CN107739439B - Preparation method of hyperbranched polythioether - Google Patents
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- CN107739439B CN107739439B CN201711045172.0A CN201711045172A CN107739439B CN 107739439 B CN107739439 B CN 107739439B CN 201711045172 A CN201711045172 A CN 201711045172A CN 107739439 B CN107739439 B CN 107739439B
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- C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
- C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
Abstract
The invention relates to a preparation method of hyperbranched polythioether. The invention takes difunctional asymmetric alkene compounds and trifunctional mercaptan as raw materials, and utilizes the mercapto-alkene non-isoactive addition reaction to synthesize hyperbranched polythioether by a one-pot method. The method has the advantages of easily obtained raw materials and simple steps, and the prepared hyperbranched polythioether has the end group of sulfydryl and can be further subjected to functional modification, so that the hyperbranched polythioether with specific performance is prepared.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to a preparation method of hyperbranched polythioether, belonging to the field of organic polymers.
[ background of the invention ]
The hyperbranched polymer molecule has a three-dimensional ellipsoidal structure, a cavity is arranged in the molecule, a large number of reactive groups are arranged at the tail end, and compared with the dendritic polymer, the hyperbranched polymer has simple synthesis steps and good industrial application prospect.
Currently, hyperbranched polythioethers are mainly AB2And A2+B3Two preparation methods are provided. Chinese patent (CN2016105865276) synthesizes AB containing sulfydryl and double bond by multi-step reaction with thioctic acid as raw material2The hyperbranched polythioether based on the lipoic acid is prepared by using a monomer and a sulfydryl-alkene click chemistry reaction. But AB2The types of monomers are few, and most of the monomers need complicated organic synthesis processes; and A is2+B3The polymer system is very easy to crosslink due to poor selectivity in the reaction process.
The invention takes bifunctional asymmetric alkene compound as AA' monomer and trifunctional thiol as B3The hyperbranched polythioether with a controllable structure is synthesized by using a mercapto-alkene non-isoactive addition reaction and a one-pot method by using monomers. The AA ' monomer adopted by the invention comprises 3- (acryloyloxy) -2-hydroxypropyl methacrylate, 2- (acryloyloxy) ethyl methacrylate, allyl acrylate and allyl methacrylate, the reactivity of the alkene with sulfydryl in A and A ' in the AA ' monomer is greatly different, wherein the acrylate has a great difference in the reactivity, and the molecular structure of the alkene is different from that of the sulfydryl>>Methacrylic acid esters>>The alkyl alkene is prepared by controlling the reaction conditions,first, an AB-like can be generated2The hyperbranched polythioether is obtained by further polymerizing the type micromolecule intermediate, and the polymerization system is controllable and effectively avoids crosslinking. The method has the advantages of easily obtained raw materials and simple steps, and the prepared hyperbranched polythioether can be further functionally modified by taking the end group of the thiol.
The invention content is as follows:
the invention relates to a preparation method of hyperbranched polythioether, which can be applied to various aspects, such as resin auxiliary agents, photocuring coatings, biological medicines, food packaging materials, electronic packaging materials and other fields.
A hyperbranched polythioether characterized in that: the skeleton contains thioether, the end group is sulfydryl, the weight-average molecular weight is 1.5-50 KDa, the polydispersity index is 1.1-1.6, and the degree of branching of the polymer is 0.5-0.8; the hyperbranched polymer has the following structural formula:
the one-pot method for preparing hyperbranched polythioether according to claim 1 comprises the following steps: adding 1.0-1.2 mol of trifunctional mercaptan, 1.0 mol of difunctional asymmetric alkene monomer, 0-0.05 mol of catalyst, 0-0.02 mol of initiator and solvent into a reactor at one time, and reacting at a certain temperature for 12-96 h; and after the reaction is finished, carrying out rotary evaporation and concentration on the reaction liquid, dissolving the reaction liquid again by using chloroform, precipitating the reaction liquid in anhydrous ether, repeating the dissolving-precipitating operation for 3 times, and drying the precipitate in vacuum to obtain the hyperbranched polythioether product.
The one-pot process for preparing a hyperbranched polythioether of claim 2, wherein the solvent is selected from the group consisting of tetrahydrofuran, dioxane, and N, N-dimethylformamide.
The one-pot process for preparing hyperbranched polythioethers as defined in claim 2 wherein the catalyst is selected from one of triethylamine, dimethylaminopyridine, 1, 5-diazabicyclo [4.3.0] -5-nonene, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene.
The one-pot process for preparing hyperbranched polythioethers as defined in claim 2, wherein the initiator is selected from the group consisting of azobisisobutyronitrile and dibenzoyl peroxide.
The invention has the advantages that:
1. the hyperbranched polythioether with adjustable and controllable active end group is prepared by a one-pot method, the reaction activities of alkene with sulfydryl in A and A 'different molecular structures in AA' monomer are greatly different, and the acrylate is>>Methacrylic acid esters>>The alkyl alkene can firstly generate similar AB by controlling the reaction conditions2And (4) further polymerizing the small molecule type intermediate to form the hyperbranched polythioether. In the whole reaction process, no gel phenomenon occurs, the synthetic raw materials are cheap and easy to obtain, the synthetic method is simple, and the yield is high.
2. The preparation of the hyperbranched polythioether has high selective activity, thioether is in a product skeleton, the end group is sulfydryl, and the molecular weight and the branching degree are high and controllable; this method has unique advantages over conventional methods, such as: not easy to gel, simple and easy to operate, high controllability and the like.
Description of the drawings:
FIG. 1 is a schematic diagram of the chemical structures of hyperbranched polythioethers prepared in examples 1-10.
FIG. 2 is a Fourier infrared absorption spectrum of a hyperbranched polythioether prepared in example 1.
FIG. 3 is a drawing of hyperbranched polythioethers prepared in example 11H-NMR spectrum.
FIG. 4 is a gel permeation chromatogram of a hyperbranched polythioether prepared in example 1.
The specific implementation method comprises the following steps:
the invention is further illustrated below with reference to specific embodiments. It is to be understood that the present invention is not limited to the following embodiments, which are regarded as conventional methods unless otherwise specified. The materials are commercially available from the open literature unless otherwise specified.
Cases 1-10 are examples of preparation of hyperbranched polythioethers.
Example 1:
9.965g (25mmol) of 2-ethyl acetateGlycerol trimercaptopropionate, 75mL of tetrahydrofuran and 5.355g (25mmol) of 3- (acryloyloxy) -2-hydroxypropyl methacrylate and 0.1265g (1.25mmol) of triethylamine were added in one portion to a reactor at 40 ℃ under N2Protection reaction is carried out for 48 h; after the reaction is finished, the reaction liquid is concentrated by rotary evaporation, dissolved again by chloroform and precipitated in anhydrous ether, the operations of dissolution and precipitation are repeated for 3 times, and the precipitate is dried in vacuum to obtain a colorless viscous liquid product, namely the hyperbranched polythioether (12.68 g, the yield is 82.8%).
FIG. 2 is an infrared absorption spectrum of the hyperbranched polythioether prepared in example 1, wherein a stretching vibration absorption peak of OH is at 3505cm-1, a characteristic absorption peak of sulfydryl is at 2540cm-1, and the characteristic peak of double bond at 1600cm-1 disappears completely, thus proving that the hyperbranched polythioether is successfully synthesized.
FIG. 3 is a nuclear magnetic hydrogen spectrum of the hyperbranched polythioether prepared in example 1, wherein the proton signal peak of the terminal thiol group is at 1.64ppm, and the branching degree of the hyperbranched polythioether is calculated by the integral of characteristic peaks to be 0.65.
FIG. 4 is a gel permeation chromatogram of a hyperbranched polythioether prepared in example 1, having M of the hyperbranched polythioetherwAt 7500 Da, the polymer polydispersity PDI was 1.40.
Example 2:
9.965g (25mmol) 2-ethylglycerol trimercaptopropionate, 75mL dioxane and 5.355g (25mmol)3- (acryloyloxy) -2-hydroxypropyl methacrylate and 0.1265g (1.25mmol) triethylamine were added in one portion to a reactor at 40 ℃ under N2Protection reaction is carried out for 48 h; after the reaction is finished, the reaction liquid is concentrated by rotary evaporation, dissolved again by chloroform and then precipitated in anhydrous ether, the operations of dissolution and precipitation are repeated for 3 times, and the precipitate is dried in vacuum to obtain a colorless viscous liquid product, namely the hyperbranched polythioether (12.44 g, the yield is 81.2%).
Example 3:
10.961g (27.5mmol) 2-ethylglycerol trimercaptopropionate, 75mL tetrahydrofuran and 5.355g (25mmol)3- (acryloyloxy) -2-hydroxypropyl methacrylate and 0.1265g (1.25mmol) triethylamine were added in one portion to a reactor at 40 ℃ C. under the condition of N2Protection reaction is carried out for 24 h; after the reaction is finished, the reaction solutionConcentrating by rotary evaporation, dissolving again by chloroform, precipitating in anhydrous ether, repeating the dissolving-precipitating operation for 3 times, and drying the precipitate in vacuum to obtain the product of the hyperbranched polythioether (11.13g, 68.2% yield) as colorless viscous liquid.
Example 4:
9.965g (25mmol) 2-ethylglycerol trimercaptopropionate, 75mL tetrahydrofuran and 5.355g (25mmol)3- (acryloyloxy) -2-hydroxypropyl methacrylate were added in one portion to a reactor at 40 ℃ under N2Protection reaction is carried out for 96 h; after the reaction is finished, the reaction liquid is concentrated by rotary evaporation, redissolved by chloroform and precipitated in anhydrous ether, the operations of dissolution and precipitation are repeated for 3 times, and the precipitate is dried in vacuum to obtain a colorless viscous liquid product, namely the hyperbranched polythioether (12.91g, the yield is 84.3%).
Example 5:
9.965g (25mmol) of 2-ethylglycerol trimercaptopropionate, 75mL of tetrahydrofuran and 5.355g (25mmol) of 3- (acryloyloxy) -2-hydroxypropyl methacrylate and 0.174g (1.25mmol) of 1,5, 7-triazabicyclo- [4.4.0]Adding the-deca-5-ene into a reactor at one time, and adding N at 40 DEG C2Protection reaction is carried out for 48 h; after the reaction is finished, the reaction liquid is concentrated by rotary evaporation, redissolved by chloroform and precipitated in anhydrous ether, the operations of dissolution and precipitation are repeated for 3 times, and the precipitate is dried in vacuum to obtain a colorless viscous liquid product, namely the hyperbranched polythioether (12.0g, the yield is 78.2%).
Example 6:
9.965g (25mmol) of 2-ethylglycerol trimercaptopropionate, 75mL of N, N-dimethylformamide, 3.154g (25mmol) of allyl methacrylate, 0.1265g (1.25mmol) of triethylamine and 0.082g (0.5mmol) of azobisisobutyronitrile were added in one portion to a reactor at 80 ℃ under N2Protection reaction is carried out for 48 h; after the reaction is finished, the reaction liquid is concentrated by rotary evaporation, dissolved again by chloroform and precipitated in anhydrous ether, the operations of dissolution and precipitation are repeated for 3 times, and the precipitate is dried in vacuum to obtain the product of the hyperbranched polythioether (9.50 g of colorless viscous liquid, the yield is 72.4%).
Example 7:
4.357g (25mmol) of trimercaptan, 75mL of tetrahydrofuran and 5.355g (25mmol) of 3- (acryloyloxy) -2-hydroxypropyl methacrylate and 0.1265g (1.25mol) triethylamine were added in one portion to the reactor at 50 ℃ N2Protection reaction is carried out for 72 h; after the reaction is finished, the reaction liquid is concentrated by rotary evaporation, dissolved again by chloroform and then precipitated in anhydrous ether, the operations of dissolution and precipitation are repeated for 3 times, and the precipitate is dried in vacuum to obtain a colorless viscous liquid product, namely the hyperbranched polythioether (7.05g, the yield is 72.6%). Example 8:
4.357g (25mmol) of trimebuthiol, 75mL of N, N-dimethylformamide, 3.154g (25mmol) of allyl methacrylate, 0.1265g (1.25mmol) of triethylamine and 0.082g (0.5mmol) of azobisisobutyronitrile were added in one portion to the reactor at 80 ℃ under N2Protection reaction is carried out for 48 h; after the reaction is finished, the reaction liquid is concentrated by rotary evaporation, dissolved again by chloroform and then precipitated in anhydrous ether, the operations of dissolution and precipitation are repeated for 3 times, and the precipitate is dried in vacuum to obtain a colorless viscous liquid product, namely the hyperbranched polythioether (5.21g, the yield is 69.4%).
Example 9:
9.238g (25mmol) ((3-mercaptopropionyl) dialkyl) bis (ethane-2, 1-diyl) bis (3-mercaptopropionate), 75mL of tetrahydrofuran and 5.355g (25mmol) of 2-hydroxypropyl 3- (acryloyloxy) -methacrylate and 0.1265g (1.25mol) of triethylamine were charged in one portion to a reactor at 40 ℃ under N2Protection reaction is carried out for 48 h; after the reaction is finished, the reaction liquid is concentrated by rotary evaporation, dissolved again by chloroform and then precipitated in anhydrous ether, the operations of dissolution and precipitation are repeated for 3 times, and the precipitate is dried in vacuum to obtain a colorless viscous liquid product, namely the hyperbranched polythioether (10.74g, the yield is 73.6%).
Example 10:
9.238g (25mmol) ((3-mercaptopropionyl) dialkyl) bis (ethane-2, 1-diyl) bis (3-mercaptopropionate), 75mL of N, N-dimethylformamide and 3.154g (25mmol) of allyl methacrylate, 0.1265g (1.25mmol) of triethylamine and 0.082g (0.5mmol) of azobisisobutyronitrile were added in one portion to the reactor at 80 ℃ under N2Protection reaction is carried out for 48 h; after the reaction is finished, the reaction liquid is evaporated and concentrated in a rotary mode, dissolved again by chloroform and then precipitated in anhydrous ether, the operations of dissolving and precipitating are repeated for 3 times, and the precipitate is dried in vacuum to obtain a colorless viscous liquid product, namely the hyperbranched polythioether (9.52g, product yield)The rate was 76.8%).
Claims (5)
1. A preparation method of hyperbranched polythioether is characterized in that difunctional asymmetric alkene compounds and trifunctional mercaptan are used as raw materials, and a one-pot method is used for preparing the hyperbranched polythioether by utilizing a mercapto-alkene non-equal activity addition reaction; the hyperbranched polythioether is characterized in that: the skeleton contains thioether, the end group is sulfydryl, the weight-average molecular weight is 1.5-50 KDa, the polydispersity index is 1.1-1.6, and the branching degree is 0.5-0.8; the hyperbranched polythioether has the following structure:
the above-mentioned
The attachment positions in (a) are three propionate termini.
2. The method for preparing a hyperbranched polythioether according to claim 1, wherein the one-pot method is used for preparing the hyperbranched polythioether by the following specific steps: adding 1.0-1.2 mol of trifunctional mercaptan, 1.0 mol of difunctional asymmetric alkene monomer, 0-0.05 mol of catalyst, 0-0.02 mol of initiator and solvent into a reactor at one time, and reacting at a certain temperature for 12-96 h; and after the reaction is finished, carrying out rotary evaporation and concentration on the reaction liquid, dissolving the reaction liquid again by using chloroform, precipitating the reaction liquid in anhydrous ether, repeating the dissolving-precipitating operation for 3 times, and drying the precipitate in vacuum to obtain the hyperbranched polythioether product.
3. The method of claim 2, wherein the solvent is selected from the group consisting of tetrahydrofuran, dioxane, and N, N-dimethylformamide.
4. The method of claim 2, wherein the catalyst is one selected from the group consisting of triethylamine, dimethylaminopyridine, 1, 5-diazabicyclo [4.3.0] -5-nonene, and 1,5, 7-triazabicyclo [4.4.0] dec-5-ene.
5. The method of claim 2, wherein the initiator is selected from the group consisting of azobisisobutyronitrile and dibenzoyl peroxide.
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| CN108912360A (en) * | 2018-07-02 | 2018-11-30 | 仲恺农业工程学院 | A kind of high flexibility hemicellulose film and preparation method thereof |
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| CN110283314B (en) * | 2019-06-20 | 2022-04-22 | 江南大学 | Method for preparing hyperbranched polythioether |
| CN110760064B (en) * | 2019-10-30 | 2021-12-24 | 贵州民族大学 | Multi-responsiveness dendritic polymer prepared by visible light-initiated thiol-ene click reaction and method thereof |
| CN110698672A (en) * | 2019-10-30 | 2020-01-17 | 贵州民族大学 | Multi-responsiveness dendritic polythioether polymer prepared by visible light-initiated thiol-ene click reaction and method thereof |
| CN111450307B (en) * | 2020-04-08 | 2021-06-04 | 江南大学 | Preparation method of double-component medical adhesive |
| CN114031707B (en) * | 2020-07-20 | 2023-08-15 | 中国石油化工股份有限公司 | Cured material composition and application thereof, cured resin and preparation method and application thereof |
| CN111944392B (en) * | 2020-08-25 | 2021-08-24 | 江南大学 | Hyperbranched polythioether/epoxy acrylate resin composite photocureable coating and preparation method and application thereof |
| CN115232311B (en) * | 2022-08-09 | 2023-11-14 | 河源然生新材料有限公司 | Synthesis method of hyperbranched methacrylate |
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| CN102181054A (en) * | 2011-02-22 | 2011-09-14 | 浙江大学 | Method for preparing hyperbranched polymer through dual click chemistry |
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| US7361728B1 (en) * | 2004-09-30 | 2008-04-22 | Tda Research, Inc. | Electrically conducting materials from branched end-capping intermediates |
| CN102153751A (en) * | 2011-02-22 | 2011-08-17 | 浙江大学 | Method for preparing hyperbranched polymer by adopting consecutive click chemical reaction |
| CN102181054A (en) * | 2011-02-22 | 2011-09-14 | 浙江大学 | Method for preparing hyperbranched polymer through dual click chemistry |
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