CN104628897B - Styrene type poly chain transfer agent, its preparation method and the application in preparing process for preparing column type polymer brush thereof - Google Patents
Styrene type poly chain transfer agent, its preparation method and the application in preparing process for preparing column type polymer brush thereof Download PDFInfo
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Abstract
The invention discloses a kind of styrene type poly chain transfer agent, its preparation method and the application in preparing process for preparing column type polymer brush, this styrene type poly chain transfer agent, for structure polymer as shown in formula (I), wherein, n is 10～20000, m is 1～20000, and molecular weight distribution is 1.01～4.0, and R is alkyl or phenyl；R ' is alkyl, phenyl, alkoxyl, alkylthio group, phenoxy group or thiophenyl.Its preparation method, with controlled the gathering vinyl benzyl ester as precursor of molecular weight, prepares polystyrene backbone poly chain transfer agent through post-functional reactions such as hydrolysis, chloro, replacements.Poly chain transfer agent used in the present invention, the degree of polymerization, up to 20000, can be used for regulating and controlling multiclass and prepares process for preparing column type polymer brush containing double bond monomer by R end growth pattern polymerization.
Description
Technical field
The invention belongs to polymer brush preparation field, be specifically related to a kind of styrene type poly chain transfer agent, its preparation method
And the application in synthesis process for preparing column type polymer brush.
Background technology
Process for preparing column type polymer brush is as the one-dimensional nano structure of a class uniqueness, the topological structure special due to it and physicochemical property
The most studied.Its medicine load, prepare template as nano material, functional nanomaterials field has extensively
Application prospect and meaning.
The synthetic method of polymer brush mainly includes activity/controllable free-radical polymerisation such as ATRP at present
(ATRP), the reversible addion-fragmentation chain transfer polymerization method such as (RAFT), nitroxide-mediated stable free-radical polymerization (NMP).Wherein RAFT gathers
Conjunction has the advantages such as functional groups better tolerance, polymerisable monomer kind is many, non-metal catalyst is easily purified, and RAFT is polymerized conjunction
Polymer is become to be brushed with two ways: R end mode and Z end mode.R end mode chain tra nsfer group is in outside polymer brush, Z end side
Formula chain tra nsfer group is in inside polymer brush, and compared with Z mode, the advantage that R end mode synthesizes is that polymer brush side arm is tied
Structure is more stable and fine and close.
The synthesis of RAFT method synthetic polymer brush it is critical only that the synthesis of poly chain transfer agent main chain, and wherein polystyrene is
The poly chain transfer agent of main chain has a structure the most degradable to ph stability, however only have at present the degree of polymerization less than 150 based on
Synthesis report (J.Polym.Sci., the Part A:Polym.Chem.2002,2956-of polystyrene backbone poly chain transfer agent
2966 and Macromol.Rapid Commun.2014,35,234-241).
Summary of the invention
It is an object of the invention to provide a kind of styrene type poly chain transfer agent, its preparation method and be polymerized in synthesis column
Application in thing brush, the degree of polymerization of this styrene type poly chain transfer agent is controlled, can increase synthesis process for preparing column type polymer in R end mode
Brush.
A kind of styrene type poly chain transfer agent, for structure polymer as shown in formula (I):
In formula (I), n is 10～20000, and m is 1～20000, and molecular weight distribution is 1.01～4.0；
R is the one in replacement or unsubstituted alkyl, replacement or unsubstituted phenyl；
R ' for replace or unsubstituted alkyl, replacement or unsubstituted phenyl, replacement or unsubstituting alkoxy, replacement or
Person's unsubstituted alkylthio group, replacement or unsubstituting phenoxy, replacement or unsubstituting phenenyl sulfenyl；
The described substituent on alkyl, phenyl, alkoxyl, alkylthio group, phenoxy group or thiophenyl is independently selected from C1～C5
Alkyl, C1～C5Alkoxyl, C1～C5Thiazolinyl or halogen.
In the present invention, the styrene type poly chain transfer agent shown in formula (I) is random copolymer.
The degree of polymerization of the styrene type poly chain transfer agent of the present invention is controlled, can increase synthesis process for preparing column type polymer in R end mode
Brush, the polymer brush obtained is using polystyrene backbone as skeleton, to ph stability non-degradable；Polymer brush backbone length can
Control, can reach 2000 and molecular weight distribution narrower.
As preferably, R is substituted or unsubstituted C1～C18One in alkyl, substituted or unsubstituted phenyl；
R ' is substituted or unsubstituted C1～C18Alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted C1～C18
Alkoxyl, substituted or unsubstituted C1～C18In alkylthio group, substituted or unsubstituted phenoxy group, substituted or unsubstituted thiophenyl
One.
As preferably, backbone structure is polystyrene, and side chain is containing chain tra nsfer groups such as dithioesters, three thioesters, xanthates.
Present invention also offers the preparation method of a kind of described styrene type poly chain transfer agent, comprise the steps:
(1) vinyl benzyl ester is carried out radical polymerization or activity/controllable free-radical polymerisation obtains poly-to vinyl benzyl
Ester；
Shown in the described structure to vinyl benzyl ester such as formula (II):
In formula (II), R and n is as defined above described in literary composition, and molecular weight distribution is 1.01～4.0；
(2) under the effect of alkali, poly-obtain vinyl benzyl ester generation hydrolysis that step (1) obtains gathers vinyl
Benzylalcohol；
(3) under the effect of chlorinating agent, step (2) obtain poly-vinyl benzyl alcohol generation chlorination is obtained poly-right
Vinyl benzyl chloride；
(4) gathering that step (3) obtains carries out substitution reaction to vinyl benzyl chloride with dithionate or thiocarbonate,
To described styrene type poly chain transfer agent.
In step (1), the polymerization of general radical that the polymerization of vinyl benzyl ester is included under initiator, light or heat effect with
And RAFT polymerization, ATRP polymerization, NMP polymerization activity/controllable free-radical polymerisation, the temperature of described polymerisation is 30 DEG C～110
DEG C, polymerization time is 1 hour～3 days.
As preferably, in step (1), it is aggregated under the effect of thiobenzoate cumyl ester and azodiisobutyronitrile and carries out.
In step (2) and step (3), by poly-vinyl benzyl ester precursor being hydrolyzed, the reaction such as replacement introduce chain
Transfer group side base, degree of functionalization m/n is 0.1%～100%.
As preferably, in step (4), described dithionate or thiocarbonate are dodecyl trithiocarbonic acid
Sodium, dithiobenzoic acid sodium or sodium ethylxanthate.
Present invention also offers the preparation method of a kind of process for preparing column type polymer brush, including:
Under the effect of initiator or heat, described styrene type poly chain transfer agent with carry out RAFT containing double bond monomer and be polymerized
Reaction, obtains described process for preparing column type polymer brush.
As preferably, described includes acrylic acid, acrylate, acrylamide, methacrylic acid, methyl containing double bond monomer
Acrylate, Methacrylamide, vinylacetate, Styrene and its derivatives.
As preferably, the temperature of described RAFT polymerisation is 30 DEG C～110 DEG C, and the time of polymerisation is 1 hour
～3 days.
Present invention also offers a kind of process for preparing column type polymer brush, described preparation method prepare.
Compared with prior art, the invention has the beneficial effects as follows: (1) prepares length controllable narrow distribution styrene main chain first
Poly chain transfer agent；And prior art can only prepare the backbone polymerization degree poly chain transfer agent less than 150, cause the column finally synthesized
Polymer brush loses its column feature to a certain extent.(2) the poly chain transfer agent used in the present invention has the property that
(i) polystyrene backbone as polymer brush skeleton structure to ph stability non-degradable；(ii) polymer brush backbone length can
Control, can reach 2000；(iii) polymer brush (≤1.4) of narrow molecular weight distribution can be prepared；(iv) can be according to R group
With double bond monomer homopolymerization or the combined polymerization that the difference of X atom regulates and controls number of different types.
Accompanying drawing explanation
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the product that embodiment 4 obtains.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further detailed.
Resulting polymers and process for preparing column type polymer brush use GPC to measure.Number-average molecular weight and the molecular weight distribution of polymer exist
Measuring in gel permeation chromatography (Waters 1515Isocratic efficient liquid-phase chromatographic pump), THF, as flowing phase, 40 DEG C, flows
Speed is 1.0mL/min.
The synthesis to vinyl benzyl ester of the embodiment 1 poly-acetic acid
3.0g (17.0mmol) acetic acid is added to vinyl benzyl ester, 3mg (0.011mmol) thiobenzoate in reaction bulb
Cumyl ester and 0.1mg azodiisobutyronitrile, seal and be placed in 60 DEG C of oil baths reaction 12h, pour the mixture into 100mL after reaction
Precipitating in methanol solution, filter, be vacuum dried by the polymer of gained and obtain product, yield is 60%.Resulting polymers number is equal
Molecular weight is 80,000, and molecular weight distribution is 1.2.
The poly-synthesis to vinyl benzyl alcohol of embodiment 2
The poly-acetic acid that addition 1.3g embodiment 1 obtains in reaction bulb is to vinyl benzyl ester (8.5mmol ester group) and 0.3g
NaOH (8.5mmol), is dissolved in room temperature reaction 12h after oxolane, pours the mixture into precipitation, mistake in ether after reaction
Filter, is vacuum dried the polymer of gained and obtains product, and yield is 92%.Resulting polymers number-average molecular weight is 70,000, molecular weight
It is distributed as 1.2.
The poly-synthesis to vinyl benzyl chloride of embodiment 3
What in reaction bulb, addition 1.1g embodiment 2 obtained is poly-to vinyl benzyl alcohol (8.5mmol hydroxyl), is dissolved in 20mL
Add 5mL thionyl chloride room temperature reaction 12h after oxolane, pour the mixture into after reaction in 200mL ether and precipitate, filter,
Being vacuum dried by the polymer of gained and obtain product, yield is 85%.Resulting polymers number-average molecular weight is 70,000, and molecular weight divides
Cloth is 1.2.
Embodiment 4 side base is the poly chain transfer agent synthesis of three thioesters
What in reaction bulb, addition 0.65g embodiment 3 obtained is poly-to vinyl benzyl chloride (4.3mmol halogen atom), dissolves
0.14g dodecyl trithiocarbonic acid sodium (4.6mmol) room temperature reaction 12h is added after 20mL oxolane, will be mixed after reaction
Compound is poured in 200mL ether and is precipitated, filters, and is vacuum dried by the polymer of gained and obtains product, and yield is 73%.Gained gathers
Compound number-average molecular weight is 130,000, and molecular weight distribution is 1.3.Hydrogen nuclear magnetic spectrum (the CDCl of product3) as shown in Figure 1.In Fig. 1 respectively
Signal peak can be belonged to by formula (3), it was demonstrated that successfully obtains the poly chain transfer agent of three thioesters side bases.
Embodiment 5 side base is the poly chain transfer agent synthesis of dithioesters
Other reaction conditions are the same as in Example 4, except that dodecyl trithiocarbonic acid sodium is replaced with two sulphur
For Sodium Benzoate, final polymer yield is 70%.Resulting polymers number-average molecular weight is 130,000, and molecular weight distribution is 1.3.
Embodiment 6 side base is the poly chain transfer agent synthesis of xanthate
Other reaction conditions are the same as in Example 4, except that dodecyl trithiocarbonic acid sodium is replaced with ethyl
Sodium xanthogenate, final polymer yield is 80%.Resulting polymers number-average molecular weight is 130,000, and molecular weight distribution is 1.3.
Embodiment 7 side chain is the process for preparing column type polymer brush synthesis of PMA
Poly chain transfer agent (the 0.05mmol chain that side base is three thioesters that 18.9mg embodiment 4 obtains is added in reaction bulb
Transfer agent group), 0.4g methyl acrylate (5mmol) and 2mg azodiisobutyronitrile, dissolve rear 60 DEG C of reactions 5 with 4mL methyl phenyl ethers anisole
Hour, pour the mixture into afterwards in 100mL ether and precipitate, filter, the polymer of gained is vacuum dried and obtains product, yield
It is 40%.Resulting polymers number-average molecular weight is 600,000, and molecular weight distribution is 1.3.
Embodiment 8 side chain is the process for preparing column type polymer brush synthesis of PNIPAM
Other polymerizing conditions are same as in Example 7, except that monomer replaces with 0.5g N-isopropylacrylamide
(5mmol), after 6h is reacted in 60 DEG C of oil baths, pour in 100mL ether and precipitate, after filtering the polymer vacuum drying of gained, receive
Rate is 35%.Resulting polymers number-average molecular weight is 560,000, and molecular weight distribution is 1.3.
Embodiment 9 side chain is the synthesis of polyacrylic process for preparing column type polymer brush
Other polymerizing conditions are same as in Example 7, except that monomer replaces with 0.36g acrylic acid (5mmol), and 60 DEG C
After reacting 6h in oil bath, pouring in 100mL ether and precipitate, after filtering the polymer vacuum drying of gained, yield is 40%.
Embodiment 10 side chain is the process for preparing column type polymer brush synthesis of polymethyl methacrylate
Other polymerizing conditions are same as in Example 7, except that monomer replaces with 0.4g methyl methacrylate
(5mmol), after 5h is reacted in 60 DEG C of oil baths, pour in 100mL ether and precipitate, after filtering the polymer vacuum drying of gained, receive
Rate is 40%.Resulting polymers number-average molecular weight is 670,000, and molecular weight distribution is 1.3.
Embodiment 11 side chain is the process for preparing column type polymer brush synthesis of poly-isopropyl methyl acrylamide
Other polymerizing conditions are same as in Example 7, except that monomer replaces with 0.5g isopropyl methyl acrylamide
(5mmol), after 6h is reacted in 60 DEG C of oil baths, pour in 100mL ether and precipitate, after filtering the polymer vacuum drying of gained, receive
Rate is 35%.Resulting polymers number-average molecular weight is 560,000, and molecular weight distribution is 1.3.
Embodiment 12 side chain is the process for preparing column type polymer brush synthesis of polymethylacrylic acid
Other polymerizing conditions are same as in Example 7, except that monomer replaces with 0.36g methacrylic acid (5mmol),
After reacting 6h in 60 DEG C of oil baths, pouring in 100mL ether and precipitate, after filtering the polymer vacuum drying of gained, yield is 43%.
Embodiment 13 side chain is the process for preparing column type polymer brush synthesis of polystyrene
Other polymerizing conditions are same as in Example 7, except that monomer replaces with 0.5g styrene (5mmol), poly chain
Transfer agent replaces with poly chain transfer agent (the 0.05mmol chain-transferring agent base that side base is dithioesters that 18.7mg embodiment 5 obtains
Group).After reacting 12h in 60 DEG C of oil baths, pouring in 100mL methyl alcohol and precipitate, after filtering the polymer vacuum drying of gained, yield is
25%.Resulting polymers number-average molecular weight is 500,000, and molecular weight distribution is 1.3.
Embodiment 14 side chain is the process for preparing column type polymer brush synthesis of polyvinyl acetate
Other polymerizing conditions are same as in Example 7, except that monomer replaces with 0.4g vinyl acetate (5mmol),
Poly chain transfer agent replaces with poly chain transfer agent (the 0.05mmol chain tra nsfer that side base is xanthate that 18.4mg embodiment 6 obtains
Agent group).After 5h is reacted in 60 DEG C of oil baths, pour in 100mL n-hexane and precipitate, after filtering the polymer vacuum drying of gained,
Yield is 35%.Resulting polymers number-average molecular weight is 680,000, and molecular weight distribution is 1.3.
Embodiment 15 side chain is the process for preparing column type polymer brush synthesis of methyl acrylate and N-isopropylacrylamide copolymer
Other polymerizing conditions are same as in Example 7, except that be simultaneously introduced 0.5g N-isopropylacrylamide (5mmol)
As comonomer.After reacting 5h in 60 DEG C of oil baths, pouring in 100mL n-hexane and precipitate, the polymer vacuum filtering gained is done
After dry, yield is 35%.Resulting polymers number-average molecular weight is 900,000, and molecular weight distribution is 1.3.
Embodiment 16 side chain is the process for preparing column type polymer brush of PMA and PNIPAM block copolymer
Synthesis
Other polymerizing conditions are the same as in Example 8, except that poly chain transfer agent replaces with in 0.16g embodiment 7
Side chain is the process for preparing column type polymer brush (0.05mmol chain-transferring agent group) of PMA.After 7h is reacted in 60 DEG C of oil baths, fall
Entering in 100mL ether and precipitate, after filtering the polymer vacuum drying of gained, yield is 55%.Resulting polymers number-average molecular weight
Being 1,040,000, molecular weight distribution is 1.3.
Claims (9)
1. a styrene type poly chain transfer agent, it is characterised in that for structure polymer as shown in formula (I):
In formula (I), n is 10～20000, and m is 1～20000, and molecular weight distribution is 1.01～4.0；
R is the one in replacement or unsubstituted alkyl, replacement or unsubstituted phenyl；
R ' is for replacing or unsubstituted alkyl, replacement or unsubstituted phenyl, replacement or unsubstituting alkoxy, replacement or not
Substituted alkane sulphur base, replacement or unsubstituting phenoxy, replacement or unsubstituting phenenyl sulfenyl；
The described substituent on alkyl, phenyl, alkoxyl, alkylthio group, phenoxy group or thiophenyl is independently selected from C1～C5Alkane
Base, C1～C5Alkoxyl, C1～C5Thiazolinyl or halogen.
Styrene type poly chain transfer agent the most according to claim 1, it is characterised in that R is substituted or unsubstituted C1~
C18One in alkyl, substituted or unsubstituted phenyl；
R ' is substituted or unsubstituted C1～C18Alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted C1～C18Alcoxyl
Base, substituted or unsubstituted C1～C18In alkylthio group, substituted or unsubstituted phenoxy group, substituted or unsubstituted thiophenyl one
Kind.
3. the preparation method of a styrene type poly chain transfer agent as claimed in claim 1 or 2, it is characterised in that include as
Lower step:
(1) vinyl benzyl ester is carried out radical polymerization or activity/controllable free-radical polymerisation obtains poly-to vinyl benzyl ester；
The described poly-structure such as formula (II) to vinyl benzyl ester is shown:
In formula (II), the definition of R with n is identical with claim 1 or 2, and molecular weight distribution is 1.01～4.0；(2) in the effect of alkali
Under, poly-obtain vinyl benzyl ester generation hydrolysis that step (1) obtains gathers vinyl benzyl alcohol；
(3) under the effect of chlorinating agent, poly-obtain vinyl benzyl alcohol generation chlorination that step (2) obtains gathers ethene
Base benzyl chlorine；
(4) gathering that step (3) obtains carries out substitution reaction to vinyl benzyl chloride with dithionate or thiocarbonate, obtains institute
The styrene type poly chain transfer agent stated.
The preparation method of styrene type poly chain transfer agent the most according to claim 3, it is characterised in that in step (1), poly-
The temperature closed is 30 DEG C～110 DEG C, and the time of polymerization is 1 hour～3 days.
The preparation method of styrene type poly chain transfer agent the most according to claim 3, it is characterised in that in step (4), institute
The dithionate stated or thiocarbonate are alkyl trithiocarbonate, dithiobenzoic acid salt or alkyl xanthate.
6. the preparation method of a process for preparing column type polymer brush, it is characterised in that including:
Under the effect of initiator or heat, the styrene type poly chain transfer agent regulation and control described in claim 1 or 2 are entered containing double bond monomer
Row RAFT polymerisation, obtains described process for preparing column type polymer brush.
The preparation method of process for preparing column type polymer brush the most according to claim 6, it is characterised in that described containing double bond monomer bag
Include acrylic acid, acrylate, acrylamide, methacrylic acid, methacrylate, Methacrylamide, vinylacetate, benzene
Ethene and derivative thereof.
The preparation method of process for preparing column type polymer brush the most according to claim 6, it is characterised in that described RAFT polymerisation
Temperature be 30 DEG C～110 DEG C, the time of polymerisation is 1 hour～3 days.
9. a process for preparing column type polymer brush, it is characterised in that prepared by the preparation method described in any one of claim 6～8.
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