CN103906776A - Polymeric structure - Google Patents
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- CN103906776A CN103906776A CN201280045442.7A CN201280045442A CN103906776A CN 103906776 A CN103906776 A CN 103906776A CN 201280045442 A CN201280045442 A CN 201280045442A CN 103906776 A CN103906776 A CN 103906776A
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- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/52—Polymerisation initiated by wave energy or particle radiation by electric discharge, e.g. voltolisation
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- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
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- 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
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/62—Plasma-deposition of organic layers
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- 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
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
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Abstract
A method of creating a polymer brush bearing covalently bound polymeric side chains, comprising the steps of: (a) deposition, onto a substrate, of a halogen containing initiator film or a precursor which is derivatized into a halogen containing initiator film; (b) surface ATRP growth, from the halogen containing initiator film formed in step (a), of a polymeric brush backbone incorporating side groups; (c) growth, from the polymeric brush backbone formed in step (b), of polymeric side chains on the polymeric brush backbone, to form the polymer brush in which the polymeric side chains constitute the bristles of the brush.
Description
Invention field
The present invention relates to produce the purposes as lubricant with method, the polymer brush forming by described method and the described polymer brush of the polymer brush of the polymeric side chains of covalency bond.
background of invention
Linear polymer brush with the strict restriction of the polymer lateral chain of covalency bonds is in a large number referred to as molecule bottle brush (molecular bottle brush).These polymer brushs are because their new property has significant magnetism, and these character comprise for the stimuli responsive effect of the potential application such as sensor, nano-form, photonic crystal and molecule tension testing machine and ultra-soft rheological characteristics.In addition, shown to be dispersed in solution, then the bottle brush polymkeric substance of surface adsorption is attributable in the molecule between the crowded bristle segment of densification and intermolecular repulsion and show extremely low nano friction characteristic.Based on this prerequisite, polymkeric substance bottle brush and the covalently bound crowded nano lubricating of giving improvement in space due to aggravation of solid surface that can expect strict restriction.
There is the different methods of three kinds of synthetic molecules bottle brush.First, have " being grafted to main chain (grafting to) " method, it need to be connected to preformed macromolecule side chain on polymeric skeleton.This is because space constraint is subject to the puzzlement of intrinsic Finite Density that side chain connects.Secondly, there is " large monomer polymerization (grafting through) " method, it comprises the polymerization of large monomer (with polymerizable groups and the preformed oligopolymer of complete side chain), but be easy to experience polymerization control loss along with side chain lengths increases them, cause bad polymolecularity.Finally, have " from main chain grafting (grafting from) " method, it comprises the initiation site controlled fusion of side chain from the length location of the polymer backbone along strict restriction.For this situation, in all can realizing aspect skeleton size and side chain dimensions two, controlling, thus synthetic complicated bottle brush structure.But in these cases, it is synthetic that research concentrates on solution phase, is then surface adsorption, rather than the target surface of polymkeric substance bottle brush connects.
Atom transfer radical polymerization (ATRP) is widely used in controlled/living polymerization due to related mild reaction conditions with to the suitability of k wide region monomer.This technology is often applicable to synthesizing the co-polymer of sharp outline in conjunction with the order reactivate of " activity " halogenide end-blocking end of the chain with continuous ATRP polymerization, for example, form block copolymer.Another variant comprises the linear polymer brush with the sharp outline of the polymer lateral chain of a large amount of covalency bonds, and they are called as molecule bottle brush.Recorded from the ATRP of surface site initiation in order to generate fine and close graftomer/multipolymer brush layer comprehensively.But for the crowded challenge that has more in intrinsic space due to skeleton polymer from main chain Graft Method of polymer attached bottle brush from the teeth outwards, this has hindered the growth of side chain (bristle).This space is crowded reflects the ATRP initiation site that uses densification prepared by the individual layer (SAMs) of self-assembly to fill.Previous trial for the functionalisation of surfaces with bottle brush is confined to use large monomer polymerization method (grafting through method), produces the bristle of profile bad luck, or is the preformed bottle brush of physical adsorption from solution.The previous ATRP polymerization of also attempting adopting the SAMs mixing by uses to utilize skeleton and the continuous surface initiation of side chain segment subsequently reduce the initiator density (so that enough spacing to be provided between grafting so that the growth subsequently of side chain) of substrate surface from main chain Graft Method (grafting from approach); But, do not provide the bottle brush of sharp outline to be connected to surperficial unambiguous evidence.In addition, have the inherent defect relevant to SAMs, it is included in the moisture sensitive of the secular instability for oxidation, silane in the situation of mercaptan-Jin system and needs multi-step to synthesize to prepare suitable SAM initiator molecule.
All above-mentioned shortcomings all can be potentially by overcoming to produce ATRP initiator layer in the electroless plating of one step applying plasma.For example, Teare, D.O.H.; Barwick, D.C.; Schofield, W.C.E.; Garrod, R.P.; Ward, L.J.; Badyal, poly-(vinyl chlorination benzyl) initiator layer that J.P.S. Langmuir 2005,21,11425 discloses pulsed plasma deposition has been successfully used to the polymer brush ATRP of sharp outline to grow on many kinds of solids base material.The method was guaranteed to be covalently attached to base material (for silicon and glass baseplate via the avtive spot producing in interface by electric discharge between nanolayer deposition elementary period, Si-C key will be responsible for adhering to, similarly, for metal, M-C key will be responsible for adhering to, and for polymkeric substance, will be free radical by discharge generation).The density of the functional group existing in surface in addition, can customize by careful fine setting discharge parameter.
Plasma technique has quite been widely used for polymeric coatings to deposit to widely on surface.This technology is considered to be the clean dry type technology that produces less refuse compared with conventional wet chemistry method.Use the method, plasma body is produced by organic molecule, and organic molecule stands electric field action.In the time that this carries out in the situation that there is base material, the polymerization on this base material of the free radical of the compound in plasma body.Conventional polymkeric substance synthesizes to be easy to generate and contains with having the structure of the repeating unit of strong similarity with monomeric substance, but uses the extremely complexity of polymer network of plasma generation.The character of gained coating can be depending on the character of base material and the character of the monomer that uses and deposit its condition.Plasma polymerization is disclosed in International Patent Application WO 98/58117 with the surperficial method that produces water resistant and anti-oil.
invention statement
A first aspect of the present invention provides the method for generation with the polymer brush of the polymeric side chains of covalency bond, and it comprises the following steps:
(a) by halogen-containing initiator film or the precursor deposition that is derivatized to halogen-containing initiator film to base material;
(b) brush skeleton from the described halogen-containing initiator film surface ATRP growth forming in conjunction with the polymerization of side group step (a);
(c) be grown in the polymeric side chains on described polymerization brush skeleton from the described polymerization brush skeleton forming step (b), to form polymer brush, wherein said polymeric side chains forms the bristle of described brush.
In whole specification sheets, term " polymer " " comprise homopolymer and multipolymer.
In one embodiment, described polymer brush comprises polymkeric substance bottle brush, and it for example can be polymer nanocomposite bottle brush.
In one embodiment, the side group on described polymerization brush skeleton forming in step (b) comprises other initiation sites for polymer growth.
In one embodiment, in step (c), the growth of the polymeric side chains on described polymerization brush skeleton occurs via one or more derivative steps, and wherein pendant derivatizedization on described polymerization brush skeleton is to be formed for other initiation sites of polymer growth.
In one embodiment, described halogen-containing initiator film forms by polymerization, produces the halogen-containing initiator film of polymerization.
In one embodiment, described halogen-containing initiator film is by forming halogen-containing molecule aggregation.In one embodiment, described halogen-containing molecule is vinyl halogenation benzyl.In one embodiment, described vinyl halogenation benzyl is vinyl chlorination benzyl.
In one embodiment, the technology of chemical vapour deposition (iCVD), light deposition, ion assisted deposition, electron beam polymerization, gamma-radiation polymerization, target sputter and any combination thereof of the deposition of described halogen-containing initiator film or described precursor by being selected from plasma polymerization, thermal chemical vapor deposition, initiation is carried out.
In one embodiment, described halogen-containing initiator film passes through plasma polymerization deposition.In this embodiment, can use one or more in following condition:
A. pressure is 0.01 millibar of-1 bar, for example 0.01 or 0.1 millibar-1 millibar or 0.1-0.5 millibar, all 0.2 millibar according to appointment.
B. temperature be 0-300 ℃, for example 10 or 15-70 ℃ or 15-30 ℃, such as room temperature (it can be about 18-25 ℃, all 20 ℃ according to appointment).
C. power (or the in the situation that of pulsed plasma, peak power) is at least 0.1W or at least 1W or at least 5W or at least 10W or at least 20W; And/or 40W or at the most 50W or 60W or at the most 70W or 100W or at the most 500W at the most at the most at the most; Such as 0.1-500W, or 0.1-100W, or 5-70W or 5 or 10-50 or 60W, or 20-40W, all 30W according to appointment.
D. the in the situation that of pulsed plasma, it is 1 μ s-5ms that working cycle is connected the phase (on-period), for example 1-500 μ s or 1-200 μ s or 50-200 μ s, all 100 μ s according to appointment.
E. the in the situation that of pulsed plasma, it is 1 μ s-500ms that working cycle disconnects the phase (off-period), for example 1-250ms or 1-100ms or 1-10ms, all 4ms according to appointment.
F. the in the situation that of pulsed plasma, the working cycle phase of connecting is 1 x 10 with the ratio of the phase of disconnection
-5-1.0, or 0.001-0.1, for example 0.001-0.05, or 0.01-0.05, or 0.01-0.04, all according to appointment 0.025.
In one embodiment, described plasma polymerization is pulsed plasma polymerization.
In one embodiment, described plasma polymerization is continuous wave (CW) plasma polymerization.
In one embodiment, described plasma body contains one or more monomeric compounds that are applicable to forming described halogen-containing initiator film.In one embodiment, described plasma body contains the single monomer compound that is applicable to forming described halogen-containing initiator film.In an embodiment for the election, described plasma body contains the mixture that is applicable to the different monomers compound that forms described halogen-containing initiator film.
In one embodiment, described plasma body also contains inert carrier gas.In one embodiment, described inert carrier gas is helium or argon gas.
The deposition of described halogen-containing initiator film in step (a) on base material can comprise part or cover described base material completely.In one embodiment, in step (a), described halogen-containing initiator thin film deposition is in a part for described base material.In one embodiment, in step (a), described halogen-containing initiator film is deposited on described base material with pattern form.Described pattern for example can be by using mask to form as the template of described pattern.
In one embodiment, in step (b), be selected from vinylbenzene, acrylate, methacrylic ester and vinyl cyanide for the grow monomer of described polymerization brush skeleton of surfaces A TRP.In one embodiment, described monomer comprises glycidyl methacrylate.
In one embodiment, in step (c), the growth of the polymeric side chains on described polymerization brush skeleton occurs via controlled graft polymerization.
In one embodiment, in step (c), the ATRP that is grown to of the polymeric side chains on described polymerization brush skeleton grows.
In one embodiment, in step (c), the ATRP initiation site that pendant derivatizedization on described polymerization brush skeleton grown to be formed for the ATRP of described polymeric side chains.
In one embodiment, pendant derivatizedization on described polymerization brush skeleton is to form halo ATRP initiation site.
In one embodiment, the side group on described polymerization brush skeleton is by reacting and derivatize with bromoacetic acid.
In one embodiment, in step (c), be selected from vinylbenzene, acrylate, methacrylic ester and vinyl cyanide for the monomer of the described polymeric side chains of growing.In one embodiment, described monomer comprises Sodium styrene sulfonate.
The bristle of the polymer brush forming in step (c) in one embodiment, is formed by PSS side chain.
In one embodiment, the polymer brush forming in step (c) is polyelectrolyte brush.
In one embodiment, the base material in step (a) is selected from glass, metal, silicon, weaves or non woven fibre, natural fiber, synthon, pottery, semi-conductor, cellulose materials, paper, timber and the polymkeric substance such as tetrafluoroethylene, polyethylene or polystyrene.
A second aspect of the present invention provides the polymer brush forming by the method for first aspect.
In one embodiment, the step of described method (b) produces ATRP grafting layer on described base material, and described layer has the mean thickness that is less than 10 microns.
In one embodiment, described polymer brush forms by described method, wherein, in step (b), comprise that for the grow monomer of described polymerization brush skeleton of surfaces A TRP glycidyl methacrylate and described ATRP grafting layer are poly-(glycidyl methacrylate) layer.
A third aspect of the present invention provides the purposes as lubricant according to the polymer brush of second aspect.
In the present invention, the polymer brush that surface connects is by being grafted to macromole evocating agent polymerization brush skeleton ATRP on poly-(vinyl chlorination benzyl) initiator nano thin-film of plasma chemistry deposition, then having made described polymeric side chains (bristle) ATRP grow to prepare.The surface density of polymer brush can accurately customize by changing for the manufacture of the plasma chemistry deposition parameter of poly-(vinyl chlorination benzyl) initiator nano thin-film.The inspection of transverse force scanning probe microscope has shown that the surface that polymer brush is decorated causes that nano lubricating strengthens.
A fourth aspect of the present invention provides the method that produces the initiator film of growing for the ATRP subsequently of polymer brush, and described method comprises that the precursor that is deposited halogen-containing initiator film or be derivatized to halogen-containing initiator film by continuous wave plasma polymerization is to base material.
In the method for a first aspect of the present invention and fourth aspect, the polymerization of described halogen-containing initiator film through type M-X forms, and wherein M is that polymerisable group and X are halogen atom.
In one embodiment, described halogen-containing initiator film is by forming halogen-containing molecule aggregation.In one embodiment, described halogen-containing molecule is vinyl halogenation benzyl.In one embodiment, described vinyl halogenation benzyl is vinyl chlorination benzyl.
Plasma polymer typically produces by making coating formation precursor stand ionizing electric field under low pressure condition.Excite material polymerization and depositing react to form the polymeric film of growth during with substrate surface in gas phase when what the effect of precursor (free radical, ion, excite molecule etc.) is produced by electric field.
The plasma-deposited accurate condition occurring with effective means of the pulse of described initiator film or continuous wave will become and will determine by ordinary method and/or technology according to the factor such as size and structure of the character such as monomer, base material, plasma-deposited chamber.
The suitable plasma body using in method as herein described comprises nonequilibrium plasma, such as the plasma body producing by radio frequency (RF), microwave or galvanic current (DC).Known in the art, they can operate under barometric point or sub-atmospheric pressures.But specifically, they produce by radio frequency (RF).
Can produce gaseous plasma with various forms of equipment.In general, these equipment comprise container or the plasma chamber that can produce therein plasma body.The particular instance of this equipment is for example described in WO 2005/089961 and WO02/28548, but can utilize many other conventional plasma production devices.
In general, indoor to be placed on plasma chamber together with the material of gaseous state by the article of wish processing and wish deposition, the glow discharge apply suitable voltage of igniting in this chamber.
The gas using in this plasma body can only comprise the steam of monomeric compound, but it also can be with carrier gas, especially rare gas element as helium or argon gas combination.Specifically, helium is preferred carrier gas, because this can make the cracked of monomer reduce to minimum.
In the time using as mixture, the relative quantity of monomer vapor and carrier gas is determined suitably according to the program of commonly using in the art.The add-on of monomer will depend on the character of the specific monomer just using, just character, the size of plasma chamber etc. of the base material processed to a certain extent.In general, the in the situation that of conventional chamber, monomer is with the amount of 50-250mg/min, for example, with the speed transmission of 100-150mg/min.Such as the carrier gas of helium for example, with constant speed, give suitably with the speed of 5-90sccm, for example 15-30sccm.In certain situation, the ratio of monomer and carrier gas will be in 100:1 to 1:100 scope, for example, in 10:1 to 1:100 scope, and is especially about 1:1 to 1:10.Selected accurate ratio will guarantee to realize the flow velocity that described method needs.
In some cases, the plasma body (preliminary continuous power plasma) of preliminary continuous rating can hit (struck) for example 2-10 minute, all 4 minutes according to appointment in described chamber.This can serve as surface preparation step, guarantees that monomer itself easily is attached to surface, thereby along with polymerization occurs, coating " growth " from the teeth outwards.This pre-treatment step can be carried out before monomer is introduced to described chamber in the situation that only there is rare gas element.
Glow discharge is ignited suitably by applying for example high-frequency voltage under 13.56MHz.This uses electrode to apply suitably, and described electrode can be in the inside of described chamber or outside, but the in the situation that of larger chamber, it is in the inside of described chamber.
Described gas, steam or gaseous mixture are suitably with at least 1 standard cubic centimeters per minute (sccm) and the preferably speed supply of 1-100sccm.
The in the situation that of monomer vapor, according to the character of monomer, its suitably with 80-300mg/min, for example, with the speed supply of about 120mg/min, apply described voltage simultaneously.
Gas or steam can be sucked or is pumped in plasma body region.Specifically, in the situation that using plasma chamber, gas or steam can be inhaled in described chamber due to the pressure decreased being caused by use return pump in described chamber, or as conventional in liquid treatment, they can be pumped or be injected in described chamber.
Use the steam of initiator film precursor to carry out suitably polymerization, the steam of described initiator film precursor maintains under the pressure of 0.1-200mtorr, suitably under about 80-100mtorr.
Described applied field has following power (or the in the situation that of pulsed plasma, peak power): at least 0.1W or at least 1W or at least 5W or at least 10W or at least 20W suitably; And/or 40W or at the most 50W or 60W or at the most 70W or 100W or at the most 500W at the most at the most at the most; Such as 0.1-500W, or 0.1-100W, or 5-70W or 5 or 10-50 or 60W, or 20-40W, all 30W according to appointment.
According to the character of described precursor and the article just processed etc., described applies 30 seconds-90 minutes suitably, preferably 5-60 minute.
The plasma chamber using has the volume that is enough to hold multiple article suitably.
Specially suitable equipment and method according to the present invention for the manufacture of article are described in WO 2005/089961.
These conditions are particularly suitable in large chamber, for example plasma slab has the 500cm of being greater than therein
3, for example 0.5m
3or more, such as 0.5m
3-10m
3and about 1m suitably
3the chamber of volume in deposit the good uniform coating of quality.The layer forming in this way has good physical strength.
To select the size of described chamber to hold the special article of just processing.For example, conventionally cubic chamber can be applicable to various application, if but need, can construct long strip shape or rectangular chamber or in fact it is shape cylindrical or that any other is suitable.
Described chamber can be sealable container, and to allow batch process, or it can comprise that the entrance and exit of using for article, material or yarn is to allow it in continuous processing.Specifically, in a rear situation, in described chamber, produce the necessary pressure condition of plasma discharge and use high volumetric pump to maintain, as common in institute in the device of for example " whistling and leaking (whistling leak) " having.But, also can or approach under barometric point at barometric point and process some article, eliminate the needs for " whistle and leak ".
The method is applicable to various base materials.For example, described base material can be selected from glass, metal, silicon, weave or non woven fibre, natural fiber, synthon, pottery, semi-conductor, cellulose materials, paper, timber and the polymkeric substance such as tetrafluoroethylene, polyethylene or polystyrene.
The preferred feature of each side of the present invention can be as described in conjunction with any in other aspects.For example, the preferred feature of a second aspect of the present invention, the third aspect and fourth aspect can be as above described in conjunction with first aspect, and vice versa.
In the specification sheets and claims of present specification, word " comprises " and the variant of " containing " and these words referred to " including but not limited to " and do not get rid of other parts, additive, component, integer or step as " comprising (comprising) " and " comprising (comprises) ".
In the specification sheets and claims of present specification, unless the context requires otherwise, otherwise odd number is contained plural number.Specifically, in the situation that using indefinite article, unless the context requires otherwise, otherwise present specification will be understood to consider plural number and odd number.
Other features of the present invention will be apparent from following examples.In general, the present invention extends to the combination of the feature of in present specification (comprising any claim of enclosing and accompanying drawing) any one novel feature in disclosed feature or any novelty.Therefore, feature, integer, characteristic, compound, chemical part or the group of describing in conjunction with particular aspects of the present invention, embodiment or embodiment will be regarded as being applicable to any other aspect as herein described, embodiment or embodiment, unless incompatible with it.
In addition, except as otherwise noted, otherwise disclosed any feature all can select feature to substitute by the confession that identical or similar applications are provided in this article.
In present specification, except as otherwise noted, the compound property of mentioning refers under envrionment conditions, the character of measuring under barometric point and for example, at the temperature of 16-22 ℃ or 25 ℃ or 18-22 ℃ or 25 ℃, approximately 20 ℃ or approximately 25 ℃.
To only by embodiment and with reference to the illustrative embodiments of enclosing, the present invention be described now, wherein:
Fig. 1 represents the infrared spectra of following thing: (a) vinyl chlorination benzyl monomer; (b) poly-(vinyl chlorination benzyl) film of pulsed plasma deposition; (c) plasma-deposited poly-(vinyl chlorination benzyl) film of continuous wave;
Fig. 2 represents the infrared spectra of following thing: (a) glycidyl methacrylate monomer; (b) from poly-(glycidyl methacrylate) of the ATRP grafting of poly-(vinyl chlorination benzyl) initiator film growth of pulsed plasma deposition; (c) (b) after being exposed to bromoacetic acid at 75 ℃ 4 hours;
Fig. 3 represents as the variation of poly-(glycidyl methacrylate) film thickness of function that is grafted to the ATRP grafting time on poly-(vinyl chlorination benzyl) initiator film of pulsed plasma deposition;
Fig. 4 represents as the PSS film thickness of function that is grafted to the ATRP grafting time on poly-(vinyl chlorination benzyl) initiator film of pulsed plasma deposition;
Fig. 5 represents the infrared spectra of following thing: (a) poly-(vinyl chlorination benzyl) ATRP initiator film of pulsed plasma deposition; (b) be grafted to the PSS of the ATRP grafting on poly-(vinyl chlorination benzyl) initiator film of pulsed plasma deposition; (c) Sodium styrene sulfonate monomer;
Fig. 6 represents to be grafted on plasma-deposited poly-(vinyl chlorination benzyl) the ATRP initiator film of continuous wave, then to be used bromoacetic acid derivatize to produce the infrared spectra that gathers (glycidyl methacrylate) brush of macromole evocating agent layer by ATRP.These are subsequently for the ATRP grafting of Sodium styrene sulfonate side chain (bristle): (a) 0 minute; (b) 30 minutes; (c) 60 minutes;
Fig. 7 represents the variation as the polymer film thickness of the function of PSS ATRP grafting time for the macromole evocating agent layer generating by the bromoacetic acid derivatize that gathers (glycidyl methacrylate) brush that is grafted to plasma-deposited poly-(the vinyl chlorination benzyl) film of continuous wave;
Fig. 8 represents the friction signal of the function of the normal load of conduct obtaining by transverse force microscopy for following thing: poly-(vinyl chlorination benzyl) film that continuous wave is plasma-deposited; Poly-(glycidyl methacrylate) of the ATRP grafting on poly-(vinyl chlorination benzyl) layer of pulsed plasma deposition; The PSS brush of the ATRP grafting on poly-(vinyl chlorination benzyl) layer of pulsed plasma deposition; Poly-(glycidyl methacrylate)-grafting-PSS bottle brush with the ATRP grafting on plasma-deposited poly-(the vinyl chlorination benzyl) layer of continuous wave; And
Fig. 9 is the schema of the key step of explanation in the formation of polymer brush of the present invention.
Embodiment
In the present invention, the controlled ATRP surface grafting of poly-(glycidyl methacrylate) brush layer uses plasma-deposited poly-(vinyl chlorination benzyl) nano thin-film to realize.As illustrated in Fig. 9, these use bromoacetic acid derivatize to introduce the needed ATRP initiation site of the grafting of ATRP subsequently of PSS side chain (bristle) along polymer brush skeleton subsequently.Fig. 9 is the schema that represents key step of the present invention, described key step comprises by ATRP grafting poly-(glycidyl methacrylate) and brushing on plasma-deposited poly-(vinyl chlorination benzyl) initiator film, then gathers (glycidyl methacrylate) to be formed for the connection macromole priming site of ATRP subsequently of PSS side chain " bristle " with bromoacetic acid esterification.
aTRP initiator film plasma-deposited
Be positioned at Faraday's cage (Faraday cage) and using 30L min
-1through liquid nitrogen cold trap, (pressure of foundation is less than 2 x 10 to rotor pump
-3millibar and leakrate are greater than 6 x 10
-9cylindrical glass reactor (the diameter: 5.5cm of mol/s) finding time; Volume: 475cm
3) in carry out plasma-deposited.The copper coil (diameter: 4mm, 10 circles are positioned at apart from 10cm place, gas inlet) that is wound around this reactor is connected to 13.56MHz radio frequency (RF) power supply through L-C matching network.Trigger this RF power supply with signal generator.Before thin film deposition, whole equipment uses washing composition and hot water fully to scrub, with propan-2-ol rinsing oven dry.Base material preparation (glass cover slide or silicon chip parts) is included in continuous ultrasound in propan-2-ol and hexanaphthene and processes 15 minutes, the center of inserting afterwards chamber.Before thin film deposition, further clean requirement operates 50W continuous wave air plasma 30 minutes under 0.2 millibar.Vinyl chlorination benzyl (+99.9%, Aldrich) precursor is loaded in sealable Glass tubing, through multiple freezing-pump-(freeze-pump-thaw) circulating degasification that thaws, and be connected to subsequently this reactor.Before electric discharge is ignited, allow subsequently monomer vapor under the pressure of 0.2 millibar, purge this equipment and last 3 minutes.The working cycle that pulsed plasma deposition uses the working cycle of 100 μ s to connect phase and 4ms disconnects the peak power of phase and 30W and carries out.Continuous wave is plasma-deposited to carry out under 30W.After plasma disappearance, make this precursor vapor continue across again this system 3 minutes, and subsequently this chamber is evacuated to pressure of foundation.
bottle brush is synthetic
For poly-(glycidyl methacrylate) grafting, plasma-deposited poly-(vinyl chlorination benzyl) functionalized base material of initiator is placed on and contains 5mmol cupric bromide (I) (+99.9%, Aldrich), 1mmol cupric bromide (II) (+99.9%, Aldrich), 12mmol 2,2 '-dipyridyl (+99.9%, Aldrich), 0.05 mol glycidyl methacrylate (+99.9%, and 4mL N Aldrich), dinethylformamide (+99.9%, Fisher) in salable Glass tubing, Fig. 9.This mixture uses freezing-pump-thaw cycles fully degassed and immerse in the oil bath maintaining at 80 ℃ and last certain grafting time (1.0-3.5 hour) subsequently.The final clean and removal of the polymkeric substance of any physical adsorption is used hot toluene to last realization in 16 hours by Soxhlet extractron (Soxhlet extraction).
Brominated macromole evocating agent film uses poly-(glycidyl methacrylate) brush of the ATRP grafting that the glass reactor in the baking oven that is placed on controlled temperature connects by surface via producing with the esterification of bromoacetic acid (+99.9%, Aldrich) steam.Bromoacetic acid is loaded in sealable Glass tubing, through multiple freezing-pump-thaw cycles is degassed and be connected to subsequently this reactor.By this system pump down to 4 x 10
-3millibar and be heated to 75 ℃.Then, bromoacetic acid purge vapor is lasted to 5 minutes, and subsequently reaction chamber and pump are separated to 4 hours and react allowing, follow cool to room temperature be evacuated to pressure of foundation.In order to ensure removing any unreacted bromoacetic acid completely, by base material fully rinsing in high-purity water and DMF (+99.9%, Fisher).
The ATRP grafting of PSS is carried out under aqueous conditions due to the limited solubility of monomer.The copper (II) that needs are higher: copper (I) compares to strengthen halogenide closed-end efficiency, and maintains thus control.From be dissolved in the 1.0g Sodium styrene sulfonate (+99.9%, Aldrich) 3mL high-purity water, remove the gas of any trapping by using minimum four freezing-pump-thaw cycles.Catalyst system is by 0.05mmol cupric bromide (I), 0.04mmol cupric bromide (II) and 0.18mmol 2, and 2 '-dipyridyl forms; These materials are added in this solution, simultaneously that it is freezing together with plasma-deposited poly-(vinyl chlorination benzyl) functionalized base material of initiator.Subsequently reaction vessel is immersed in the oil bath that is set to 50 ℃ and lasts the predetermined grafting time.Subsequently by this base material in high-purity water fully rinsing to remove the polymkeric substance of any physical adsorption and to be allowed to condition at air drying.For the PSS of grafting, charging mark (charge fraction) is 100%.
film characterization
Film thickness uses spectrophotometer (nkd-6000, Aquila Instruments Ltd.) to measure.Obtain transmissivity-reflectance curve (wavelength region 350-1000nm) and use the uncommon material model (Cauchy material model) of the improved Levenberg-Marquardt algorithm section of fitting to for each sample.
Surface-element composition is used and is equipped with polyenergetic Mg K α 1,2 X-ray source (1253.6eV) and the VG ESCALAB II electron spectrometer acquisition of semisphere analyzer with one heart by the sub-spectrography of X-ray photoelectric (XPS).Photoemissive electronics is located to collect with constant analyzer energy model (CAE, logical energy=20eV) by detected electronically in the fleet angle from 30 ° of base material normals (take-off angle).Testing definite instrumental sensitivity factor is taken as: C (1s): O (1s): Cl (2p): Br (3d): S (2p): Na (1s) equals 1.00:0.46:0.29:0.29:0.52:0.05.
Use is equipped with at 700-4000cm
-1scope is with 4cm
-1the FTIR spectrograph (Perkin-Elmer Spectrum One) of the MCT detector of the cooled with liquid nitrogen of resolution operation obtains infrared spectra.This instrument comprises for silicon wafer substrate and is set to the grazing angle of 66 ° and the variable-angle reflection-absorption appendix (Specac) for p-polarization modulation.
nano friction
Transverse force microscopy uses Nanoscope IV (Digital Instruments, Santa Barbara, CA) and the fluid chamber of containing high-purity water (3,978 1 grades of BS) and uses trilateral Si with contact mode
3n
4contact mode SPM probe tip (spring constant 0.24N m
-1, Bruker Nano Inc.) carry out.In order to ensure consistent result, use identical probe for all measurements.Nominal load uses the nominal force constant and the power-distance Curve that are provided by manufacturer calculate and change by means of contact mode setting point.Friction dates uses the sweep angle of 90 ° and the sweep rate of 3Hz to collect on 1 μ m x 1 μ m region.(dynamically) Friction dates that slides measures and is reported as the half (therefore getting rid of any scanning needle point (scanning tip) bilateral scanning commutation contribution that is attributable to stiction) of the difference of center 800nm region bilateral scanning (the trace and retrace) signal for each sweep trace with volt.These data are directly proportional to frictional force, and due to the dependency of selecting the method for measuring crossed strip constant is not changed into absolute friction force value.The method that is used in mensuration crossed strip constant is completely reliable, the frictional coefficient measuring system that still very dependence adopts and related various parameters (scanning speed, contact area, antagonism surface etc.).Therefore, for the object of this research, tribology experiments is by utilizing internal reference thing, and poly-(NaStS) brush that is connected to the ATRP-grafting of poly-(VBC) layer of pulsed plasma deposition carries out.The scanning speed of the 3Hz of AFM produces 6 μ m s
-1needle point translational speed.Each reading is taken as the mean value of 128 sweep traces.Use identical needle point for each group of comparative rub measurement, and for three different samples of all types of surface analyses.All scan-probe rub measurements repeat for several times and do not express variation (being included under higher nominal load).This shows the improvement of needlepoint form without any significance degree.
result
gather the plasma-deposited of (vinyl chlorination benzyl) ATRP initiator film
The XPS analysis of poly-(vinyl chlorination benzyl) film of pulsed plasma deposition provides elementary composition corresponding to the expected theoretical value based on vinyl chlorination benzyl monomer, therefore shows that the satisfactory texture of Benzyl Chloride functional group keeps, table 1.In addition, do not exist any Si (2p) XPS signal to confirm that the free of pinholes of silicon wafer substrate below covers.The further evidence of the structural integrity of poly-(vinyl chlorination benzyl) film of pulsed plasma deposition obtains by Infrared spectroscopy, those features that wherein fingerprint feature close match is measured for this monomer, Fig. 1.These are included in 1263cm
-1(CH
2the CH of-Cl
2sway mode) under halide functional group (ATRP cause required) subsequently and at 1495cm
-1and 1603cm
-1under flexible to substituted benzene ring.In addition, observe at 1629cm
-1under the flexible loss of vinyl double bond consistent with polymerization.In the case of plasma-deposited poly-(the vinyl chlorination benzyl) film of continuous wave, by the lower slightly cl content that detected by XPS and much weak that infrared absorbency obviously demonstrates structure deteriorate greatly, table 1 and Fig. 1 for characteristic Benzyl Chloride functional group.
Table 1: plasma-deposited poly-(vinyl chlorination benzyl) film and the polymer brush of ATRP grafting and the XPS of bottle brush are elementary composition.
the ATRP grafting of glycidyl methacrylate and Sodium styrene sulfonate
On self-structure poly-(glycidyl methacrylate) brush of the ATRP grafting of poly-(vinyl chlorination benzyl) ATRP initiator film growth of the pulsed plasma deposition of sharp outline produce with for gather that (glycidyl methacrylate) calculate elementary composition to approach consistent XPS elementary composition, table 1 and Fig. 9.Do not exist from Cl (2p) the XPS signal of initiator film below and confirm to be aggregated the covering completely of thing brush.Both characteristic infrared absorbency of measurement of poly-(glycidyl methacrylate) layer for glycidyl methacrylate monomer and ATRP grafting are included in 1726cm
-1(for this monomer, owing to being combined with vinyl, 1714cm
-1) under ester C=O flexible and at 1152cm
-1under C-O flexible, Fig. 2.At 1637cm
-1(C=C is flexible) and 941cm
-1(vinyl CH
2wave) loss that absorbs of the monomer vinyl located provides the further proof that ATRP occurs.The linearity that the controlled character of the ATRP that cause on surface is gathered (glycidyl methacrylate) the film thickness relative grafting time by monitoring increases, produces 76 ± 6nm hr
-1sedimentation rate confirm, Fig. 3.Poly-(vinyl chlorination benzyl) film thickness of finding ATRP film growth rate and pulsed plasma deposition is irrelevant, confirms that thus ATRP initiation must constrain in plasma polymer surface.In addition, in the situation that other conditions are all identical, omit catalytic copper material from this reaction mixture and cause not detecting poly-(glycidyl methacrylate) grafting after 4 hours, therefore eliminated the autopolymerization possibility of explaining for choosing as reported observe phenomena.
Discovery be grafted to the elementary composition and characteristic infrared absorbency of the XPS of poly-(glycidyl methacrylate) of the ATRP grafting of plasma-deposited poly-(the vinyl chlorination benzyl) film of continuous wave with for corresponding pulses plasma-deposited to gather those of (vinyl chlorination benzyl) ATRP initiator measured thin film consistent, table 1.But polymer brush film thickness is respectively 26 ± nm and 137 ± 5nm after ATRP grafting in 2 hours, and consistent with the bad structural integrity of the plasma-deposited layer of the plasma-deposited layer of continuous wave relative pulse.
Similarly, the XPS analysis of the PSS of the ATRP grafting of growing on poly-(vinyl chlorination benzyl) the initiator film of pulsed plasma produce with the theoretical value of calculating approach consistent elementary composition, table 1.Do not exist Cl (2p) signal list Benq material to be completely covered.The amount of finding measured sodium gegenion is more much lower and be attributable to the protonated formation acid of sulfonate ester group than the amount of sulphur.ATRP grafted polymer brushes thickness relative time shows 31 ± 2nm hr
-1linear growth rate, Fig. 4.The grafting time that exceedes 90 minutes arrives summit out of control, and this is attributable to the oxygenolysis of catalytic specie (for some common materials of water ATRP).The infrared spectra of the PSS layer of ATRP grafting has disclosed the fingerprint feature of those the fingerprint feature couplings relevant to monomer, Fig. 5.These are included in 1140cm
-1, 1188cm
-1and 1234cm
-1(unsymmetrically SO
2flexible) and 1058cm
-1(symmetrical SO
2flexible) under absorbancy.At 1638cm
-1lower monomer vinyl C=C disappears after stretching and being absorbed in ATRP polymerization.
bottle brush is manufactured
Poly-(glycidyl methacrylate) brush of poly-(vinyl chlorination benzyl) layer grafting from plasma-deposited is exposed to bromoacetic acid to introduce ATRP macromole priming site, Fig. 9 along poly-(glycidyl methacrylate) brush skeleton.Mixing by XPS ultimate analysis of bromine confirms, table 1.Other evidences that react that dangle between epoxide group and bromoacetic acid in poly-(glycidyl methacrylate) are found by infrared spectroscopy, Fig. 2.At 1254cm
-1(oxirane ring breathing), 906cm
-1(unsymmetrically annular strain) and 841cm
-1(symmetrical ring distortion) locates to roll into a ball to epoxide functional that relevant absorbancy all decays and at 1245cm
-1under owing at CH
2cH on-Br
2other absorbancys of waving are obvious.In addition, at 1726cm
-1the flexible multiple ester environment that absorb broadening confirmation existence expection in gained macromole evocating agent film of lower ester C=O.
For the sufficient space of side chain " bristle " growth is provided, best macromole evocating agent grafting density is realized by causing the ATRP of poly-(glycidyl methacrylate) and subsequently polymer brush is exposed to bromoacetic acid from continuous wave plasma-deposited poly-(vinyl chlorination benzyl).PSS side chain confirms by infrared spectroscopy from these macromole evocating agent layers ATRP grafting, Fig. 6 and Fig. 9.With at 1058cm
-1under symmetrical SO
2flexible comparing, from brush skeleton at 1726cm
-1under the flexible relative intensity of ester carbonyl group along with the PSS grafting time increases and reduces, this shows the growth of PSS bristle.Confirmation in addition obtains by the increase of the ATRP grafting time of the relative PSS side chain of monitoring film thickness, Fig. 7.In order to prove that PSS side chain occurs from the ATRP grafting of poly-(glycidyl methacrylate) brush of derivatize, make poly-(glycidyl methacrylate) brush and the acetic acid vapor reaction (identical derivative chemistry, but shortage halogen initiator atom) that replaces bromoacetic acid of corresponding ATRP grafting.The ATRP condition that is exposed to subsequently Sodium styrene sulfonate continues 120 minutes, result film thickness does not have measurable increase, and the reactivate of therefore having eliminated poly-(glycidyl methacrylate) end of the chain will cause the choosing that supplies that forms segmented copolymer to explain and illustrated the reason of the variation of observing in film thickness and infrared spectra.
Other control experiment comprises that poly-(glycidyl methacrylate) that derived by bromoacetic acid brushed to the macromole evocating agent forming is grafted to gathering on (vinyl chlorination benzyl) initiator film of pulsed plasma deposition, and produce the identical bromine content obtaining by XPS analysis, table 1.But, in the time comparing with the macromole evocating agent based on plasma-deposited poly-(the vinyl chlorination benzyl) nano thin-film of continuous wave, make PSS ATRP grafting within 120 minutes, cause film thickness to increase the sulphur of decay (5nm is to 24nm) and lower amount, table 1.
nano friction
Friction between slip SPM probe tip and polymkeric substance brush layer is measured as the function of nominal load in aqueous environments, Fig. 8.Record Friction dates and height image simultaneously, and select uniform 1 μ m x 1 μ m region (r.m.s. roughness < 2nm) for data gathering.Plasma-deposited poly-(vinyl chlorination benzyl) layer shows around the friction of 130nN nominal load and increases sharply, and this represents polymer chain replacement (displacement) and wearing and tearing.In addition, compare with poly-(glycidyl methacrylate) and PSS brush layer (from pulsed plasma deposition gather (vinyl chlorination benzyl) initiator film grafting), described bottle brush layer constantly provides lower friction reading.This enhancing is attributable to space repulsion and the water solvent of bottle brush, causes permeability resistance (and improving thus lubricated).These tribology experiments design to utilize internal reference thing in this way, i.e. poly-(NaStS) brush of ATRP grafting on poly-(VBC) layer of pulsed plasma deposition.Even owing to being derived from Atmospheric CO
2being dissolved in pure water medium makes pH reduce the less contribution of the electronegative coulombic repulsion existence of generation, for poly-(NaStS) brush of surfaces A TRP grafting and poly-(the GMA)-grafting of surfaces A TRP grafting-poly-(NaStS) bottle brush, also will expect this factor of existence.By considering this possibility, tribology meter is shown in grafting-poly-(NaStS) bristle comprising in bottle brush and shows the low frictional force of poly-(NaStS) brush counterpart than its linear surface grafting.
In the situation that polymer phase slides to solid surface, proposed frictional force with the variation of shearing rate owing to the transformation from coil to flexible conformation, and therefore expect and need Frictional force gauge to reveal the low dependency to shearing rate for the polymkeric substance brush layer (existing with the conformation of stretching under good solvent condition) of fine and close grafting.Measure the surface force balance test of force of sliding friction between polymkeric substance brush layer and only find weak speed dependence, and be also this situation for the scan-probe friction research of the fixing polyelectrolyte in the polyelectrolyte of relatively physical adsorption and surface.Therefore, consider that bottle brush of the present invention is covalently bound to base material, can expect that frictional force is because any variation that shearing rate causes is all relatively little.
discuss
Poly-(the vinyl chlorination benzyl) that previously shown pulsed plasma deposition is the effective ATRP initiator of non-normal manner.This is attributable to stable benzyl, and this benzyl allows to extract chlorine to easily there is (because benzyl is stablized by aromatic ring) between ATRP induction period from Benzyl Chloride surface functional group.Therefore, the effective surface density of the structural integrity control ATRP initiation site of Benzyl Chloride group in the film of plasma deposition.This is obvious for crowded poly-(glycidyl methacrylate) and the PSS brush layer of densification being generated by poly-(vinyl chlorination benzyl) film of the pulsed plasma deposition of sharp outline in structure by ATRP.These are grown in a controlled manner, and wherein polymer brush thickness is linear increases, and the crowded driving chain in space adopts the conformation of extending, Fig. 3 and Fig. 4.For the surface density of polymer brush that reduces grafting is to be provided for the space of side chain (bristle) growth, by infrared and XPS analysis show plasma-deposited poly-(the vinyl chlorination benzyl) film of continuous wave because poor structural integrity contains more low-density complete Benzyl Chloride initiator group.Between continuous wave plasma-deposited poly-(vinyl chlorination benzyl) and poly-(the vinyl chlorination benzyl) of pulsed plasma deposition, this density variation of Benzyl Chloride initiation site can be explained based on they corresponding film growth mechanism.During pulsed plasma deposition, electric discharge modulation comprises that short plasma body working cycle connects the phase (microsecond) to produce avtive spot via VUV irradiation, ion and electronics bombardment in gas phase and on growing film surface, be then in the case of do not exist to any UV, ion or the electronics of growing film bring out the prolongation pulse of following at each damage disconnect the phase (millisecond) in the conventional carbon-to-carbon double bond polymerization process of generation.The conventional polymerization of this class path is strongly disturbed under continuous wave condition of plasma, and wherein in electric discharge, contained group, ion and the multiple reaction that excites material are played larger effect causing aspect structure deteriorate.In addition, compared with pulsed plasma deposition (0.7W), the mean power that is fed to vinyl chlorination benzyl precursor vapor during continuous wave plasma discharge (30W) is significantly larger.
Therefore, compared with using prepared by pulse plasma concrete conditions in the establishment of a specific crime those, significantly lower for the thickness of poly-(glycidyl methacrylate) layer of the ATRP grafting of poly-(vinyl chlorination benzyl) measured thin film of continuous wave deposition.Consider identical ATRP condition, can think that poly-(glycidyl methacrylate) brush length between the initiator nano thin-film of pulsed plasma deposition and the plasma-deposited initiator nano thin-film of continuous wave of grafting is suitable, therefore the avalanche conformation that lower film thickness is attributable to gather (glycidyl methacrylate) chain in a rear situation, this comes from lower surperficial initiation site density.
Poly-(glycidyl methacrylate) brush that above-mentioned surface connects is exposed to the fixing macromole evocating agent material in surface of bromoacetic acid generation sharp outline subsequently.The method is followed the conduct of previous report and is brushed and synthesize for the solution phase macromole evocating agent of the precursor of bottle brush, the esterification of the hydroxyl that dangles based on poly-(hydroxyethyl methylacrylate) skeleton polymer.In the present invention research, the epoxy-functional comprising in poly-(glycidyl methacrylate) brush is for provide larger reaction handling with the esterification of bromoacetic acid steam, Fig. 9, table 1 and Fig. 2.This overall ATRP method is the key (by contrast, lack the control relevant to conventional polymerization starter and cause indefinite macromole evocating agent brush and side chain) that forms the macromole evocating agent brush of sharp outline and synthesize subsequently bottle brush bristle.
The sign of surperficial fixing bottle brush polymkeric substance is challenging.Method is to analyze the polymkeric substance forming in solution and the sample obtaining via introducing sacrifice property initiator material, but it is as crowded in space that this fails to illustrate the exclusive problem of surface connection.In the present invention's research, the sulfonate ester group of PSS side chain (bristle) provides strong characteristic infrared absorbency, and it increases with film thickness, Fig. 6 and Fig. 7.Confirm that when lack these two trend (with the esterification of acetic acid replacement bromoacetic acid, Fig. 9) in the time that poly-(glycidyl methacrylate) brush skeleton does not exist initiator bromo PSS chain (bristle) only just forms in the time there is initiation site along polymer brush.
Consider intrinsic control is provided aspect macromolecular conformation, the bottle brush polymkeric substance of the sharp outline that the surface of preparing by ATRP connects has tempting prospect for the new surface properties of research and development as oilness, especially nano lubricating.The customization of skeleton and bristle segment can be used " from main chain grafting " method to realize; In addition, the surface density of skeleton grafting also can be used the plasma chemistry deposition of initiation site to control independently to allow predetermined side chain (bristle) growth.
Compare with neutral hydrophilic brush, polyelectrolyte brush shows high osmotic pressure (charge repulsion) in aqueous environments, and this has strengthened their oilness.Also report that surface grafting polyelectrolyte brush shows this class behavior.In the present invention's research, find that the bottle brush of the surface connection of studying is compared and shown even lower frictional force with their composition linear polymer brush counterpart.This characteristic is attributable to that the former is compacter (and for hydration), described in the early report in and low asymmetric rub measurement result that for polyelectrolyte brush observe lubricated to the similar wetting ability bottle brush enhancing by polymer on base material about physical adsorption.PSS brush and being dried of bottle brush layer for scan-probe rub measurement highly all keep identical (50nm, Fig. 8).XPS analysis shows, sulfur content in the surface of PSS bottle brush is less than the sulfur content of brush layer (is respectively 3 ± 1 and 7 ± 1%, table 1), this shows lower gegenion density, the viewpoint that the negative friction reducing increases owing to the number of gegenion in per unit area thus.Therefore the friction, reducing is relevant with molecular geometry (linear vs bottle brush).Can expect and increase macromole rigidity from polymer backbone graft side chain to form bottle brush structure.
The key advantage of the inventive method relates to and bottle brush is independent of to base material covalency is anchored to surface, and it provides than the counterpart of they physical adsorptions scope of suitability more widely.The potential application of the bottle brush that this class surface connects can comprise actuator, sensor, nanostructure tectonic element, generate the template of metal nanometer line and there is the simulation biomolecules (being connected Saliva Orthana with epithelium such as protein-polysaccharide) of the bottle brush structure for carrying out Biolubrication.
conclusion
The initiator film that the polymkeric substance bottle brush that surface connects is deposited by plasma chemistry by ATRP generates.The variation of plasma-deposited parameter makes it possible to customize the surface density of ATRP initiation site, and this allows to control the spacing of macromole evocating agent then, thereby allows growing polymer brush side chain (bristle).Transverse force scanning probe microscopy has shown to gather (glycidyl methacrylate)-grafting-PSS bottle brush-combination with decorative surfaces and has caused lubricated enhancing.
Claims (15)
1. generation is with the method for the polymer brush of the polymeric side chains of covalency bond, and it comprises the following steps:
(a) by halogen-containing initiator film or the precursor deposition that is derivatized to halogen-containing initiator film to base material;
(b) brush skeleton from the described halogen-containing initiator film surface ATRP growth forming in conjunction with the polymerization of side group step (a);
(c) be grown in the polymeric side chains on described polymerization brush skeleton from the described polymerization brush skeleton forming step (b), to form polymer brush, wherein said polymeric side chains forms the bristle of described brush.
2. the process of claim 1 wherein, the side group on the described polymerization brush skeleton forming in step (b) comprises other initiation sites for polymer growth.
3. the method for claim 1 or 2, wherein, in step (c), the growth of the polymeric side chains on described polymerization brush skeleton occurs via one or more derivative steps, and wherein pendant derivatizedization on described polymerization brush skeleton is to be formed for other initiation sites of polymer growth.
4. the method for any one in aforementioned claim, wherein said halogen-containing initiator film passes through such as vinyl halogenation benzyl as the polymerization formation of the halogen-containing molecule of vinyl chlorination benzyl.
5. the method for any one in aforementioned claim, the technology of chemical vapour deposition (iCVD), light deposition, ion assisted deposition, electron beam polymerization, gamma-radiation polymerization, target sputter and any combination thereof of the deposition of wherein said halogen-containing initiator film or described precursor by being selected from plasma polymerization, thermal chemical vapor deposition, initiation is carried out.
6. the method for claim 5, wherein said halogen-containing initiator film passes through plasma polymerization deposition.
7. the method for any one in aforementioned claim, wherein, in step (b), is selected from vinylbenzene, acrylate, methacrylic ester and vinyl cyanide for the grow monomer of described polymerization brush skeleton of surfaces A TRP.
8. the method for claim 7, wherein said monomer comprises glycidyl methacrylate.
9. the method for any one in aforementioned claim, wherein, in step (c), the ATRP that is grown to of the polymeric side chains on described polymerization brush skeleton grows.
10. the method for claim 3 or its any dependent claims, wherein, in step (c), the ATRP initiation site that pendant derivatizedization on described polymerization brush skeleton grown to be formed for the ATRP of described polymeric side chains.
The method of 11. claims 10, wherein the side group on described polymerization brush skeleton is for example by reacting derivatize to form halo ATRP initiation site with bromoacetic acid.
The method of any one in 12. aforementioned claims, wherein, in step (c), is selected from vinylbenzene, acrylate, methacrylic ester and vinyl cyanide for the monomer of the described polymeric side chains of growing.
The method of 13. claims 12, wherein said monomer comprises Sodium styrene sulfonate.
The polymer brush that 14. methods by any one in claim 1-13 form.
The polymer brush of 15. claims 14 is as the purposes of lubricant.
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| GB1112369.2 | 2011-07-19 | ||
| PCT/GB2012/051721 WO2013011314A1 (en) | 2011-07-19 | 2012-07-19 | Polymeric structure |
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| CN (1) | CN103906776A (en) |
| GB (2) | GB201112369D0 (en) |
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| CN107376867A (en) * | 2017-06-28 | 2017-11-24 | 西北大学 | A kind of molecule bottle brush type reverse phase absorption agent and preparation method and application |
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| EP2999738B1 (en) | 2013-05-22 | 2019-02-20 | Triblue Corporation | Methods of forming a polymer layer on a polymer surface |
| US10294359B2 (en) | 2014-12-30 | 2019-05-21 | Rohm And Haas Electronic Materials Llc | Copolymer formulation for directed self assembly, methods of manufacture thereof and articles comprising the same |
| US10011713B2 (en) | 2014-12-30 | 2018-07-03 | Dow Global Technologies Llc | Copolymer formulation for directed self assembly, methods of manufacture thereof and articles comprising the same |
| US11021630B2 (en) | 2014-12-30 | 2021-06-01 | Rohm And Haas Electronic Materials Llc | Copolymer formulation for directed self assembly, methods of manufacture thereof and articles comprising the same |
| TWI627219B (en) | 2015-02-26 | 2018-06-21 | 羅門哈斯電子材料有限公司 | Copolymer formulation for directed self-assembly, methods of manufacture thereof and articles comprising the same |
| TWI612379B (en) | 2015-02-26 | 2018-01-21 | Rohm And Haas Electronic Materials Llc | Copolymer formulation for directed self-assembly, methods of manufacture thereof and articles comprising the same |
| TWI588200B (en) | 2015-02-26 | 2017-06-21 | 羅門哈斯電子材料有限公司 | Copolymer formulation for directed self-assembly, methods of manufacture thereof and articles comprising the same |
| TWI669337B (en) | 2015-02-26 | 2019-08-21 | 美商羅門哈斯電子材料有限公司 | Copolymer formulation for directed self-assembly, methods of manufacture thereof and articles comprising the same |
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| PT988412E (en) | 1997-06-14 | 2006-05-31 | Secr Defence | SURFACE COATINGS |
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2011
- 2011-07-19 GB GB201112369A patent/GB201112369D0/en not_active Ceased
-
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- 2012-07-19 GB GB201212794A patent/GB2493095B/en not_active Expired - Fee Related
- 2012-07-19 WO PCT/GB2012/051721 patent/WO2013011314A1/en active Application Filing
- 2012-07-19 TW TW101126142A patent/TW201313751A/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1320062A (en) * | 1998-07-24 | 2001-10-31 | 英国国防部 | Surface coatings |
| WO2006097719A1 (en) * | 2005-03-16 | 2006-09-21 | University Of Durham | A method for producing a grafted polymer coating and substrates formed in accordance with the method |
| WO2007021180A1 (en) * | 2005-08-16 | 2007-02-22 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Method of modifying materials surfaces |
| CN102015850A (en) * | 2008-04-25 | 2011-04-13 | 巴斯夫欧洲公司 | Modified halogenated polymer surfaces |
| CN101497252A (en) * | 2009-03-06 | 2009-08-05 | 华东理工大学 | Polymer brush structure of polymer-based composite material interface as well as method and application for building the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107376867A (en) * | 2017-06-28 | 2017-11-24 | 西北大学 | A kind of molecule bottle brush type reverse phase absorption agent and preparation method and application |
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| Publication number | Publication date |
|---|---|
| GB2493095B (en) | 2014-03-19 |
| EP2734559A1 (en) | 2014-05-28 |
| GB201112369D0 (en) | 2011-08-31 |
| WO2013011314A1 (en) | 2013-01-24 |
| TW201313751A (en) | 2013-04-01 |
| GB201212794D0 (en) | 2012-09-05 |
| GB2493095A (en) | 2013-01-23 |
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