CN108864333B - Preparation method of liquid siloxanyl fluorine polymer - Google Patents
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Abstract
The invention discloses a preparation method of a liquid siloxanyl fluoropolymer. Firstly, preparing a liquid end carboxyl chloride-based fluoropolymer by taking the liquid end carboxyl fluoropolymer as a raw material and taking thionyl chloride or oxalyl chloride as an acylation reagent, wherein the carboxyl conversion rate can reach 70-88%; then, the liquid acyl chloride-terminated fluorine polymer and the siloxane compound containing amino are subjected to amidation reaction, and the liquid siloxane-terminated fluorine polymer is prepared by adopting an indirect method and a direct method respectively, wherein the conversion rate of the amidation reaction is close to 100%. The invention has simple preparation process, low raw material cost and high product yield, and the product can be used as an adhesive, a joint mixture, a coating, a processing accessory ingredient and the like.
Description
Technical Field
The invention relates to a preparation method of a liquid siloxanyl fluorine polymer.
Background
Liquid fluoropolymers have gradually become high-performance materials essential in the national defense and aviation industries due to their excellent thermal stability, chemical resistance, and incomparable properties of fluidity, plasticity, easy processing, etc. of solid fluoropolymers.
At present, a common liquid fluoropolymer is a liquid fluoropolymer containing terminal carboxyl and terminal hydroxyl, and since the reactivity of the terminal group directly affects the thermal stability and curing performance of the liquid fluoropolymer, introducing a functional group with related performance into the molecular chain of the liquid fluoropolymer is the most direct and effective method for further improving the thermal stability and reducing the curing temperature of the liquid fluoropolymer. Among many polymers, the polymer containing siloxane groups often has the properties of normal temperature curing, good fluidity, high temperature resistance and the like, so that the siloxane functional groups are introduced into the liquid fluorine polymer, so that the good fluidity can be kept, the thermal stability can be improved, and the curing temperature can be reduced. Therefore, the preparation of liquid-end siloxanyl fluoropolymers has important significance and value.
Disclosure of Invention
The invention discloses a preparation method of a liquid siloxanyl fluoropolymer. Firstly, preparing a liquid end carboxyl chloride-based fluoropolymer by taking the liquid end carboxyl fluoropolymer as a raw material and taking thionyl chloride or oxalyl chloride as an acylation reagent, wherein the carboxyl conversion rate can reach 70-88%; then, the liquid acyl chloride-terminated fluorine polymer and the siloxane compound containing amino are subjected to amidation reaction, and the liquid siloxane-terminated fluorine polymer is prepared by research through an indirect method and a direct method respectively, wherein the conversion rate of the amidation reaction is close to 100%. The invention has simple preparation process, low raw material cost and high product yield, and the product can be used as an adhesive, a joint mixture, a coating, a processing accessory ingredient and the like.
The invention is realized by the following technical scheme: specifically, a liquid carboxyl-terminated fluoropolymer is used as a raw material, and firstly, the liquid carboxyl-terminated fluoropolymer is prepared through acylation reaction; then, carrying out amidation reaction on the liquid end acyl chloride-based fluorine polymer and a siloxane compound containing amino, and respectively preparing the liquid end siloxane-based fluorine polymer by adopting an indirect method or a direct method, wherein the method specifically comprises the following steps:
(a) first, a liquid end-chloro-fluoropolymer was prepared by mixing a polymer having a number average molecular weight of 0.5 × 103～5×104Dissolving the liquid carboxyl-terminated fluoropolymer in an organic solvent in a single-mouth bottle, quickly adding an acylation reagent into the single-mouth bottle at room temperature, adding a catalyst, reacting at a certain temperature, and obtaining a product containing the liquid acyl chloride-terminated fluoropolymer after the reaction is finished. Wherein the acylating reagent can be anhydrous thionyl chloride or oxalyl chloride, is preferably thionyl chloride, the molar ratio of carboxyl to thionyl chloride is 1: 1.5-1: 3.0, is preferably 1: 2.0-1: 2.5, and the reaction is carried out for 4-10 hours at 65-90 ℃, the reaction temperature is preferably 70-80 ℃, and the reaction time is preferably 4-8 hours; when the acylating reagent is oxalyl chloride, the molar ratio of carboxyl to oxalyl chloride is 1: 3.0-1: 5.0, the reaction temperature is 25-60 ℃, and the reaction time is 6-40 hours; the catalyst can be anhydrous pyridine, triethylamine or N, N-dimethylformamide, and is preferably pyridine; the dosage of the catalyst is 0.05-0.5% of the mass of the raw materials, and preferably 0.15-0.25%.
(b) Then, a liquid-end siloxanyl fluoropolymer was prepared: adding a siloxane compound containing amino and a catalyst into the product obtained in the step (a), magnetically stirring at room temperature for reaction, washing the crude product by using petroleum ether after the reaction is finished, and removing the solvent by rotary evaporation to obtain the liquid siloxane-based fluoropolymer. Wherein the siloxane compound containing amino group can be 3-aminopropyltriethoxysilane, diethylaminomethyltriethoxysilane or p-aminophenyltrimethoxysilane, preferably 3-aminopropyltriethoxysilane, p-aminophenyltrimethoxysilane; the molar ratio of the acyl chloride group to the amino group in the siloxane compound is 1: 1.0-1: 2.0, preferably 1: 1.1-1: 1.5; the catalyst can be anhydrous pyridine, triethylamine or N, N-dimethylformamide, and is preferably triethylamine; the dosage of the catalyst is 0.05-0.3% of the mass of the raw materials, preferably 0.1-0.2% of the mass of the raw materials; the reaction is carried out for 4 to 28 hours, and the reaction time is preferably 6 to 24 hours.
Further, in the above technical scheme, in the step (a), after the reaction is finished, the solvent is removed by rotary evaporation to obtain a viscous liquid, namely the liquid end acyl chloride-based fluoropolymer; and (b) dissolving the product obtained in the step (a) in an organic solvent again and then continuing the subsequent process.
Further, in the above technical solution, the liquid carboxyl-terminated fluoropolymer raw material is an oligomer having a fluorine atom in a main chain or a side chain carbon atom and a carboxyl group at a chain end.
Further, in the above technical solution, the liquid carboxyl-terminated fluoropolymer may be a fluoroolefin binary copolymer containing terminal carboxyl, and is selected from vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, vinylidene fluoride-perfluoromethyl vinyl ether copolymer, vinylidene fluoride-hexafluoropropylene copolymer, and vinylidene fluoride-perfluoroethyl vinyl ether copolymer; the copolymer may be a fluoroolefin terpolymer containing a terminal carboxyl group, selected from vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, vinylidene fluoride-tetrafluoroethylene-perfluoromethyl vinyl ether terpolymer and vinylidene fluoride-tetrafluoroethylene-perfluoroethyl vinyl ether terpolymer, preferably a vinylidene fluoride-hexafluoropropylene copolymer, a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer and a vinylidene fluoride-tetrafluoroethylene-perfluoromethyl vinyl ether terpolymer.
Further, in the above technical scheme, the organic solvent for dissolving the raw materials is one or a compound organic solvent. Dichloromethane, cyclohexane, acetonitrile, toluene, acetone and tetrahydrofuran can be selected, and dichloromethane, acetone and tetrahydrofuran are preferred.
Further, the liquid siloxane-terminated fluoropolymer is characterized by infrared spectroscopy (FTIR), which is as follows: the infrared spectrum of the product is shown in 1128cm-1A stretching vibration peak of-Si-O-Si-group appears at 1684cm-1The characteristic peak of carbonyl connected with amine appears at 2984cm-1And 2891cm-1A clear C-H absorption peak appears at 3432cm-1The stretching vibration peak of-NH-appears.
The method takes liquid carboxyl-terminated fluorine polymer as a raw material, and firstly synthesizes the liquid acyl chloride-terminated fluorine polymer by a functional group conversion method; and then, selecting a siloxane compound containing amino to perform amidation reaction with the liquid acyl chloride-terminated fluoropolymer to prepare the liquid siloxane-terminated fluoropolymer. The preparation process is simpler, and the target product can be prepared by adopting an indirect method and a direct method; the cost of raw materials is lower, and expensive pentafluorophenol and a compound catalytic system are not needed to participate in the reaction. The product prepared by the invention can be used as an adhesive, a joint mixture, a coating, a processing accessory ingredient and the like.
Advantageous effects of the invention
The invention not only can prepare the liquid siloxane-based fluoropolymer, but also provides a new idea for converting the functional group of the liquid fluoropolymer terminal. According to the property and reaction mechanism of organic functional groups, the liquid acyl chloride-terminated fluoropolymer with high-activity end groups is designed and prepared, and a universal reactive group is provided for continuous functional group conversion. The liquid acyl chloride-terminated fluorine polymer is reacted with the siloxane compound containing amino, and the flowable liquid siloxane-terminated fluorine polymer with better thermal stability can be prepared by both an indirect method and a direct method. The invention has simple preparation process, low raw material cost and high product yield, and the product can be used as an adhesive, a joint mixture, a coating, a processing accessory ingredient and the like.
Detailed Description
The following non-limiting examples will allow one of ordinary skill in the art to more fully understand the present invention, but are not intended to limit the invention in any way.
The liquid carboxyl-terminated fluoropolymer used in the following examples is self-made in the laboratory, but is not limited to the liquid carboxyl-terminated fluoropolymer used in the examples, and the preparation method is described in patent CN 101717464A.
Example 1
20g of liquid carboxyl-terminated fluorine polymer (vinylidene fluoride-hexafluoropropylene copolymer, 2.5 percent of carboxyl by mass and 3500 percent of number average molecular weight), 11.1mmol of carboxyl content is dissolved in 200ml of tetrahydrofuran, thionyl chloride (2.64g, 22.2mmol) and 40mg of pyridine are added, the temperature is raised to 70 ℃ for reflux reaction for 6 hours, after the reaction is finished, the solvent is removed by rotary evaporation to obtain viscous liquid, then 200m L of tetrahydrofuran is added into the first-step product at room temperature for complete dissolution again, after the sample is dissolved, 3-aminopropyl triethoxysilane (2.36g, 10.65mmol) and 30mg of triethylamine are added for reaction for 18 hours at room temperature, after the reaction is finished, the crude product is poured into petroleum ether for washing, then the solvent in the product is removed by rotary evaporation, the carboxyl conversion rate of the liquid fluorine polymer can reach 86.7 percent, compared with the liquid carboxyl-terminated fluorine rubber, the liquid siloxane-terminated fluorine rubber has good thermal decomposition temperature which is raised from 241 ℃ to 274 ℃ and has carbon residue rate which is up to 600 ℃ and is 47.98 percent and has good fluidity.
Example 2
The preparation and the test were carried out according to example 1, except that the acylation reaction was carried out under different conditions, i.e., at 75 ℃ for 4 hours, and the conversion rate reached 72.4%.
Example 3
The preparation and testing were carried out as in example 1, except that the amounts of acylating agent and catalyst were different, thionyl chloride (2.91g, 24.4mmol), and pyridine as catalyst were 30mg, and the conversion reached 80.7%.
Example 4
The preparation and testing were carried out as in example 1, except that 3-aminopropyltriethoxysilane was used in a different amount, 3-aminopropyltriethoxysilane (2.79g, 12.59mmol) achieved a conversion of 86.8%.
Example 5
Preparation and testing were carried out as in example 1, except that the siloxane compound was different, p-aminophenyltrimethoxysilane (2.27g, 10.65mmol), and the conversion reached 87.1%.
Example 6
The preparation and the test are carried out according to the example 1, except that the catalyst dosage is different, the catalyst triethylamine dosage is 40mg, and the conversion rate reaches 81.2%.
Example 7
The preparation and the test were carried out as in example 1, except that the amidation reaction time was different, the reaction time was 8h, and the conversion rate reached 86.4%.
Example 8
The preparation and the test were carried out according to example 1, except that the acylation reaction was carried out in a solvent of 50m L dichloromethane and 50ml acetone, and the conversion rate reached 80.2%.
Example 9
The preparation and the test were carried out as in example 1, with the difference that no intermediate work-up procedure was carried out, the amidation reaction time was 6 hours, the catalyst triethylamine was 20mg, and the conversion rate reached 84.6%.
Example 10
20g of liquid carboxyl-terminated fluorine polymer (vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, the mass percentage of carboxyl is 3.2%, and the number average molecular weight is 4200), the content of carboxyl is 14.2mmol, the fluorine polymer is dissolved in 200ml of tetrahydrofuran, thionyl chloride (4.23g, 35.5mmol) and 40mg of pyridine are added, the temperature is raised to 70 ℃ for reflux reaction for 8h, after the reaction is finished, the solvent is removed by rotary evaporation, viscous liquid is obtained, 200m L of tetrahydrofuran is added into the first-step product at room temperature, the first-step product is completely dissolved again, after the sample is dissolved, 3-aminopropyltriethoxysilane (4.15g, 18.76mmol) and 40mg of triethylamine are added, the reaction is carried out for 24h at room temperature, after the reaction is finished, the crude product is poured into petroleum ether for washing, the solvent in the pure product is removed by rotary evaporation, the carboxyl conversion rate of the liquid fluorine polymer can reach 87.3%, compared with the liquid carboxyl-terminated fluorine rubber, the thermal decomposition temperature of the liquid-terminated silicone-terminated fluorine rubber is raised to 312 ℃, the carbon has a high residual rate of 49.3% when the temperature reaches 600 ℃, and the residual rate is high, compared with.
Example 11
The preparation and the test are carried out according to the embodiment 10, and the difference is an amidation reaction solvent and reaction time, wherein the solvent comprises 50ml of dichloromethane and 50ml of tetrahydrofuran, the reaction time is 10 hours, and the conversion rate can reach 86.5 percent;
example 12
20g of liquid carboxyl-terminated fluorine polymer (vinylidene fluoride-tetrafluoroethylene-perfluoromethyl vinyl ether copolymer, 3.4 percent of carboxyl by mass and 3500 percent of number average molecular weight), 15.1mmol of carboxyl is dissolved in 200ml of tetrahydrofuran, thionyl chloride (3.95g, 33.2mmol) and 35mg of pyridine are added, the temperature is raised to 80 ℃ for reflux reaction for 5 hours, after the reaction is finished, the solvent is removed by rotary evaporation to obtain viscous liquid, 200m L of tetrahydrofuran is added into the first-step product at room temperature to be completely dissolved again, after the sample is dissolved, p-aminophenyltrimethoxysilane (3.89g, 18.25mmol) and 25mg of triethylamine are added for reaction for 20 hours at room temperature, after the reaction is finished, the crude product is poured into petroleum ether for washing, the solvent in the product is removed by rotary evaporation, the carboxyl conversion rate of the liquid fluorine polymer can reach 85.8 percent, compared with the liquid carboxyl-terminated fluorine rubber, the thermal decomposition temperature of the liquid-terminated siloxane-terminated fluorine rubber is raised from 252 ℃ to 305 ℃ and the carbon residue rate when the temperature is raised to 600 ℃ is high and has good fluidity and has 50.06 percent.
The products of examples 1 to 12 were characterized by infrared spectroscopy (FTIR) at 1128cm-1A stretching vibration peak of-Si-O-Si-group appears at 1684cm-1The characteristic peak of carbonyl connected with amine appears at 2984cm-1And 2891cm-1A clear C-H absorption peak appears at 3432cm-1The stretching vibration peak of-NH-appears.
The embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (8)
1. A method for preparing a liquid siloxanyl fluoropolymer is characterized by comprising the following steps:
(a) first, a liquid acid-terminated chloro-fluoropolymer was prepared by placing the polymer in a single-neck flask at a number average molecular weight of 0.5 × 103~5×104Dissolving liquid carboxyl-terminated fluoropolymer in an organic solvent, quickly adding an acylating reagent at room temperature, adding a catalyst, reacting at a certain temperature, and obtaining a product containing the liquid acyl chloride-terminated fluoropolymer after the reaction is finished;
(b) then, a liquid siloxane-terminated fluoropolymer is prepared: adding a siloxane compound containing amino and a catalyst into the product obtained in the step (a), magnetically stirring at room temperature for reaction, washing the crude product by using petroleum ether after the reaction is finished, and removing the solvent by rotary evaporation to obtain a liquid siloxane-based fluoropolymer;
in step (a), the acylating agent is selected from anhydrous thionyl chloride and oxalyl chloride; when the acylating agent is thionyl chloride, the molar ratio of carboxyl to thionyl chloride is 1: 1.5-1: 3.0; when the acylating reagent is oxalyl chloride, the molar ratio of carboxyl to oxalyl chloride is 1: 3.0-1: 5.0;
in steps (a) and (b), the catalyst is selected from anhydrous pyridine, triethylamine, N-dimethylformamide; the dosage of the acylation reaction catalyst is 0.05-0.5% of the mass of the raw materials; the dosage of the amidation reaction catalyst is 0.05-0.3% of the mass of the raw materials;
in step (a), the acylation reaction temperature; when the acylating reagent is thionyl chloride, the reaction temperature is 65-90 ℃; when the acylating reagent is oxalyl chloride, the reaction temperature is 25-60 ℃;
in the step (a), when the acylation reaction time is thionyl chloride, the reaction time is 2-10 hours; when the acylating reagent is oxalyl chloride, the reaction time is 6-40 hours;
in the step (b), the molar ratio of the acyl chloride group to the amino group in the siloxane compound is 1: 1.0-1: 2.0;
in the step (b), the amidation reaction time is 4-28 hours.
2. The method of claim 1, wherein said liquid carboxyl-terminated fluoropolymer is a polymer containing fluorine atoms at the carbon atoms of the backbone or side chain and carboxyl groups at the chain end, said polymer being an oligomer.
3. The method of claim 1, wherein said liquid carboxyl-terminated fluoropolymer is a carboxyl-terminated fluoroolefin-based co-or terpolymer.
4. The method of claim 1, wherein the liquid carboxyl-terminated fluoropolymer is a carboxyl-terminated fluoroolefin-based copolymer selected from the group consisting of vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, vinylidene fluoride-perfluoromethyl vinyl ether copolymer, vinylidene fluoride-hexafluoropropylene copolymer, and vinylidene fluoride-perfluoroethyl vinyl ether copolymer.
5. The method of claim 1, wherein the liquid carboxyl-terminated fluoropolymer is a carboxyl-terminated fluoroolefin terpolymer selected from the group consisting of vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, vinylidene fluoride-tetrafluoroethylene-perfluoromethyl vinyl ether terpolymer, and vinylidene fluoride-tetrafluoroethylene-perfluoroethyl vinyl ether terpolymer.
6. The method according to claim 1, wherein the organic solvent is selected from one or more of dichloromethane, cyclohexane, acetonitrile, toluene, acetone and tetrahydrofuran.
7. The method according to claim 1, wherein the amino group-containing siloxane compound is selected from the group consisting of 3-aminopropyltriethoxysilane, diethylaminomethyltriethoxysilane, and p-aminophenyltrimethoxysilane.
8. The method according to any one of claims 1 to 7, wherein in the step (a), after the reaction is finished, the solvent is removed by rotary evaporation to obtain a viscous liquid, namely the liquid end acyl chloride-based fluoropolymer; and (b) dissolving the product obtained in the step (a) in an organic solvent again and then continuing the subsequent process.
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| US4853737A (en) * | 1988-05-31 | 1989-08-01 | Eastman Kodak Company | Roll useful in electrostatography |
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| US4853737A (en) * | 1988-05-31 | 1989-08-01 | Eastman Kodak Company | Roll useful in electrostatography |
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| Title |
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| 一种新型封端剂的合成、表征和应用;廖明义等;《合成橡胶工业》;20140115;第72页 * |
| 不同酰化试剂合成液体端酰氯基氟橡胶的研究;李东翰等;《橡塑技术与装备》;20171201;第43卷(第23期);第11-17页 * |
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