CN107353366A - A kind of siloxanes pre-polymerization liquid and its manufacture method - Google Patents
A kind of siloxanes pre-polymerization liquid and its manufacture method Download PDFInfo
- Publication number
- CN107353366A CN107353366A CN201610305869.6A CN201610305869A CN107353366A CN 107353366 A CN107353366 A CN 107353366A CN 201610305869 A CN201610305869 A CN 201610305869A CN 107353366 A CN107353366 A CN 107353366A
- Authority
- CN
- China
- Prior art keywords
- polymerization liquid
- siloxanes
- siloxanes pre
- azo
- performed polymer
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/60—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing nitrogen in addition to the carbonamido nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F226/10—N-Vinyl-pyrrolidone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/42—Impregnation with macromolecular compounds
-
- 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
- C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
- C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C09D139/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
-
- 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
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
- D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/06—Polysulfones; Polyethersulfones
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Silicon Polymers (AREA)
Abstract
The present invention relates to a kind of siloxanes pre-polymerization liquid, the siloxanes pre-polymerization liquid is made up of performed polymer and inert organic solvents, the performed polymer is the copolymer that more alkoxy silanes are polymerize to obtain with functional monomer, more alkoxy silanes are vinyltrimethoxy silane, VTES, methyl vinyl diethoxysilane, at least one of methacryloxypropyl trimethyl silane, the functional monomer is hydroxyethyl methacrylate, hydroxy propyl methacrylate, dimethylaminoethyl acrylate methyl ammonia ethyl ester, acrylic acid, N (3 dimethylamino-propyl) Methacrylamide, polyethylene glycol methacrylate-styrene polymer, methyl methacrylate, acrylamide, at least one of N vinyl pyrrolidones.The invention further relates to a kind of preparation method of siloxanes pre-polymerization liquid.
Description
Technical field
The present invention relates to surface modifying material to synthesize field, more particularly to a kind of for surface-crosslinked
Modified siloxanes pre-polymerization liquid and preparation method thereof.
Background technology
In recent years, organosilicon material especially type siloxane has obtained extensively in material surface modifying
General application.Because siloxanes carries 1 functional group and 1~3 alkoxy base, alkoxy
With facile hydrolysis, thus siloxanes can be made to self condense to form silane film in material surface.Obtain
Silane film it is often very thin (be generally less than 1 micron), so as to assign material surface feature (work(
Can group) while farthest reduce change to the original surface topography of material.So
And existing silicone products, typically siloxanyl monomers, such as vinyl triethoxyl silicon
Alkane, MTMS, (3- mercaptopropyis) trimethoxy silane, γ-aminopropyltriethoxy
Diethoxy silane etc., performance comparision is single, and the superficial film formed after being condensed is to material table
Face functionalization improves few.Someone by siloxanes with organic matter is compound prepares composite coating, however,
One side organic matter forms one layer of new polymeric layer as coated substance in porous material surface,
It is often poor as adhesion of the functional layer with porous material surface under normal conditions, the opposing party
Face, it is this that silane is directly incorporated into organic matter or is grafted on the coating system obtained on organic matter
In, because silane molecule is smaller, chemism is higher, be likely to occur dissolution in use and
Lose function of surface.
The content of the invention
In view of this, the present invention provides a kind of silicon for solving existing at least one technical problem
Oxygen alkane pre-polymerization liquid and preparation method thereof.
The present invention provides a kind of siloxanes pre-polymerization liquid, and the siloxanes pre-polymerization liquid is by performed polymer and lazy
Property organic solvent composition, the performed polymer be more alkoxy silanes polymerize with functional monomer
Obtained copolymer, more alkoxy silanes are vinyltrimethoxy silane, vinyl three
Ethoxysilane, methyl vinyl diethoxysilane, methacryloxypropyl trimethyl
At least one of silane, the functional monomer are hydroxyethyl methacrylate, metering system
Sour hydroxypropyl acrylate, dimethylaminoethyl acrylate methyl ammonia ethyl ester, acrylic acid, N- (3- dimethylamino-propyls)
Methacrylamide, polyethylene glycol methacrylate-styrene polymer, methyl methacrylate, acrylamide,
At least one of NVP.
Preferably, the inert organic solvents be ethanol, triethyl phosphate, N, N- dimethyl methyls
Acid amides, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, tripotassium phosphate
At least one of ester.
Preferably, the ratio of the performed polymer and the inert organic solvents is (2g~50g):
100mL。
Preferably, the ratio of the performed polymer and the inert organic solvents is (5g~30g):
100mL。
Preferably, the mass ratio of more alkoxy silanes and functional monomer is 2:1~1:3.
The present invention provides the preparation method of above-mentioned siloxanes pre-polymerization liquid, and it comprises the following steps:
(1) more alkoxy silanes, functional monomer and initiator are added into inert organic solvents
In, obtain a mixture;And
(2) mixture is heated and carries out polymerisation under an inert atmosphere, obtain the silicon
Oxygen alkane pre-polymerization liquid.
Preferably, the initiator is that organic peroxide initiator and/or azo trigger
Agent.
Preferably, the organic peroxide initiator is dibenzoyl peroxide, dialkyl group
At least one of peroxide, the azo-initiator are azo-bis-isobutyl cyanide, azo two
At least one of different cyanogen in heptan, azo-bis-iso-dimethyl, azo isobutyl cyano group formamide.
Preferably, more alkoxy silanes, functional monomer, initiation described in the step (1)
The ratio of agent and inert organic solvents is:
(1g~25g):(1g~25g):(0.05g~0.5g):100mL.
Preferably, the reaction temperature of polymerisation described in the step (2) is 50 degrees Celsius
~100 degrees Celsius, the reaction time is 2 hours~48 hours.
Compared with prior art, advantages of the present invention is as follows:By introducing functional monomer,
Functional monomer is polymerize to obtain performed polymer with more alkoxy silanes.Feature list can be passed through
Body independent assortment, obtain simple function reinforcing or multi-functional compound performed polymer.Pass through extraction
Performed polymer in siloxanes pre-polymerization liquid, and tested through gel permeation chromatograph, the results showed that this is pre-
The molecular weight distribution of aggressiveness is narrower, thus should the material containing the siloxanes pre-polymerization liquid of the performed polymer
Expect that processing characteristics is preferable, it is various not to assign material surface when it is applied to material surface modifying
Same function.It is also, poly- with more alkoxy silanes due to being realized in the form of functional monomer
Close, the performed polymer can porous material surface formed silane film, with reference to SEM,
The phenetic analysis such as x-ray photoelectron power spectrum and infrared spectrum, the silane film very thin thickness formed
(≤100 nanometers), surface modification is carried out using the siloxanes pre-polymerization liquid, to material surface
Pattern influences little.In addition, the siloxanes pre-polymerization liquid solution clarification, it is no emulsification, precipitation,
The bad phenomenons such as muddiness, it can for a long time preserve and never degenerate.The siloxanes pre-polymerization liquid in application
After dilution, change available for the surface modification of various types of materials and the surface-crosslinked of each polyporous materials
Property, it can effectively realize the functions such as hydrophiling, antipollution and the antibacterial of material surface.
The preparation method of the siloxanes pre-polymerization liquid has that condition is relatively gentle, technique is simply excellent
Point, suitable for large-scale production.
Brief description of the drawings
Fig. 1 be the gained siloxanes pre-polymerization liquid of embodiment 2 in performed polymer infrared spectrogram (wherein,
Curve a corresponds to NVP monomer, and curve b corresponds to described performed polymer).
Fig. 2 is the gel permeation chromatography spectrogram of the gained siloxanes pre-polymerization liquid of embodiment 3.
Embodiment
Siloxanes pre-polymerization liquid provided by the invention and preparation method thereof will be made furtherly below
It is bright.
The present invention provides a kind of preparation method of siloxanes pre-polymerization liquid, and it includes following step
Suddenly:
S1, more alkoxy silanes, functional monomer and initiator are added in inert organic solvents,
Obtain a mixture;
S2, the mixture is heated and carries out polymerisation under an inert atmosphere, obtains the silicon
Oxygen alkane pre-polymerization liquid.
In step sl, the function that the functional monomer can be modified according to surface needs and selected
Select, specific is the monomer containing unsaturated carbon-carbon double bond (C=C).More alkoxy silanes
For more alkoxy silanes containing unsaturated carbon-carbon double bond (C=C).More alkoxy silanes with
Polymerisation occurs in the presence of the initiator and obtains performed polymer for functional monomer.Specifically
, more alkoxy silanes be vinyltrimethoxy silane, VTES,
In methyl vinyl diethoxysilane, methacryloxypropyl trimethyl silane at least
It is a kind of.The functional monomer is hydroxyethyl methacrylate, hydroxy propyl methacrylate, first
Base acrylic acid diformazan ammonia ethyl ester, acrylic acid, N- (3- dimethylamino-propyls) Methacrylamide,
Polyethylene glycol methacrylate-styrene polymer, methyl methacrylate, acrylamide, N- vinyl pyrroles
At least one of alkanone.
The initiator act as initiated polymerization.The initiator is organic peroxide
Class initiator and/or azo-initiator.The organic peroxide initiator is peroxidating
At least one of dibenzoyl, dialkyl peroxide, the azo-initiator are azo
The different cyanogen in heptan of two isobutyl cyanogen, azo two, azo-bis-iso-dimethyl, azo isobutyl cyano group formyl
At least one of amine.The dosage of the initiator is less, can according to specific reactant and its
Depending on dosage.
The mass ratio of more alkoxy silanes and functional monomer is 2:1~1:3, be preferably,
2:1~1:2.
The performed polymer for acting as obtaining of the inert organic solvents preserves in liquid form,
Isolate the induction such as moisture, prevent performed polymer from hydrolytic crosslinking occurring in storage process, and be allowed to
In relatively steady state, and can preserve for a long time.The inert organic solvents be ethanol,
Triethyl phosphate, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO),
At least one of 1-METHYLPYRROLIDONE, trimethyl phosphate.The dosage of the inert organic solvents
Depending on according to specific needs, it is however generally that, the dosage of the inert organic solvents is less, with side
Just the needs for preserving and transporting.That is, described more alkoxy silanes and the inert organic solvents
Ratio be:(1g~25g):(80mL~150mL).
Preferably, more alkoxy silanes, functional monomer, initiator and inertia are organic molten
The ratio of agent is:(1g~25g):(1g~25g):(0.05g~0.5g):100mL.
In step s 2, the reaction temperature of the polymerisation is 50 degrees Celsius~100 Celsius
Degree, reaction time are 2 hours~48 hours.Preferably, the reaction temperature is 65 Celsius
~85 degrees Celsius of degree, reaction time are 8 hours~24 hours.
After reaction terminates, obtained performed polymer and the ratio of the inert organic solvents are
(2g~50g):100mL, it is preferably, (5g~30g):100mL.
The present invention also provides a kind of siloxanes pre-polymerization liquid being prepared using the above method.It is described
Siloxanes pre-polymerization liquid is made up of performed polymer and inert organic solvents, and the performed polymer is more alkoxies
Silane is polymerize obtained copolymer with functional monomer.
Compared with prior art, advantages of the present invention is as follows:By introducing functional monomer,
Functional monomer is polymerize to obtain performed polymer with more alkoxy silanes.Feature list can be passed through
Body independent assortment, obtain simple function reinforcing or multi-functional compound performed polymer.Pass through extraction
Performed polymer in siloxanes pre-polymerization liquid, and tested through gel permeation chromatograph, the results showed that this is pre-
The molecular weight distribution of aggressiveness is narrower, thus should the material containing the siloxanes pre-polymerization liquid of the performed polymer
Expect that processing characteristics is preferable, it is various not to assign material surface when it is applied to material surface modifying
Same function.It is also, poly- with more alkoxy silanes due to being realized in the form of functional monomer
Close, the performed polymer forms silane film in porous material surface, with reference to SEM, X
The phenetic analysis such as X-ray photoelectron spectroscopy X and infrared spectrum, the silane film very thin thickness formed
(≤100 nanometers), surface modification is carried out using the siloxanes pre-polymerization liquid, to material surface
Pattern influences little.In addition, the siloxanes pre-polymerization liquid solution clarification, it is no emulsification, precipitation,
The bad phenomenons such as muddiness, it can for a long time preserve and never degenerate.The siloxanes pre-polymerization liquid in application
After dilution, change available for the surface modification of various types of materials and the surface-crosslinked of each polyporous materials
Property, it can effectively realize the functions such as hydrophiling, antipollution and the antibacterial of material surface.
The preparation method of the siloxanes pre-polymerization liquid has that condition is relatively gentle, technique is simply excellent
Point, suitable for large-scale production.
Hereinafter, will be in conjunction with specific embodiments to siloxanes pre-polymerization liquid of the present invention and its preparation
Method further illustrates.
Embodiment 1
(1) by 1g hydroxyethyl methacrylate, 1g vinyltrimethoxy silane and
0.05g benzoyl peroxide is added sequentially in 100mL absolute ethyl alcohol, is passed through Industrial Nitrogen
Gas, and 200r/min mechanical agitations 20min at normal temperatures;
(2) open heating and gradually rise temperature to 65 DEG C, in the atmosphere of industrial nitrogen, with
200r/min rotating speed mechanical agitation is simultaneously reacted 36 hours.After reaction terminates, heating is closed,
Hydroxyethyl methacrylate/vinyltrimethoxy silane copolymer is obtained after abundant cooling
Pre-polymerization liquid.
Polyurethane sponge is soaked into the dilute solution of gained pre-polymerization liquid, through surface-crosslinked processing
Afterwards, the hydrophily on polyurethane sponge surface can be improved.
Embodiment 2
(1) by 4g NVP, 3g VTES and
The 0.1g different cyanogen in heptan of azo two is added sequentially in 100mL triethyl phosphate, is passed through high-purity
Nitrogen, and 250r/min mechanical agitations 30min at normal temperatures;
(2) open heating and gradually rise temperature to 80 DEG C, in the atmosphere of high pure nitrogen, with
250r/min rotating speed mechanical agitation is simultaneously reacted 24 hours.Question response closes heating after terminating,
NVP/VTES copolymer is obtained after abundant cooling
Pre-polymerization liquid.
Polypropylene non-woven fabric is soaked into the dilute solution of gained pre-polymerization liquid, through surface-crosslinked place
After reason, the polypropylene non-woven fabric with super hydrophilic characteristic can be obtained.
As seen from Figure 1, performed polymer is (see curve b) in 1704cm-1Place (corresponds to raw material list
C=C double bonds in body) without obvious characteristic absorption peak, only it is left in 1640cm-1Place is (right
Should in NVP starting monomer C=O double bonds) characteristic absorption peak, this says
Bright NVP monomer and VTES monomer are in radical polymerization
Effectively it is polymerize during thing.
Embodiment 3
(1) by 6g dimethylaminoethyl acrylate methyl ammonia ethyl ester, 4g vinyl triethoxyl silicon
Alkane and 0.15g azo-bis-isobutyl cyanide are added sequentially to 100mL N, N- dimethyl formyls
In amine, high pure nitrogen, and 250r/min mechanical agitations 40min at normal temperatures are passed through;
(2) open heating and gradually rise temperature to 90 DEG C, in the atmosphere of high pure nitrogen, with
250r/min rotating speed mechanical agitation is simultaneously reacted 18 hours.Question response closes heating after terminating,
Dimethylaminoethyl acrylate methyl ammonia ethyl ester/VTES copolymerization is obtained after abundant cooling
The pre-polymerization liquid of thing.
PLA microporous barrier is soaked into the dilute solution of gained pre-polymerization liquid, through surface-crosslinked place
After reason, the anti-bovine serum albumin(BSA) contaminative of PLA microporous barrier is remarkably improved.
From Figure 2 it can be seen that the molecular weight distribution of the performed polymer in gained pre-polymerization liquid is narrower, it is flat
Average molecular weight MnAbout 2000.
Embodiment 4
(1) by 15g dimethylaminoethyl acrylate methyl ammonia ethyl ester, 12g methyl ethylene diethyl
TMOS and 0.25g dialkyl peroxide are added sequentially to 100ml N, N- diformazans
In yl acetamide, ordinary nitrogen, and 300r/min mechanical agitations 60min at normal temperatures are passed through;
(2) open heating and gradually rise temperature to 70 DEG C, in the atmosphere of ordinary nitrogen, with
300r/min rotating speed mechanical agitation is simultaneously reacted 48 hours.Question response closes heating after terminating,
Dimethylaminoethyl acrylate methyl ammonia ethyl ester/methyl vinyl diethoxysilane is obtained after abundant cooling
The pre-polymerization liquid of copolymer.
After tested, polyvinylidene fluoride microporous film is soaked into the dilute solution of gained pre-polymerization liquid,
After surface-crosslinked processing, the anti-bovine serum albumin(BSA) of polyvinylidene fluoride microporous film is remarkably improved
Contaminative.
The pre-polymerization liquid of gained is stood 30 days in 100 DEG C of constant temperature.As a result show, it is prepared
Pre-polymerization liquid keeps clarification, does not occur the bad phenomenons such as muddiness, precipitation, particle.
Embodiment 5
(1) by 8g N- (3- dimethylamino-propyls) Methacrylamide, 6g methyl
Acryloxypropyl trimethyl silane and 0.1g azo-bis-iso-dimethyl sequentially add
To 100ml 1-METHYLPYRROLIDONE, argon gas, and 300r/min machineries at normal temperatures are passed through
Stir 50min;
(2) open heating and gradually rise temperature to 80 DEG C, in the atmosphere of ordinary nitrogen, with
300r/min rotating speed mechanical agitation is simultaneously reacted 30 hours.Question response closes heating after terminating,
N- (3- dimethylamino-propyls) Methacrylamide/methacryl is obtained after abundant cooling
The pre-polymerization liquid of epoxide oxypropyl trimethyl silane copolymer.
After tested, polyvinylidene fluoride microporous film is soaked into the dilute solution of gained pre-polymerization liquid,
After surface-crosslinked processing, the anti-protein contamination of polyvinylidene fluoride microporous film is remarkably improved.
It is quaternized that surface-crosslinked modified polyvinylidene fluoride microporous film is further subjected to surface
Processing, obtains polyvinylidene fluoride microporous film of the surface with cationic characteristic.Surveyed through anti-Escherichia coli
Examination, can form obvious inhibition zone phenomenon, illustrate prepared polyvinylidene fluoride microporous film to big
Enterobacteria has good inhibitory action.
Embodiment 6
(1) by 8g N- (3- dimethylamino-propyls) Methacrylamide, 8g N-
Vinyl pyrrolidone, 10g methacryloxypropyl trimethyl silane and 0.2g idol
The isobutyl dimethyl phthalate of nitrogen two is added sequentially to 100ml 1-METHYLPYRROLIDONE, is passed through argon gas,
And 300r/min mechanical agitations 50min at normal temperatures;
(2) open heating and gradually rise temperature to 80 DEG C, in the atmosphere of ordinary nitrogen, with
300r/min rotating speed mechanical agitation is simultaneously reacted 30 hours.Question response closes heating after terminating,
N- (3- dimethylamino-propyls) Methacrylamide/N- vinylpyridines are obtained after abundant cooling
The pre-polymerization liquid of pyrrolidone/methacryloxypropyl trimethyl silicane alkyl copolymer.
After tested, polyvinylidene fluoride microporous film is soaked into the dilute solution of gained pre-polymerization liquid,
After surface-crosslinked processing, the hydrophily of polyvinylidene fluoride microporous film and anti-albumen are remarkably improved
Contaminative.
Embodiment 7
The polyvinylidene fluoride microporous film of surface-crosslinked modification prepared by embodiment 6 is subjected to table
The quaternized processing in face, obtain polyvinylidene fluoride of the surface with cationic characteristic and with super hydrophilic characteristic
Alkene microporous barrier.Tested through anti-Escherichia coli, obvious inhibition zone phenomenon can be formed, illustrated made
Standby polyvinylidene fluoride microporous film has good inhibitory action to Escherichia coli.
Embodiment 8
(1) by 6g hydroxy propyl methacrylate, 4g N- polyethylene glycol methacrylic acids
Ester, 5g methyl vinyl diethoxysilane/3g VTES and 0.15g
Azo isobutyl cyano group formamide be added sequentially to 100ml dimethyl sulfoxide (DMSO), be passed through nitrogen,
And 200r/min mechanical agitations 60min at normal temperatures;
(2) open heating and gradually rise temperature to 100 DEG C, in the atmosphere of ordinary nitrogen,
With 200r/min rotating speed mechanical agitation and react 10 hours.Question response closes heating after terminating,
Hydroxy propyl methacrylate/N- polyethylene glycol methacrylate-styrene polymers/methyl is obtained after abundant cooling
The pre-polymerization liquid of methylvinyldiethoxysilane/VTES copolymer.
After tested, polysulphone super-filter membrane is soaked into the dilute solution of gained pre-polymerization liquid, through surface
After crosslinking Treatment, the polysulphone super-filter membrane of gained shows good hydrophily and anti-protein contamination
Property.
Embodiment 9
The polysulphone super-filter membrane of surface-crosslinked modification prepared by embodiment 8 is subjected to surface quaternary ammonium
Change.Show after tested, prepared polysulphone super-filter membrane has good hydrophily and anti-albumen dirty
Metachromia, while there is significant antibiotic property.
Embodiment 10
(1) by the azo of 10g acrylic acid, 6g VTES and 0.2g
Isobutyl cyano group formamide is added sequentially in 100ml triethyl phosphate, is passed through nitrogen, and
200r/min mechanical agitations 60min under normal temperature;
(2) open heating and gradually rise temperature to 80 DEG C, in the atmosphere of nitrogen, with
200r/min rotating speed mechanical agitation is simultaneously reacted 24 hours.Question response closes heating after terminating,
The pre-polymerization liquid of acrylic acid/VTES copolymer is obtained after abundant cooling.
Polyvinylidene fluoride microporous film is soaked into the dilute solution of gained pre-polymerization liquid, handed over through surface
After connection processing, then soaked 8 hours in nano-Au solution, obtain the poly- of area load nanogold
Vinylidene microporous barrier.After tested, prepared polyvinylidene fluoride microporous film to sodium borohydride also
Former p-nitrophenol has excellent catalytic effect.
Embodiment 11
(1) by 20g NVP, 20g VTES
And 0.15g azo isobutyl cyano group formamide is added sequentially in 100ml absolute ethyl alcohol, lead to
Enter nitrogen, and 200r/min mechanical agitations 60min at normal temperatures;
(2) open heating and gradually rise temperature to 60 DEG C, in the atmosphere of ordinary nitrogen, with
200r/min rotating speed mechanical agitation is simultaneously reacted 48 hours.Question response closes heating after terminating,
NVP/VTES copolymer is obtained after abundant cooling
Pre-polymerization liquid.
By the uniform coating of the dilute solution of gained pre-polymerization liquid and metal sheet surface.Treat naturally dry
Afterwards, after tested, metal sheet surface shows the super imbibition characteristic of water droplet.
The explanation of above example is only intended to help method and its core think of for understanding the present invention
Think.It should be pointed out that for those skilled in the art, this hair is not being departed from
On the premise of bright principle, some improvement and modification can also be carried out to the present invention, these improve and
Modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, professional and technical personnel in the field are enable to realize
Or use the present invention.A variety of modifications to these embodiments come to those skilled in the art
Say and will be apparent, generic principles defined herein can not depart from the present invention's
In the case of spirit or scope, realize in other embodiments.Therefore, the present invention will not be by
The embodiments shown herein is limited to, and is to fit to and principles disclosed herein and new
The consistent most wide scope of clever feature.
Claims (10)
1. a kind of siloxanes pre-polymerization liquid, it is characterised in that the siloxanes pre-polymerization liquid is had by performed polymer and inertia
Solvent forms, and the performed polymer is the copolymer that more alkoxy silanes are polymerize to obtain with functional monomer,
More alkoxy silanes are vinyltrimethoxy silane, VTES, methyl ethylene
At least one of diethoxy silane, methacryloxypropyl trimethyl silane, the feature list
Body be hydroxyethyl methacrylate, hydroxy propyl methacrylate, dimethylaminoethyl acrylate methyl ammonia ethyl ester, acrylic acid,
N- (3- dimethylamino-propyls) Methacrylamide, polyethylene glycol methacrylate-styrene polymer, methyl methacrylate,
At least one of acrylamide, NVP.
2. siloxanes pre-polymerization liquid as claimed in claim 1, it is characterised in that the inert organic solvents are
Ethanol, triethyl phosphate, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO), N-
At least one of methyl pyrrolidone, trimethyl phosphate.
3. siloxanes pre-polymerization liquid as claimed in claim 1, it is characterised in that the performed polymer with it is described lazy
The ratio of property organic solvent is (2g~50g):100mL.
4. siloxanes pre-polymerization liquid as claimed in claim 3, it is characterised in that the performed polymer with it is described lazy
The ratio of property organic solvent is (5g~30g):100mL.
5. siloxanes pre-polymerization liquid as claimed in claim 1, it is characterised in that more alkoxy silanes with
The mass ratio of functional monomer is 2:1~1:3.
6. a kind of preparation method of such as any one of Claims 1 to 5 siloxanes pre-polymerization liquid, it comprises the following steps:
(1) more alkoxy silanes, functional monomer and initiator are added in inert organic solvents, it is mixed obtains one
Compound;And
(2) mixture is heated and carries out polymerisation under an inert atmosphere, obtain the siloxanes pre-polymerization
Liquid.
7. the preparation method of siloxanes pre-polymerization liquid as claimed in claim 6, it is characterised in that the initiation
Agent is organic peroxide initiator and/or azo-initiator.
8. the preparation method of siloxanes pre-polymerization liquid as claimed in claim 7, it is characterised in that described organic
Peroxide type initiators are dibenzoyl peroxide, at least one of dialkyl peroxide, the idol
Nitrogen class initiator is azo-bis-isobutyl cyanide, the different cyanogen in heptan of azo two, azo-bis-iso-dimethyl, azo isobutyl
At least one of cyano group formamide.
9. the preparation method of siloxanes pre-polymerization liquid as claimed in claim 6, it is characterised in that the step
(1) more alkoxy silanes described in, functional monomer, the ratio of initiator and inert organic solvents are:
(1g~25g):(1g~25g):(0.05g~0.5g):100mL.
10. the preparation method of siloxanes pre-polymerization liquid as claimed in claim 6, it is characterised in that the step
Suddenly the reaction temperature of polymerisation described in (2) is 50 degrees Celsius~100 degrees Celsius, and the reaction time is 2 hours
~48 hours.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610305869.6A CN107353366A (en) | 2016-05-10 | 2016-05-10 | A kind of siloxanes pre-polymerization liquid and its manufacture method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610305869.6A CN107353366A (en) | 2016-05-10 | 2016-05-10 | A kind of siloxanes pre-polymerization liquid and its manufacture method |
Publications (1)
Publication Number | Publication Date |
---|---|
CN107353366A true CN107353366A (en) | 2017-11-17 |
Family
ID=60272024
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610305869.6A Pending CN107353366A (en) | 2016-05-10 | 2016-05-10 | A kind of siloxanes pre-polymerization liquid and its manufacture method |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107353366A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117925005A (en) * | 2024-01-25 | 2024-04-26 | 鹤山市怡信化工厂有限公司 | Water-based ink for printing and preparation method and application thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101974118A (en) * | 2010-11-10 | 2011-02-16 | 上海交通大学 | Solvent thermal polymerization method of styrene-silane copolymer |
CN102108106A (en) * | 2011-01-05 | 2011-06-29 | 常州大学 | Method for preparing microcapsule through miniemulsion polymerization by utilizing siloxane copolymer as auxiliary stabilizing agent |
CN102504085A (en) * | 2011-10-20 | 2012-06-20 | 上海交通大学 | Solvent thermal polymerization method of methyl methacrylate-silicane copolymer |
CN103210906A (en) * | 2013-02-26 | 2013-07-24 | 中国中化股份有限公司 | Application of organosilicon-modified high-molecular compound as seed coating film-forming agent |
-
2016
- 2016-05-10 CN CN201610305869.6A patent/CN107353366A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101974118A (en) * | 2010-11-10 | 2011-02-16 | 上海交通大学 | Solvent thermal polymerization method of styrene-silane copolymer |
CN102108106A (en) * | 2011-01-05 | 2011-06-29 | 常州大学 | Method for preparing microcapsule through miniemulsion polymerization by utilizing siloxane copolymer as auxiliary stabilizing agent |
CN102504085A (en) * | 2011-10-20 | 2012-06-20 | 上海交通大学 | Solvent thermal polymerization method of methyl methacrylate-silicane copolymer |
CN103210906A (en) * | 2013-02-26 | 2013-07-24 | 中国中化股份有限公司 | Application of organosilicon-modified high-molecular compound as seed coating film-forming agent |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117925005A (en) * | 2024-01-25 | 2024-04-26 | 鹤山市怡信化工厂有限公司 | Water-based ink for printing and preparation method and application thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104926156B (en) | A kind of preparation method and its product of Transparent persistence type antifog glass | |
JP2023052061A (en) | Surface-modified porous battery separator | |
KR101190718B1 (en) | Methacrylic Particle Having Core-Shell Structure and Method of Preparing the Same | |
Machotová et al. | Water sensitivity of fluorine-containing polyacrylate latex coatings: Effects of crosslinking and ambient drying conditions | |
CN104672403A (en) | Environment-friendly silicon-acrylate emulsion and preparation method thereof | |
CN102605621A (en) | Method for preparing waterproof moisture-permeability fabric coating agent with nano SiO2 modified polyacrylate | |
CN111058334A (en) | Modified polyacrylate waterproof anti-sticking agent, preparation method and application | |
US20220127425A1 (en) | Coating Composition Comprised of a Hydrophilic Crosslinker, a Hydrophobic Crosslinker and Optionally a Hydrogel and Methods of Making and Using the Same | |
JPH01152139A (en) | Method for improving function characteristic of polyolefin article by polymerization started by electron beam | |
CN107353366A (en) | A kind of siloxanes pre-polymerization liquid and its manufacture method | |
CN106519152A (en) | Polymer nanoparticle, composite hydrogel, and preparation method thereof | |
CN107349808A (en) | A kind of modified polymer microporous film and its manufacture method | |
CN109331544B (en) | Polyethylene filter element modified through lasting hydrophilization and preparation method thereof | |
CN106752623B (en) | A kind of preparation method of heat curing type polyacrylate hydrophilic antifogging coating | |
Zhou et al. | Synthesis and characterization of organic fluorine and nano-SiO2 modified polyacrylate emulsifier-free latex | |
CN105418861B (en) | One kind is based on polyaminoacid molecule cross-link hydrogel and preparation method thereof | |
TWI544053B (en) | Optical film | |
Chen et al. | A novel fast responsive thermo-sensitive poly (N-isopropylacrylamide)-clay nanocomposites hydrogels modified by nanosized octavinyl polyhedral oligomeric silsesquioxane | |
US20150140222A1 (en) | Hydrophobic Coating Composition And Method Of Imparting Hydrophobicity Onto A Surface | |
CN102643381B (en) | Method for preparing polyacrylate/montmorillonite composite leather finishing agent by adopting reactive emulsifier | |
CN102007153B (en) | Polymerisable substance with connected nanoparticles | |
CN107213112B (en) | Preparation method of silicon-based hydrogel drug-loading system for selectively identifying ofloxacin | |
CN106317714A (en) | Method of modifying nano-aluminium oxide using cold plasma | |
CN109824817A (en) | A kind of hydrophobic acrylic acid's aqueous dispersion and preparation method thereof | |
Yoo et al. | Preparation of acrylic copolymers and crosslinking agents and properties as a film |
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: 20171117 |