CN116903790A - Application of 1-boric acid pinacol ester styrene in preparation of alternating copolymer - Google Patents
Application of 1-boric acid pinacol ester styrene in preparation of alternating copolymer Download PDFInfo
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- CN116903790A CN116903790A CN202310844206.1A CN202310844206A CN116903790A CN 116903790 A CN116903790 A CN 116903790A CN 202310844206 A CN202310844206 A CN 202310844206A CN 116903790 A CN116903790 A CN 116903790A
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- styrene
- acid pinacol
- copolymer
- pinacol ester
- borate
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- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229920005603 alternating copolymer Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- -1 acrylic ester Chemical class 0.000 claims abstract description 16
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 16
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 14
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims abstract description 14
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 13
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 52
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 239000003999 initiator Substances 0.000 claims description 21
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 14
- 150000003254 radicals Chemical class 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 125000000864 peroxy group Chemical group O(O*)* 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000012934 organic peroxide initiator Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- BMQDAIUNAGXSKR-UHFFFAOYSA-N (3-hydroxy-2,3-dimethylbutan-2-yl)oxyboronic acid Chemical compound CC(C)(O)C(C)(C)OB(O)O BMQDAIUNAGXSKR-UHFFFAOYSA-N 0.000 claims 1
- 125000005396 acrylic acid ester group Chemical group 0.000 claims 1
- 238000001704 evaporation Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 239000000758 substrate Substances 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing boron
- C08F230/065—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing boron the monomer being a polymerisable borane, e.g. dimethyl(vinyl)borane
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides application of 1-boric acid pinacol ester styrene in preparation of an alternating copolymer, belongs to the fields of polymer synthesis and application, and can expand the variety range of a reaction substrate by utilizing the 1-boric acid pinacol ester styrene to synthesize the alternating copolymer, so that the reaction substrate can be expanded to acrylic ester, acrylamide, acrylonitrile, maleic anhydride or maleimide and the like, a series of poly (1-boric acid pinacol ester styrene-alternating-copolymer) can be synthesized, and the problem of limitation of the reaction substrate is solved. The raw materials used in the invention are commercially available compounds, the cost is low, the operation is simple and convenient, and the product has no metal residue.
Description
Technical Field
The invention belongs to the field of polymer synthesis and application, and particularly relates to application of 1-boric acid pinacol ester styrene in preparation of an alternating copolymer.
Background
Alternating copolymers are of great interest for important applications in the polymer field. Among them, the alternating copolymer product of styrene and maleic anhydride is widely used in industry and life for molding resin, polymer additive, pigment dispersant, ink modification, powder coating, leather retanning, floor care product, etc., showing the great application value of the alternating copolymer in real life. The most commonly known synthetic methods are free radical synthesis, the most commonly used initiators are benzoyl peroxide and azobis (isobutyronitrile), and the copolymerization can be carried out in bulk and in common organic solvents such as tetrahydrofuran, acetone, benzene, carbon tetrachloride, saturated hydrocarbons and the like. However, under the above conditions, styrene can only be polymerized with a strong electron-withdrawing monomer such as maleic anhydride or maleimide to obtain an alternating copolymer. The substrate range of the reaction is greatly limited.
Disclosure of Invention
The invention aims to provide an application of 1-boric acid pinacol styrene in preparation of an alternating copolymer, and the alternating copolymer is synthesized by using the 1-boric acid pinacol styrene, so that the variety range of reaction substrates can be expanded, the reaction substrates can be expanded to acrylic ester, acrylamide, acrylonitrile, maleic anhydride or maleimide and the like, a series of poly (1-boric acid pinacol styrene-alternating-copolymer) can be synthesized, and the problem of limitation of the reaction substrates is solved.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
use of pinacol 1-borate styrene for the preparation of alternating copolymers, in particular, 1-boronic acid pinacol styrene as comonomer.
Further, the pinacol 1-borate styrene is used as a comonomer for preparing an alternating copolymer, the preparation steps comprising:
using free radical initiator, using 1-boric acid pinacol ester styrene as one comonomer, and one of acrylic ester, acrylamide, acrylonitrile, maleic anhydride and maleimide as another comonomer, wherein the two comonomers are in N 2 And (3) carrying out reaction in an organic solvent under the protection of atmosphere to obtain the alternating copolymer poly (1-boric acid pinacol styrene-alternating-copolymer).
Further, the reaction formulas are as follows:
in the formula I, ia represents 1-boric acid pinacol ester styrene, IIa represents acrylic ester, R 1 Represents various alkyl groups, IIIa represents poly (pinacol 1-borate styrene-alternate-copolymer);
in formula II, ia represents 1-boronic acid pinacol ester styrene, IIb represents acrylamide, R 2 And R is 3 Represents various alkyl groups, IIIb represents a poly (pinacol 1-borate styrene-alternate-copolymer);
in formula III, ia represents 1-boronic acid pinacol ester styrene, IIc represents acrylonitrile, IIIc represents poly (1-boronic acid pinacol ester styrene-alternating copolymer);
in formula IV, ia represents 1-boronic acid pinacol ester styrene, IId represents maleic anhydride, IIId represents poly (1-boronic acid pinacol ester styrene-alternate-copolymer);
in the formula V, ia represents 1-boric acid pinacol ester styrene, IIe represents maleimide, R 4 Represents various alkyl groups, IIIe represents poly (pinacol 1-borate styrene-alternate-copolymer).
Further, alkyl radicals R in formula I 1 Is an alkyl group having 1 to 10 carbon atoms.
Further, alkyl R in formula II 2 、R 3 Is an alkyl group having 1 to 10 carbon atoms.
Further, alkyl in formula VR 4 Is an alkyl group having 1 to 10 carbon atoms.
Further, the free radical initiator is azo initiator or organic peroxy initiator.
Further, azo initiator is azobisisobutyronitrile, and organic peroxide initiator is dibenzoyl peroxide.
Among the free radical initiators used in the method of the invention, azo initiators such as azobisisobutyronitrile are available commercial reagents, and no special treatment is required; organic peroxy initiators such as dibenzoyl peroxide are used after recrystallization to remove water.
Further, the free radical initiator is used in an amount of 1% -5% by mole of the pinacol styrene 1-borate.
Further, the copolymer monomer acrylic ester, acrylamide, acrylonitrile, maleic anhydride and maleimide are all available commercialized reagents, wherein the acrylic ester, the acrylamide and the acrylonitrile need to be subjected to redistillation treatment to remove polymerization inhibitors; the maleic anhydride and maleimide require recrystallization treatment.
Further, the copolymer monomer acrylate, acrylamide, acrylonitrile, maleic anhydride and maleimide are used in an amount of 33-100% by mole of the pinacol styrene 1-borate.
Further, the organic solvent is selected from but not limited to toluene. The organic solvent is a commercial reagent, and is distilled under nitrogen atmosphere after being dried by sodium metal, and the dosage of the organic solvent is preferably 100 microliters/0.5 mmol of 1-boric acid pinacol ester styrene.
Further, the reaction time was 24 to 96 hours, wherein the reaction temperature for azobisisobutyronitrile was 65℃and for dibenzoyl peroxide was 70 ℃.
Further, the heating process of the reaction can adopt a metal heating module for heating or an oil bath (such as silicone oil, paraffin oil and the like) or other heating modes.
Further, the product is subjected to post-treatment after the completion of the reaction, including precipitation or purification by means of preparative permeation gel chromatography, followed by drying by means of a vacuum oven; wherein, the precipitation is only feasible for the product IIIc, IIId, IIIe, methanol can be used as a poor solvent in the precipitation process, and dichloromethane is used as a good solvent; the purification by using the preparative permeation gel chromatograph is applicable to all products, and chloroform is used as eluent in the purification process; the drying by using the vacuum drying oven is suitable for all products, and the duration of the drying process is more than 24 hours.
The method for preparing the alternating copolymer by taking the 1-boric acid pinacol ester styrene as a comonomer can respectively carry out free radical copolymerization with acrylic ester, acrylamide, acrylonitrile, maleic anhydride and maleimide, has low reaction cost and can obtain valuable alternating copolymer. Compared with the prior art, the invention has the following advantages:
1. the invention takes 1-boric acid pinacol ester styrene as a comonomer, which can expand the range of substrates, such as acrylic ester, acrylamide, acrylonitrile, maleic anhydride, maleimide and the like, and can construct various alternative copolymers;
2. the invention takes the 1-boric acid pinacol ester styrene as a comonomer, is a commercially available compound, and has low cost and convenient acquisition;
3. the invention takes 1-boric acid pinacol ester styrene as a comonomer, the reaction condition does not involve metal participation, and the product has no metal residue;
4. the invention takes 1-boric acid pinacol ester styrene as a comonomer, has mild reaction conditions and is convenient and simple to operate.
5. According to the invention, the 1-boric acid pinacol ester styrene is used as a comonomer, and the prepared copolymer has higher glass transition temperature, so that the copolymer can supplement the application range of polystyrene.
Detailed Description
In order to make the technical features and advantages or technical effects of the above technical solution of the present invention more obvious and understandable, the following detailed description is given with reference to the embodiments.
Example 1
Synthesis of Poly (1-boronic acid pinacol ester styrene-alternate-n-butyl acrylate)
The 1-boronic acid pinacol styrene (921 mg,4.0mmol,2.0 equiv), the initiator azobisisobutyronitrile (6.56 mg,0.04mmol,0.02 equiv), n-butyl acrylate (256 mg,2.0mmol,1.0 equiv) and toluene (400 μl) were added to a 4mL vial of a polytetrafluoroethylene cap under a nitrogen atmosphere. The reaction system was heated to 65℃and reacted for 96 hours. The polymerization was brought back to room temperature and quenched. The reaction system was diluted with chloroform and purified by preparative permeation gel chromatography. The separated product is dried in a vacuum drying oven to obtain a pure product. The product was a white powdery solid in 68% yield. The structure of the product is shown below:
the nuclear magnetic data are as follows:
1 H NMR(400MHz，CD 2 Cl 2 )：δ7.52-6.68(m，5H)，3.56-0.62(m，26H)； 13 C NMR(151MHz，CD 2 Cl 2 )：δ175.9，143.1，128.9，127.3，125.0，83.3，63.7，43.5，39.8，34.5，30.2，25.0，20.2，13.9。
example 2
Synthesis of Poly (1-boronic acid pinacol ester styrene-alternate-N, N-dimethylacrylamide)
The 1-boronic acid pinacol styrene (921 mg,4.0mmol,2.0 equiv), the initiator azobisisobutyronitrile (6.56 mg,0.04mmol,0.02 equiv), N, N-dimethylacrylamide (198mg, 2.0mmol,1.0 equiv) and toluene (400 μl) were added to a 4mL vial of a polytetrafluoroethylene vial cap under a nitrogen atmosphere. The reaction system was heated to 65℃and reacted for 96 hours. The polymerization was brought back to room temperature and quenched. The reaction system was diluted with chloroform and purified by preparative permeation gel chromatography. The separated product is dried in a vacuum drying oven to obtain a pure product. The product was a white powdery solid in 46% yield. The structure of the product is shown below:
the nuclear magnetic data are as follows:
1 H NMR(400MHz，CD 2 Cl 2 )：δ7.06(br，5H)，2.95-0.80(m，23H)； 13 C NMR(151MHz，CD 2 Cl 2 )：δ175.3，144.2，129.5，127.4，125.2，83.1，46.5，36.8，35.6，25.6。
example 3
Synthesis of Poly (1-boronic acid pinacol ester styrene-alternan-acrylonitrile)
The 1-boronic acid pinacol styrene (921 mg,4.0mmol,2.0 equiv), the initiator azobisisobutyronitrile (6.56 mg,0.04mmol,0.02 equiv), acrylonitrile (106 mg,2.0mmol,1.0 equiv) and toluene (400 μl) were added to a 4mL vial of a polytetrafluoroethylene vial cap under a nitrogen atmosphere. The reaction system was heated to 65℃and reacted for 96 hours. The polymerization was brought back to room temperature and quenched. The reaction system was precipitated with methanol at room temperature. The separated product is dried in a vacuum drying oven to obtain a pure product. The product was a white powdery solid in 75% yield. The structure of the product is shown below:
the nuclear magnetic data are as follows:
1 H NMR(400MHz，CD 2 Cl 2 )：δ7.22(br，5H)，2.46-1.36(m，5H)，1.37-0.92(m，12H)； 13 C NMR(151MHz，CD 2 Cl 2 )：δ142.4，141.8，128.8，128.1，126.9，123.0，84.8，84.6，43.3，40.5，36.7，34.7，25.4，25.1。
example 4
Synthesis of Poly (1-boronic acid pinacol ester styrene-alternate-maleic anhydride)
The 1-boronic acid pinacol styrene (690 mg,3.0mmol,1.5 equiv), the initiator azobisisobutyronitrile (6.56 mg,0.04mmol,0.02 equiv), maleic anhydride (196 mg,2.0mmol,1.0 equiv) and toluene (400 μl) were added to a 4mL vial of polytetrafluoroethylene cap under nitrogen. The reaction system was heated to 65℃and reacted for 24 hours. The polymerization was brought back to room temperature and quenched. The reaction system was precipitated with methanol at room temperature. The separated product is dried in a vacuum drying oven to obtain a pure product. The product was a white powdery solid in 68% yield. The structure of the product is shown below:
the nuclear magnetic data are as follows: 1 H NMR(400MHz，CD 2 Cl 2 )：δ8.28-6.17(m，5H)，4.01-1.75(m，4H)，1.19(br，12H)； 13 C NMR(151MHz，CD 2 Cl 2 )：δ174.07，172.75，139.96，129.86，128.86，86.62，86.39，84.83，76.34，43.69，38.28，26.63，25.89，25.72，25.43。
example 5
Synthesis of Poly (1-boronic acid pinacol ester styrene-alternate-N-ethylmaleimide)
The 1-boronic acid pinacol styrene (69mg, 3.0mmol,1.5 equiv), the initiator azobisisobutyronitrile (6.56 mg,0.04mmol,0.02 equiv), N-ethylmaleimide (250 mg,2.0mmol,1.0 equiv) and toluene (400 μl) were added to a 4mL vial of a polytetrafluoroethylene vial cap under a nitrogen atmosphere. The reaction system was heated to 65℃and reacted for 48 hours. The polymerization was brought back to room temperature and quenched. The reaction system was precipitated with methanol at room temperature. The separated product is dried in a vacuum drying oven to obtain a pure product. The product was a white powdery solid in 68% yield. The structure of the product is shown below:
the nuclear magnetic data are as follows:
1 H NMR(400MHz，CD 2 Cl 2 )：δ7.08(br，5H)，3.93-0.39(m，21H)； 13 C NMR(151MHz，CD 2 Cl 2 )：δ179.2，143.2，128.0，84.2，83.5，40.6，36.7，34.2，25.7，13.3。
although the present invention has been described with reference to the above embodiments, it should be understood that the invention is not limited thereto, and that modifications and equivalents may be made thereto by those skilled in the art, which modifications and equivalents are intended to be included within the scope of the present invention as defined by the appended claims.
Claims (10)
- Use of pinacol 1-borate styrene for the preparation of an alternating copolymer, characterized in that pinacol 1-borate styrene is used as comonomer for the preparation of an alternating copolymer.
- 2. Use according to claim 1, wherein the pinacol 1-borate styrene is used as comonomer for the preparation of an alternating copolymer, the preparation step comprising:using free radical initiator, using 1-boric acid pinacol ester styrene as one comonomer, and one of acrylic ester, acrylamide, acrylonitrile, maleic anhydride and maleimide as another comonomer, wherein the two comonomers are in N 2 And (3) carrying out reaction in an organic solvent under the protection of atmosphere to obtain the alternating copolymer poly (1-boric acid pinacol styrene-alternating-copolymer).
- 3. The use according to claim 2, wherein the equations are each as follows:in the formula I, ia represents 1-boric acid pinacol ester styrene, IIa represents acrylic ester, R 1 Represents various alkyl groups, IIIa represents poly (pinacol 1-borate styrene-alternate-copolymer);in formula II, iaTABLE 1 pinacol borate styrene, IIb represents acrylamide, R 2 And R is 3 Represents various alkyl groups, IIIb represents a poly (pinacol 1-borate styrene-alternate-copolymer);in formula III, ia represents 1-boronic acid pinacol ester styrene, IIc represents acrylonitrile, IIIc represents poly (1-boronic acid pinacol ester styrene-alternating copolymer);in formula IV, ia represents 1-boronic acid pinacol ester styrene, IId represents maleic anhydride, IIId represents poly (1-boronic acid pinacol ester styrene-alternate-copolymer);in the formula V, ia represents 1-boric acid pinacol ester styrene, IIe represents maleimide, R 4 Represents various alkyl groups, IIIe represents poly (pinacol 1-borate styrene-alternate-copolymer).
- 4. The use according to claim 3, wherein R in formula I 1 Is an alkyl group having 1 to 10 carbon atoms; r in formula II 2 、R 3 Is an alkyl group having 1 to 10 carbon atoms; r in V 4 Is an alkyl group having 1 to 10 carbon atoms.
- 5. Use according to claim 2 or 3, wherein the free radical initiator is selected from azo initiators or organic peroxy initiators; azo initiator is azobisisobutyronitrile, and organic peroxide initiator is dibenzoyl peroxide; the free radical initiator is used in an amount of 1-5% by mole of the pinacol 1-borate styrene.
- 6. Use according to claim 2 or 3, characterized in that acrylic acid esters, acrylamide, acrylonitrile are treated by re-evaporation to remove polymerization inhibitors and then used as comonomers; maleic anhydride and maleimide are used as comonomers after recrystallization treatment.
- 7. Use according to claim 2 or 3, characterized in that the copolymer monomer acrylate, acrylamide, acrylonitrile, maleic anhydride or maleimide is used in an amount of 33% to 100% by mole of the 1-boronic acid pinacol styrene.
- 8. Use according to claim 2 or 3, characterized in that toluene is used as the organic solvent, which is distilled under nitrogen after drying with sodium metal, in an amount of 100 μl/0.5 mmol of 1-boronic acid pinacol ester styrene.
- 9. Use according to claim 2 or 3, characterized in that the reaction time is 24-96h.
- 10. Use according to claim 2 or 3, wherein the product is subjected to a post-treatment after the reaction is completed, said post-treatment comprising: first, precipitation is carried out, or purification is carried out by using a preparative permeation gel chromatograph; and then dried using a vacuum drying oven.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310844206.1A CN116903790A (en) | 2023-07-11 | 2023-07-11 | Application of 1-boric acid pinacol ester styrene in preparation of alternating copolymer |
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| CN202310844206.1A CN116903790A (en) | 2023-07-11 | 2023-07-11 | Application of 1-boric acid pinacol ester styrene in preparation of alternating copolymer |
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