Block polymer containing perfluoropolyether structure
阅读说明：本技术 一种含全氟聚醚结构的嵌段聚合物 (Block polymer containing perfluoropolyether structure ) 是由 郭寅天 徐文前 陈清 郑昀红 于 2018-08-06 设计创作，主要内容包括：本发明公开了一种具有结构式(I)的含全氟聚醚结构的嵌段聚合物,<Image he="409" wi="700" file="DDA0001754706150000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>各取代基见说明书。本发明还公开了所述含全氟聚醚结构的嵌段聚合物的制备方法。本发明提供的制备方法转化率高、物金属残留,制备得到的嵌段聚合物结构新颖、稳定性高。(The invention discloses a block polymer containing a perfluoropolyether structure with a structural formula (I), each substituent is shown in the specification. The invention also discloses a preparation method of the block polymer containing the perfluoropolyether structure. The preparation method provided by the invention has the advantages of high conversion rate and metal residue, and the prepared block polymer has a novel structure and high stability.)
1. A block polymer containing a perfluoropolyether structure has the following structural formula (I):
wherein:
n is an integer of 5 to 200;
a is selected from 1 or 2;
q is selected from O or NH;
R1independently selected from-H or-CH3；
R2Independently selected from-H, -CH3Or
R3Independently selected from-H, -CH3、-F、-CF3or-CN;
R4independently selected from-H, -CH3、-CH2CH3、
the PFPE is a perfluoropolyether structure, and the number average molecular weight of the PFPE is 500-10000, wherein:
a) when a is selected from 1, PFPE is selected from one of the following structural formulas shown in K type, Z type and D type:
b) when a is selected from 2, PFPE is selected from one of the following structural formulas shown as K ', Z ' and D ':
wherein:
Ra、Ra'Du' aloneSelected from- (CH)2CH2O) m, m is independently selected from an integer of 0-10;
-Rfis independently selected from
w, x, y and z are independently selected from integers of 4-60, and x/y is more than or equal to 1 and less than or equal to 3.
2. The block polymer containing a perfluoropolyether structure according to claim 1, characterized in that:
n is an integer of 5 to 100;
q is selected from O;
R1independently selected from-H;
R2independently selected from-H or-CH3；
R3Independently selected from-H, -CH3or-CN;
R4is independently selected from-CH3、
The PFPE is a perfluoropolyether structure, and the number average molecular weight of the PFPE is 500-7000, wherein:
Ra、Ra' is independently selected from- (CH)2CH2O) m, m is independently selected from an integer of 0-5;
-Rfis independently selected fromr is independently selected from an integer of 0-5;
w, x, y and z are independently selected from integers of 4-40, and x/y is more than or equal to 1 and less than or equal to 3.
3. The block polymer containing a perfluoropolyether structure according to claim 2, characterized in that:
n is an integer of 0 to 50;
R2independently selected from-H;
R3independently selected from-H or-CH3；
R4Is independently selected from-CH3、-CH2CF3、-CH2CH2(CF2)5CF3or-CH2CH2(CF2)7CF3；
The PFPE is a perfluoropolyether structure, and the number average molecular weight of the PFPE is 1000-4000, wherein:
Ra、Ra' is independently selected from- (CH)2CH2O) m, m is independently selected from an integer of 0-3;
-Rfis independently selected fromr is independently selected from an integer of 0 to 3;
w, x, y and z are independently selected from integers of 4-25, and x/y is more than or equal to 1 and less than or equal to 3.
4. The block polymer containing a perfluoropolyether structure according to claim 3, characterized in that:
the PFPE is a perfluoropolyether structure, and the number average molecular weight of the PFPE is 1000-2000, wherein:
Ra、Ra' is independently selected from- (CH)2CH2O) m, m is independently selected from an integer of 0-3;
-Rfis independently selected from
w, x, y and z are independently selected from integers of 4-12, and x/y is more than or equal to 1 and less than or equal to 3.
5. The block polymer containing a perfluoropolyether structure according to claim 1, characterized in that said block polymer containing a perfluoropolyether structure is prepared by a process comprising:
firstly, PFPE selected from at least one of K type, Z type, D type, K ' type, Z ' type and D ' type reacts with an alkali metal compound or a complex compound to obtain perfluoropolyether alkoxide, and then the perfluoropolyether alkoxide initiates the polymerization of a vinyl-containing monomer to obtain a block copolymer containing a perfluoropolyether structure shown in a structural formula (I);
the alkali metal compound or complex is at least one selected from the group consisting of sodium hydride, potassium hydride, dimethylsulfoxide-sodium complex, naphthalene-sodium complex, [ 18-crown-6 ] -sodium complex, [ 15-crown-5 ] -sodium complex, [ 12-crown-4 ] -sodium complex, dimethylsulfoxide-potassium complex, naphthalene-potassium complex, [ 18-crown-6 ] -potassium complex, [ 15-crown-5 ] -potassium complex and [ 12-crown-4 ] -potassium complex.
6. The block polymer containing a perfluoropolyether structure according to claim 5, characterized in that:
the alkali metal compound or complex is at least one selected from the group consisting of potassium hydride, dimethylsulfoxide-sodium complex, naphthalene-sodium complex, dimethylsulfoxide-potassium complex, naphthalene-potassium complex, [ 18-crown-6 ] -potassium complex, and [ 15-crown-5 ] -potassium complex;
the molar ratio of the alkali metal compound or the complex compound to the PFPE is 0.5-5: 1.
7. The block polymer containing a perfluoropolyether structure according to claim 6, characterized in that:
the alkali metal compound or complex is at least one selected from potassium hydride, dimethyl sulfoxide-sodium complex, naphthalene-sodium complex, dimethyl sulfoxide-potassium complex and naphthalene-potassium complex;
the molar ratio of the alkali metal compound or the complex compound to the PFPE is 0.9-3: 1.
8. The block polymer containing a perfluoropolyether structure according to claim 5, characterized in that:
in an aprotic organic solvent, firstly, reacting at least one PFPE selected from K type, Z type, D type, K ' type, Z ' type and D ' type with an alkali metal compound or a complex compound to obtain perfluoropolyether alkoxide, and then initiating polymerization of a vinyl-containing monomer by the perfluoropolyether alkoxide to obtain a block copolymer containing a perfluoropolyether structure shown in a structural formula (I);
the aprotic organic solvent is at least one selected from tetrahydrofuran, toluene, benzene, dimethyl sulfoxide, N-dimethylformamide, diethyl ether, isopropyl ether, carbon tetrachloride, cyclohexane, N-hexane, petroleum ether, dioxane, triethylamine, 1,1,1,3, 3-pentafluorobutane, 1,1, 1-trifluorotrichloroethane, 1,1, 2-trifluorotrichloroethane, trichloromethane, trifluorotoluene, methyl perfluoropropyl ether, methyl perfluorobutyl ether, methyl perfluoroisobutyl ether, ethyl perfluorobutyl ether and ethyl perfluoroisobutyl ether;
the molar ratio of the vinyl-containing monomer to the perfluoropolyether alkoxide is 5-500: 1;
the reaction temperature is-20 to 80 ℃.
9. The block polymer containing a perfluoropolyether structure according to claim 8, characterized in that:
the aprotic organic solvent is at least one selected from tetrahydrofuran, 1,1,1,3, 3-pentafluorobutane, 1,1, 1-trifluorotrichloroethane, trifluorotoluene, methyl perfluorobutyl ether and ethyl perfluorobutyl ether;
the molar ratio of the vinyl-containing monomer to the perfluoropolyether alkoxide is 8-150: 1;
the reaction temperature is 20-55 ℃.
10. The block polymer having a perfluoropolyether structure according to claim 1, wherein the number average molecular weight of the block polymer having a perfluoropolyether structure is 2000 to 100000.
Technical Field
The invention belongs to the field of organic high molecular compounds, and relates to a block polymer containing a perfluoropolyether structure.
Background
The block polymer is a high molecular compound having a composition of at least two successive different structural units. Taking a diblock copolymer as an example, by performing block copolymerization using two monomers having completely different properties, it is possible to realize the characteristics of a homopolymer having two monomers on the same molecular chain at the same time. The block copolymer can be used as shape memory material, thermoplastic elastomer, amphiphilic polymer, etc. and has wide application foreground.
Perfluoropolyethers and their derivatives have a wide range of applications in a variety of fields due to their good thermal stability, oxidation resistance, insulation, low surface energy, low volatility, and biocompatibility. The properties of perfluoropolyethers are closely related to their chain structure, and the common perfluoropolyether structures are Z type (perfluoromethoxy/perfluoroethoxy copolymer), K type (polyperfluoro-1, 2-propanediol) and D type (polyperfluoro-1, 3-propanediol). When the perfluoropolyether is functionalized, the perfluoropolyether is easier to regulate when being used for the structural design of the polymer, such as: (a) the carboxyl-terminated perfluoropolyethers can be used for block copolymerization with polyglycerol to make biocompatible microfluidics (Wagner, o., Thiele, j., Weinhart, m., Mazutis, l., Weitz, d.a., Huck, w.t., & hag, R. (2016.). Lab on a Chip,16(1), 65-69); (b) hydroxyl-terminated perfluoropolyethers can be used to prepare atom transfer radical polymerization initiators (ATRP initiators) to initiate acrylate polymerization (Woods, h.m., novvel, c., lace, p., Irvine, d.j., & Howdle, S.M. (2005). Macromolecules,38(8), 3271-; (c) perfluoropolyether ester derivatives can also be copolymerized with acrylamide monomers (Yarbrough, j.c., Rolland, j.p., DeSimone, j.m., Callow, m.e., Finlay, j.a., & Callow, J.A. (2006.) Macromolecules,39(7), 2521-2528).
The block polymer containing the perfluoropolyether structure can be obtained by copolymerizing perfluoropolyether and other monomers, and the excellent characteristics of the perfluoropolyether can be introduced into the block polymer, so that the application field of the block polymer is expanded. The block polymer has outstanding performances in the fields of biomedicine, surface modification and the like.
For the preparation of block polymer containing perfluoropolyether structure by copolymerization of perfluoropolyether and other monomers, the prior art generally adopts ATRP method, firstly uses perfluoropolyether terminal hydroxyl functionalization, and prepares ATRP initiator with 2-bromine isobutyryl bromide and the like, and then initiates polymerization reaction under the action of transition metal complexes such as CuCl and the like to obtain the block polymer. In the method, on one hand, because transition metals such as Cu and the like are not consumed in the polymerization process, the transition metals are bound to remain in the product and are difficult to purify, so that the performance of the polymer is reduced; on the other hand, since the polymer backbone is grafted with 2-bromoisobutyryl bromide to carry ester groups, it is degraded under certain conditions, resulting in a decrease in polymer stability. Another method for preparing the block polymer containing the perfluoropolyether structure is to obtain the block polymer containing the perfluoropolyether structure through aminolysis and ester exchange reaction of the functionalized end of the perfluoropolyether. The method has the advantages of long preparation route, limited conversion rate of each step and low total conversion rate.
Disclosure of Invention
The invention aims to provide a block polymer containing a perfluoropolyether structure, which has the following structural formula (I):
wherein:
n is an integer of 5 to 200;
a is selected from 1 or 2;
q is selected from O or NH;
R1is selected from-H or-CH3；
R2Is selected from-H, -CH3Or
R3Is selected from-H, -CH3、-F、-CF3or-CN;
R4is selected from-H, -CH3、-CH2CH3、
the PFPE is a perfluoropolyether structure, and the number average molecular weight of the PFPE is 500-10000, wherein:
a) when a is selected from 1, PFPE is selected from one of the following structural formulas shown in K type, Z type and D type:
b) when a is selected from 2, PFPE is selected from one of the following structural formulas shown as K ', Z ' and D ':
wherein:
Ra、Ra' is independently selected from- (CH)2CH2O) m, wherein m is an integer of 0-10;
-Rfis selected from
w, x, y and z are independently selected from integers of 4-60, and x/y is more than or equal to 1 and less than or equal to 3.
The invention provides a block polymer containing a perfluoropolyether structure shown in a structural formula (I), wherein a substituent R in the structural formula1Independently selected from-H or-CH3. Preferably, R is1Independently selected from-H.
The invention provides a block polymer containing a perfluoropolyether structure shown in a structural formula (I), wherein a substituent R in the structural formula2Independently selected from-H, -CH3Or
The invention provides a block polymer containing a perfluoropolyether structure shown in a structural formula (I), wherein a substituent R in the structural formula3Independently selected from-H, -CH3、-F、-CF3or-CN. Preferably, R is3Independently selected from-H, -CH3or-CN. Further preferably, R is3Independently selected from-H or-CH3。
The invention provides a block polymer containing a perfluoropolyether structure shown in a structural formula (I), wherein a substituent R in the structural formula4Independently selected from-H, -CH3、-CH2CH3、
Preferably, R4 is independently selected from-CH3、-CH2CF3-CH2CHFCF3-CH2CF2CF3-CH2CH2CF2CF3-CH2CF2CHFCF3-CH2CF2CF2CF3-CH2CH2(CF2)3CF3
Further preferably, R is4Is independently selected from-CH3、-CH2CF3、-CH2CH2(CF2)5CF3Or
The block polymer containing the perfluoropolyether structure shown in the structural formula (I) is characterized in that n in the structural formula is an integer from 5 to 200. Preferably, n is an integer of 5 to 100. More preferably, n is an integer of 0 to 50.
The invention provides a block polymer containing a perfluoropolyether structure shown in a structural formula (I), wherein Q is selected from O or NH. Preferably, Q is selected from O.
The invention provides a block polymer containing a perfluoropolyether structure shown in a structural formula (I), wherein a is selected from 1 or 2.
The invention provides a block polymer containing a perfluoropolyether structure, which is shown in a structural formula (I), wherein PFPE is a perfluoropolyether structure, and the number average molecular weight of the block polymer is 500-10000, wherein:
a) when a is selected from 1, PFPE is selected from one of the following structural formulas shown in K type, Z type and D type:
b) when a is selected from 2, PFPE is selected from one of the following structural formulas shown as K ', Z ' and D ':
wherein:
Ra、Ra' is independently selected from- (CH)2CH2O) m, m is independently selected from an integer of 0-10;
-Rfis independently selected from
w, x, y and z are independently selected from integers of 4-60, and x/y is more than or equal to 1 and less than or equal to 3.
In the perfluoropolyether structures represented by the K type, Z type, D type, K ' type, Z ' type, and D ' type, R isa、Ra' is independently selected from- (CH)2CH2O) m, m is independently selected from an integer of 0 to 10. Preferably, m is independently selected from an integer of 0 to 5. More preferably, m is independently selected from an integer of 0 to 3.
In the perfluoropolyether structures represented by the above K type, Z type, D type, K ' type, Z ' type and D ' type, -RfIs independently selected fromr is independently selected from an integer of 0 to 10. Preferably, r is independently selected from an integer of 0 to 5. More preferably, r is independently selected from an integer of 0 to 3.
In the perfluoropolyether structures shown in the K type, the Z type, the D type, the K ' type, the Z ' type and the D ' type, w, x, y and Z are independently selected from integers of 4-60, and x/y is more than or equal to 1 and less than or equal to 3. Preferably, w, x, y and z are independently selected from integers of 4-40, and 1 ≦ x/y ≦ 3. More preferably, w, x, y and z are independently selected from integers of 4-25, and 1 ≦ x/y ≦ 3.
The block polymer containing the perfluoropolyether structure shown in the structural formula (I) has the structural formula that PFPE has the number average molecular weight of 500-10000. Preferably, the number average molecular weight of the PFPE is selected from 500 to 7000. More preferably, the number average molecular weight of the PFPE is selected from 1000 to 2000.
The block polymer containing the perfluoropolyether structure shown in the structural formula (I) has the number average molecular weight of 2000-100000. Preferably, the number average molecular weight is 2000 to 70000. More preferably, the number average molecular weight is 2000 to 40000. More preferably, the number average molecular weight is 2000 to 20000.
The invention also provides a preparation method of the block polymer containing the perfluoropolyether structure shown in the structural formula (I), which comprises the steps of firstly preparing a nucleophilic reagent perfluoropolyether alkoxide, then attacking an anionic polymerization monomer containing vinyl, and initiating a polymerization reaction, thereby obtaining the block polymer containing the perfluoropolyether structure.
The invention provides a preparation method of a block polymer containing a perfluoropolyether structure, which is shown in a structural formula (I), and comprises the following steps:
firstly, PFPE selected from at least one of K type, Z type, D type, K ' type, Z ' type and D ' type reacts with an alkali metal compound or a complex compound to obtain perfluoropolyether alkoxide, and then the perfluoropolyether alkoxide initiates the polymerization of a vinyl-containing monomer to obtain the block copolymer containing the perfluoropolyether structure shown in the structural formula (I).
In the production method of the present invention, the alkali metal compound or complex used is at least one selected from the group consisting of sodium hydride, potassium hydride, dimethyl sulfoxide-sodium complex, naphthalene-sodium complex, [ 18-crown-6 ] -sodium complex, [ 15-crown-5 ] -sodium complex, [ 12-crown-4 ] -sodium complex, dimethyl sulfoxide-potassium complex, naphthalene-potassium complex, [ 18-crown-6 ] -potassium complex, [ 15-crown-5 ] -potassium complex and [ 12-crown-4 ] -potassium complex.
Preferably, the alkali metal compound or complex is at least one selected from the group consisting of potassium hydride, dimethyl sulfoxide-sodium complex, naphthalene-sodium complex, dimethyl sulfoxide-potassium complex, naphthalene-potassium complex, [ 18-crown-6 ] -potassium complex and [ 15-crown-5 ] -potassium complex.
Further preferably, the alkali metal compound or complex is at least one selected from the group consisting of potassium hydride, a dimethylsulfoxide-sodium complex, a naphthalene-sodium complex, a dimethylsulfoxide-potassium complex, and a naphthalene-potassium complex.
More preferably, the alkali metal compound or complex is at least one selected from the group consisting of potassium hydride, dimethyl sulfoxide-sodium complex, naphthalene-sodium complex, dimethyl sulfoxide-potassium complex and naphthalene-potassium complex.
The amount of alkali metal compound or complex is such that it can react with PFPE to give the perfluoropolyether alkoxide. Preferably, the molar ratio of the alkali metal compound or complex to the PFPE is 0.5-5: 1. Further preferably, the molar ratio of the alkali metal compound or complex to the PFPE is 0.9-3: 1.
The preparation method of the invention can be carried out in the presence of an organic solvent or in the absence of the organic solvent. When carried out in the presence of an organic solvent, the organic solvent is preferably an aprotic organic solvent. Among the aprotic organic solvents, aprotic organic solvents commonly used in the art may be mentioned.
Preferably, the aprotic organic solvent is at least one selected from the group consisting of tetrahydrofuran, toluene, benzene, dimethyl sulfoxide, N-dimethylformamide, diethyl ether, isopropyl ether, carbon tetrachloride, cyclohexane, N-hexane, petroleum ether, dioxane, triethylamine, 1,1,1,3, 3-pentafluorobutane, 1,1, 1-trifluorotrichloroethane, 1,1, 2-trifluorotrichloroethane, chloroform, trifluorotoluene, methyl perfluoropropyl ether, methyl perfluorobutyl ether, methyl perfluoroisobutyl ether, ethyl perfluorobutyl ether and ethyl perfluoroisobutyl ether.
Further preferably, the aprotic organic solvent is at least one selected from the group consisting of tetrahydrofuran, 1,1,1,3, 3-pentafluorobutane, 1,1, 1-trifluorotrichloroethane, trifluorotoluene, methyl perfluorobutyl ether and ethyl perfluorobutyl ether.
As the amount of the aprotic organic solvent, those commonly used in the art can be used.
In the preparation method, the ratio of the vinyl-containing monomer and the perfluoropolyether alkoxide is such that the perfluoropolyether alkoxide can initiate the polymerization of the vinyl-containing monomer, so that the polymerization reaction can be smoothly carried out to obtain the block copolymer containing the perfluoropolyether structure.
The molar ratio of the vinyl-containing monomer to the perfluoropolyether alkoxide is preferably 5 to 500:1, and more preferably 8 to 150: 1.
The preparation method of the invention has no special requirements on the reaction temperature. Preferably, the reaction temperature is-20 to 80 ℃. Further preferably, the reaction temperature is 20 to 55 ℃.
The method for testing part of indexes of the block polymer containing the perfluoropolyether structure, which is prepared by the invention, comprises the following steps:
(1) hydrogen spectrum, fluorine spectrum: measured by NMR spectroscopy using a Bruker model 600MHz NMR spectrometer. The frequency of the test is 600MHz by adopting a 5mm nuclear magnetic tube. When the sample is tested, the sample is dissolved in deuterated chloroform or 1,1, 1-trifluorotrichloroethane, the concentration is 3wt percent, and the testing temperature is 25 ℃;
(2) infrared spectrum: measured by infrared spectroscopy using a Perkin-Elmer FT-IR 2000 infrared spectrometer. The KBr tablet is adopted for testing, and the scanning wave number is 400-4000 cm-1；
(3) Thermal weight loss: determined by thermogravimetric analysis using a Perkin-Elmer Pyris 1TGA thermogravimetric analyzer. The test was measured at a temperature ramp rate of 10 ℃/min up to 800 ℃ under a nitrogen stream.
Drawings
FIG. 1 preparation of polymer from example 11H nuclear magnetic map.
FIG. 2 preparation of polymer from example 119F nuclear magnetic map.
FIG. 3 the IR spectrum of the polymer prepared in example 1.
FIG. 4 thermogravimetric curves of the polymer prepared in example 1.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.