and constant pressure funnel, 20g (2) is added into three-neck flask
The end group that step obtains is the PFPE-silane (B) and fluorine ether solvents (3M7100) that dichlorosilane is modified, and is uniformly mixed,
0 DEG C of temperature control；The diethyl ether solution (wherein allylic bromination magnesium is 6.3g) of allylic bromination magnesium is added into constant pressure funnel, slowly drop
Add, 30 DEG C of temperature control, react 10h, reaction is added dropwise methanol after terminating, is filtered to remove insoluble matter, and solvent is distilled off and obtains the more officials of 22g
End-allyl group can be rolled into a ball and be modified PFPE-silane (C)；
(4)：The polyfunctional group end-allyl group that 20g (3) step obtains is added in autoclave and is modified PFPE-silicon
Alkane (C), 7g dimethyl dichlorosilane (DMCS)s and Pt catalyst, are uniformly mixed, 80 DEG C of temperature control, react 6h, and vacuum distillation removes dereaction
Unreacted dimethyl dichlorosilane (DMCS) in mixture, wash extraction with tetrahydrofuran and fluorine ether solvents and remove Pt catalyst, obtain 22g
End group is PFPE-silane (D) that dichlorosilane is modified；
(5)：Repeat test procedure (3)-(4) 3 times, obtain dendroid end-allyl group and be modified PFPE-silane；
(6)：Under nitrogen protection, it is modified PFPE-silane to the dendroid end-allyl group that 20g (5) step obtains
Add Pt catalyst in 100ml fluorine ethereal solution (3M 7200), it is rear to add 12g trimethoxy hydrogen silanes, back flow reaction 6 hours, use first
Alcohol washs, and is evaporated under reduced pressure and removes fluorine ether solvents, obtains 21g dendroid polyfunctional group novel perfluoropolyether alkoxysilane compounds.
Comparative example 1
Using terminal hydroxy group PFPE (molecular weight is 2500) for initiation material, reacted with double bond compound and obtain PFPE
Hydrolyzable alkoxy is introduced with alkoxy hydrogen silane Si―H addition reaction again after ethylene linkage compound, PFPE alkoxy is prepared
Silane, structural formula are as follows：
PFPE-CH2O-CH2-CH2-CH2-Si-(OCH3)3。
Comparative example 2
Terminal hydroxy group PFPE (molecular weight 2500) prepares PFPE alkoxy with isocyanate alkoxysilane
Silane, structural formula are as follows：
Comparative example 3
Su Wei companies existing product S10 (both-end silicon ethoxyperfluoro polyethers, molecular weight 2000) structural formula is as follows：
The preparation and performance test of anti-fingerprint agent coating
PFPE siloxanes in dendroid PFPE-siloxanes and comparative example obtained in embodiment is respectively taken
In the fluorine ethereal solution (3M 7200) that 0.2g is dissolved in and be sprayed on glass, solidify 30min under the conditions of 150 DEG C, after connect
Feeler test, antifouling property test and rub resistance test.
Test example
(1) contact angle：Drip 2 μ l test fluids (water and hexadecane) and test contact angle in horizontal coating sample surfaces.
(2) antifouling property is tested：
Oil pen tests：With Hi-Mckee (ZEBRA) oiliness one line of stroke on coating sample, oil is then examined
Ink trace mark changes.
☆：Ink is quickly decorporated
○：Ink is decorporated
△：Ink portions are decorporated
×：Ink is not repel
Fingerprint is tested：Coating sample is to speckle with finger print, then wipes fingerprint with dry K-DAY 132-S paper handkerchief,
It is the basic erasing times for removing fingerprint below：
☆：Fingerprint can be removed by wiping in 2 times
○：3~5 ability of erasing thoroughly remove fingerprint
△：Fingerprint can not thoroughly be removed
×：Fingerprint can not be removed
(3) rub resistance is tested：Wiped necessarily on horizontal coating sample with steel wool (BONSTAR#0000,20mm diameter)
Number, then re-test water contact angle (load 1kg, wiping speed：1800mm/min).Test result is as shown in table 1：
The anti-fingerprint agent the performance test results table of table 1
From table 1 it follows that the anti-fingerprint agent (embodiment 1~4) of the present invention is with excellent antifouling property and easily
Wiping properties, while compared with common anti-fingerprint agent (single-ended or both-end PFPE siloxanes), have more excellent wear-resisting
Performance and endurance quality.Thus dendroid polyfunctional group PFPE-siloxanes of the present invention is applied to as anti-fingerprint agent
Glass surface, such as touch-screen, optical glass, building glass field, the excellent soil resistance of glass substrate surface can be assigned, resisted
Scratch resistant and durability, while keep the original transparency of glass.
The specific embodiment of the present invention is these are only, but the technical characteristic of the present invention is not limited thereto.It is any with this hair
Based on bright, to solve essentially identical technical problem, essentially identical technique effect is realized, made simple change, etc.
With replacement or modification etc., all it is covered by among protection scope of the present invention.
Claims (7)
1. a kind of preparation method of high-performance anti-fingerprint agent, it is characterised in that comprise the following steps：
(1)：Under nitrogen protection, to end-allyl group PFPE (PFPE-CH2- CH=CH2) fluorine ethereal solution in add Pt urge
Agent, the rear silicone compounds for adding silicon-hydrogen bond containing, back flow reaction 6~8 hours, is washed with methanol, then is removed through being evaporated under reduced pressure
Fluorine ether solvents are removed, obtain the Perfluoropolyether silanes compound (A) containing si-h bond；
(2)：Using the three-neck flask device for having reflux condensing tube, the PFPE containing si-h bond that (1) step obtains is added
Silane compound (A), methylvinyldichlorosilane and Pt catalyst, are uniformly mixed, controlling reaction temperature 60~100
DEG C, 6~10h is reacted, is washed with tetrahydrofuran and removes unreacted methylvinyldichlorosilane, then is remained through being evaporated under reduced pressure to remove
Fluorine ether solvents in remaining reactant mixture, it is PFPE-silane (B) that dichlorosilane is modified to obtain end group；
(3)：Using the three-neck flask device for having reflux condensing tube and constant pressure funnel, the acquisition of (2) step is added into three-neck flask
End group be dichlorosilane be modified PFPE-silane (B) and fluorine ether solvents, be uniformly mixed, controlling reaction temperature 0~
10 DEG C, the diethyl ether solution of allylic bromination magnesium is added into constant pressure funnel, is progressively added dropwise, 20~30 DEG C of controlling reaction temperature, instead
Answer 8~12h, reaction that methanol is added dropwise after terminating, be filtered to remove insoluble matter, then polyfunctional group end allyl is obtained through solvent is distilled off
Base is modified PFPE-silane (C)；
(4)：Into autoclave add (3) step obtain polyfunctional group end-allyl group be modified PFPE-silane (C),
Dimethyl dichlorosilane (DMCS) and Pt catalyst, are uniformly mixed, 60~120 DEG C of controlling reaction temperature, react 6~10h, are evaporated under reduced pressure
Unreacted dimethyl dichlorosilane (DMCS) in reactant mixture is removed, washing extraction with tetrahydrofuran and fluorine ether solvents removes Pt catalysis
Agent, it is PFPE-silane (D) that dichlorosilane is modified to obtain end group；
(5)：Repeat test procedure (3)-(4) 2~3 times, obtain dendroid end-allyl group and be modified PFPE-silane；
(6)：Under nitrogen protection, the fluorine ethereal solution of PFPE-silane is modified to the dendroid end-allyl group that (5) step obtains
Middle addition Pt catalyst, the rear silicone compounds for adding silicon-hydrogen bond containing, back flow reaction 6~8 hours, is washed with methanol, is depressurized
Fluorine ether solvents are distilled off, obtain dendroid polyfunctional group novel perfluoropolyether alkoxysilane compound.
A kind of 2. preparation method of high-performance anti-fingerprint agent according to claim 1, it is characterised in that：Institute in (1) step
State end-allyl group PFPE (PFPE-CH2- CH=CH2) molecular weight be 2000~8000, structural formula for example following formula represent：
Wherein m is at least 1 integer, and n and l are respectively at least 0 integer, the random combination of each repeat unit.
A kind of 3. preparation method of high-performance anti-fingerprint agent according to claim 1, it is characterised in that：Institute in (1) step
The silicone compounds for stating silicon-hydrogen bond containing are the one or more in following structural formula：
A kind of 4. preparation method of high-performance anti-fingerprint agent according to claim 1, it is characterised in that：Institute in (2) step
It is 1 to state the Perfluoropolyether silanes compound (A) containing si-h bond and the mol ratio of methylvinyldichlorosilane:1~1:5.
A kind of 5. preparation method of high-performance anti-fingerprint agent according to claim 1, it is characterised in that：Institute in (3) step
It is 1 to state the mol ratio that end group is PFPE-silane (B) and allylic bromination magnesium that dichlorosilane is modified:2~1:5.
A kind of 6. preparation method of high-performance anti-fingerprint agent according to claim 1, it is characterised in that：Institute in (4) step
It is 1 to state polyfunctional group end-allyl group and be modified PFPE-silane (C) and the mol ratio of dimethyl dichlorosilane (DMCS):1~1:5, reaction temperature
Spend for 60~100 DEG C.
A kind of 7. preparation method of high-performance anti-fingerprint agent according to claim 1, it is characterised in that：Institute in (6) step
The silicone compounds for stating silicon-hydrogen bond containing are one or both of trimethoxy hydrogen silane, triethoxy hydrogen silane mixture.
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| CN109439194A (en) * | 2018-09-21 | 2019-03-08 | 中国科学院宁波材料技术与工程研究所湖州新能源产业创新中心 | A kind of coating with long-acting durable super-hydrophobic property function |
| CN109942806A (en) * | 2018-03-09 | 2019-06-28 | 深圳怡钛积科技股份有限公司 | Perfluoropolyether-modified dendritic silicon alkane derivatives and its preparation method and application |
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