CN109762139B - Preparation method of thermosetting polymer capable of being welded, repaired and reprocessed and molded at medium temperature - Google Patents
Preparation method of thermosetting polymer capable of being welded, repaired and reprocessed and molded at medium temperature Download PDFInfo
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Abstract
The invention discloses a preparation method of a thermosetting polymer which can be welded and repaired at medium temperature and can be reprocessed and molded, wherein a polymer reaction monomer and a curing agent with exchangeable dynamic bonds and active groups such as carboxyl, hydroxyl or amino are reacted under the condition of a dynamic bond exchange reaction catalyst to obtain the thermosetting polymer with multiple exchangeable dynamic bonds, the thermosetting polymer with multiple exchangeable dynamic bonds can be reprocessed and molded at medium temperature, the thermosetting polymer has solvent resistance under high temperature, and the solvent is an inert high-boiling-point solvent. The method introduces multiple exchangeable dynamic bonds into the thermosetting polymer, so that the exchange reaction of various exchangeable dynamic bonds can be carried out simultaneously, the exchange reaction rate in the cross-linked network is faster, the cross-linked network is more quickly recombined, the reprocessing and forming of materials are easier, and the reprocessing, forming, welding and repairing of the thermosetting polymer are realized at medium temperature.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a preparation method of a weldable, repairable and reprocessable thermosetting polymer at a medium temperature.
Background
Thermosetting polymers (such as epoxy polymers) are widely used from aerospace to rail transit, from electronic components to household appliances, from office supplies to biological devices, because of their excellent mechanical properties, excellent structural stability and good solvent resistance. However, thermoset polymers are difficult to reprocess and recycle after molding. In contrast, uncrosslinked thermoplastic polymers can be easily reshaped and recycled under heating conditions, but lose good solvent resistance and excellent mechanical properties. Therefore, how to combine the advantages of thermosetting polymers and thermoplastic polymers remains a great problem in designing thermosetting polymers that are solvent resistant and can be reprocessed into shapes.
Leibler et al for the first time prepared a novel thermoset polymer with dynamic covalent bond exchange reaction using an epoxy resin and a polybasic acid or anhydride. In the crosslinking network, the breaking of dynamic bonds and regeneration are carried out in situ simultaneously, and the old crosslinking points are broken only by regenerating new crosslinking points, so that the crosslinking density of the polymer can be kept unchanged all the time in the reprocessing and forming process. Based on dynamic bond exchange reaction, the thermosetting polymer can realize reprocessing and forming of materials on the premise of keeping a cross-linked network structure, and has good solvent resistance even at high temperature because the cross-linked density is always kept unchanged. Along with the temperature rise, the exchange rate of covalent bonds in the thermosetting polymer based on covalent bond exchange is accelerated, the crosslinked network is recombined, and the modulus and viscosity of the polymer are gradually reduced, so that the reprocessing and molding of the thermosetting polymer at high temperature are realized. In the reworkable process of thermosetting polymers based on covalent bond exchange, the rate of covalent bond exchange plays a decisive role, which leads to the fact that reworkable processes often require high temperatures for a long time and are under severe conditions. For example, the epoxy resin based on ester bond exchange requires more than 200 ℃ to realize reprocessing and molding (Science,2011,334,965 and 968); the reprocess molding temperatures of thermosetting polymers based on transamination are also above 150 ℃ (adv. funct. mater, 2015,25, 2451-; the reprocess molding temperature of the disulfide bond-based epoxy polymer is as high as 200 deg.C (Mater Horiz,2016,3, 241-. The repair temperature of thermosetting polymers based on dynamic D-A bonds is also 130 deg.C (Science,2002,295, 1698-1702). The high-temperature reprocessing and molding not only wastes a large amount of energy, but also can cause serious damage to other important parts (such as core electronic elements) in the product, so that the preparation method of the high-temperature solvent-resistant thermosetting polymer which can be welded and repaired at medium temperature and can be reprocessed and molded can further open up a new application field for the reprocessed and molded thermosetting polymer.
Disclosure of Invention
The invention aims to provide a method for preparing a moderate temperature weldable repairable and reprocessable molded thermosetting polymer, which can prepare the moderate temperature weldable repairable and reprocessable molded and high temperature solvent-resistant thermosetting polymer by introducing multiple exchangeable dynamic bonds into the thermosetting polymer. Compared with the thermosetting polymer with only one exchangeable ester bond, in the thermosetting polymer with multiple exchangeable dynamic bonds, the exchange reaction of multiple exchangeable dynamic bonds can be carried out simultaneously, the exchange reaction rate in the cross-linked network can be faster, the recombination of the cross-linked network can be quicker, the welding and repairing and the re-processing and forming of materials can be easier, and the re-processing and forming of the thermosetting polymer and the welding and repairing can be realized at medium temperature.
In order to achieve the technical effects, the invention provides a preparation method of a weldable, repairable and reprocessable thermosetting polymer at a medium temperature, which comprises the step of reacting a polymer reaction monomer with a curing agent having exchangeable dynamic bonds and active groups such as carboxyl, hydroxyl or amino under the condition of a dynamic bond exchange reaction catalyst to obtain the thermosetting polymer with multiple exchangeable dynamic bonds, wherein the thermosetting polymer with multiple exchangeable dynamic bonds can be reprocessed and molded at the medium temperature and can be welded and repaired, the thermosetting polymer with multiple exchangeable dynamic bonds has solvent resistance under the high-temperature condition, and the solvent is an inert high-boiling-point solvent.
The further technical scheme is that the polymer monomer is any one of epoxy resin, isocyanate and organic silane monomer.
The curing agent is selected from any one of carboxylic acid curing agents with disulfide bonds, carboxylic acid or amine curing agents with siloxane and carboxylic acid curing agents capable of generating ester bonds.
The further technical proposal is that the catalyst is selected from any one of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, zinc acetate, zinc acetylacetonate or triphenylphosphine.
The further technical scheme is that the reaction temperature is 150-200 ℃, and the reaction time is 2-6 hours.
The further technical proposal is that the reaction temperature is 180 ℃ and the reaction time is 4 hours.
The further technical scheme is that the inert high-boiling point solvent is selected from one or more of trichlorobenzene, phenetole, o-dimethyl ether and o-diethyl ether, and the specific temperature under the high-temperature condition is more than 150 ℃.
Further, the exchangeable dynamic bond is selected from the group consisting of a D-A bond, a carboxylic ester bond, an ethyleneamino ester bond, a phenylboronic acid ester bond, a siloxane bond, a disulfide bond, an aromatic disulfide bond, an exchangeable alkyl group, an exchangeable olefin group, and any dynamic covalent bond and dynamic non-covalent bond capable of undergoing an exchangeable reaction.
The further technical scheme is that the processing temperature for reprocessing, forming, welding and repairing at the medium temperature is 60-120 DEG C
The further technical proposal is that the number of the exchangeable dynamic keys is 2 to n, wherein n is an integer larger than 2.
The further technical scheme is that the thermosetting polymer is selected from any polymer capable of introducing dynamic bonds, such as polyurethane, epoxy resin, organic silicon, polyimide, phenolic resin and the like.
The present invention selects the introduction of double (or multiple) exchangeable dynamic bonds as dynamic cross-linking points in the thermoset polymer, which, with increasing temperature, simultaneously start the exchange reaction in the cross-linked network. Since the cleavage and regeneration of dynamic bonds occur simultaneously in situ during the exchange reaction, the crosslinked network has excellent high temperature solvent resistance. And because the reaction rate of the double (or multiple) exchangeable dynamic bonds is higher than that of the single exchangeable dynamic bond, the recombination of the crosslinked network in the polymer is more efficient, the reprocessing and shaping of materials can be realized at moderate temperature, and the repair and welding can be realized. On the premise of keeping the high-temperature solvent resistance of the thermosetting polymer, the realization of reworkable molding, welding and repairing of the material at the medium temperature is more advantageous in practical application. The invention provides a convenient new way for reprocessing, molding and recycling the thermosetting polymer and the composite material thereof.
Drawings
FIG. 1 is a schematic representation of the intermediate temperature reprocess molding of a thermoset polymer having multiple exchangeable dynamic bonds;
FIG. 2 is a schematic representation of the excellent high temperature solvent resistance of thermosetting polymers having multiple exchangeable dynamic bonds;
FIG. 3 is a schematic illustration of the mechanism of solderable repairable and reworkable molding of a thermoset polymer having multiple exchangeable dynamic bonds;
FIG. 4 is a schematic representation of crack repair at moderate temperatures for thermoset polymers with multiple exchangeable dynamic bonds;
FIG. 5 is a schematic representation of the moderate temperature soldering of a thermosetting polymer having multiple exchangeable dynamic bonds.
Detailed Description
Example 1:
the carboxylic acid curing agent with disulfide bonds reacts with epoxy resin for crosslinking to obtain the epoxy polymer with double exchangeable dynamic bonds of disulfide bonds and carboxylic ester bonds. The specific preparation process is as follows: bisphenol A glycidyl ether is used as a reaction monomer, dithio-dibutyric acid is used as a curing agent, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene is used as an ester bond exchange catalyst, the reaction monomer, the curing agent and the catalyst are stirred uniformly at 100 ℃, and then poured into a mold to react for 4 hours at 180 ℃, so that the epoxy polymer with double exchangeable dynamic bonds of disulfide bonds and carboxylic ester bonds is prepared. Although the reactive monomer and the curing agent are both dicrotic compounds, hydroxyl groups generated by the reaction of the carboxylic acid with the epoxy can further react with the epoxy or the carboxylic acid, resulting in the formation of branched and crosslinked network structures. The solvent resistance and reworkability of epoxy polymers with double exchangeable dynamic bonds of disulfide and carboxylate bonds were investigated at moderate temperatures. The reworking and molding process of the epoxy polymer having double exchangeable dynamic bonds of disulfide bond and carboxylic ester bond when treated at 100 ℃ for 1 hour is shown in FIG. 1. The high temperature solvent resistance of epoxy polymers with double exchangeable dynamic bonds of disulfide and carboxylate bonds in trichlorobenzene solvent is shown in FIG. 2.
Example 2:
epoxy resin with aromatic disulfide bonds reacts with amine curing agent with siloxane for crosslinking to obtain the epoxy polymer with double reversible dynamic bonds of disulfide bonds and siloxane bonds. The specific preparation process is as follows: epoxy with aromatic disulfide bonds is used as a reaction monomer, amine chemicals with siloxane are used as a curing agent, the reaction monomer and the curing agent are uniformly stirred at 100 ℃, poured into a mold and reacted for 4 hours at 150 ℃, and the epoxy polymer with the double reversible dynamic bonds of disulfide bonds and silicon-oxygen bonds is obtained.
Example 3:
epoxy resin with siloxane reacts with a sebacic acid curing agent to obtain an epoxy polymer with ester bonds and double reversible dynamic bonds of the reaction of the siloxane. The specific preparation process is as follows: epoxy resin with siloxane is used as a reaction monomer, sebacic acid is used as a curing agent, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene is used as an ester bond exchange catalyst, the reaction monomer, the curing agent and the catalyst are stirred uniformly at 100 ℃, and then poured into a mold to react for 4 hours at 180 ℃, so that the epoxy polymer with double reversible dynamic bonds of ester bonds and silicon-oxygen bonds is obtained.
Comparative example 1
The specific preparation process is as follows: bisphenol A glycidyl ether is used as a reaction monomer, sebacic acid is used as a curing agent, 1,5, 7-triazabicyclo [4.4.0] dec-5-ene is used as an ester bond exchange catalyst, the reaction monomer, the curing agent and the catalyst are stirred uniformly at 100 ℃, poured into a mold and reacted for 4 hours at 180 ℃, and the epoxy polymer only with ester bonds capable of exchanging dynamic bonds is prepared. As can be seen from fig. 1, the polymers prepared by this process cannot be reprocessed at moderate temperatures.
Comparative example 2
The specific preparation process is as follows: bisphenol A glycidyl ether is used as a reaction monomer, dithio-dibutyric acid is used as a curing agent, the reaction monomer and the curing agent are uniformly mixed at 100 ℃, poured into a mould and reacted for 4 hours at 180 ℃, and the epoxy polymer only containing disulfide bond exchangeable dynamic bonds is prepared. As can be seen from fig. 1, the polymers prepared by this process cannot be reprocessed at moderate temperatures.
Although the present invention has been described herein with reference to the illustrated embodiments thereof, which are intended to be preferred embodiments of the present invention, it is to be understood that the invention is not limited thereto, and that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure.
Claims (6)
1. A method for preparing a thermosetting polymer which can be welded and repaired and reprocessed and molded at medium temperature is characterized in that a polymer reaction monomer and a curing agent with exchangeable dynamic bonds and carboxyl, hydroxyl or amino active groups are reacted under the condition of a dynamic bond exchange reaction catalyst to obtain the thermosetting polymer with multiple exchangeable dynamic bonds, the thermosetting polymer with multiple exchangeable dynamic bonds can be reprocessed and molded at medium temperature and can be welded and repaired, the thermosetting polymer with multiple exchangeable dynamic bonds has solvent resistance under high temperature, the solvent is an inert high-boiling-point solvent, the exchangeable dynamic bonds are selected from carboxylic ester bonds, ethylene urethane bonds, phenyl boronic acid ester bonds, silicon oxygen bonds and disulfide bonds, the polymer monomer is selected from epoxy resin, isocyanate and organic silicon bondsAny one of alkane monomers, the curing agent is selected from any one of carboxylic acid curing agents with disulfide bonds, carboxylic acid or amine curing agents with siloxane and carboxylic acid curing agents capable of generating ester bonds, and the processing temperature of reprocessing, molding, welding and repairing at the medium temperature is 60-120 DEG CoC。
2. The method for preparing the moderate temperature weldable repairable and reprocessable molded thermosetting polymer according to claim 1, wherein the catalyst is selected from any one of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, zinc acetate, zinc acetylacetonate or triphenylphosphine.
3. The method of claim 1, wherein the reaction temperature is 150-200 ℃ and the method comprisesoAnd C, the reaction time is 2-6 hours.
4. The method for preparing the intermediate-temperature weldable, repairable and reprocessable thermosetting polymer as claimed in claim 1, wherein the inert high-boiling-point solvent is selected from one or more of trichlorobenzene, phenetole, o-dimethylether and o-diethylether, and the specific temperature under the high-temperature condition is 150%oAnd C is higher than the C.
5. The method of claim 1, wherein the number of exchangeable dynamic bonds is 2-n, where n is an integer greater than 2.
6. The method of claim 1 wherein the thermosetting polymer is selected from the group consisting of polyurethane, epoxy, silicone, polyimide, and phenolic.
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| CN110564109B (en) * | 2019-10-14 | 2022-03-15 | 中国工程物理研究院化工材料研究所 | Preparation method of high-strength solvent-resistant epoxy fiber composite material capable of being rapidly disassembled and recycled |
| CN110627998B (en) * | 2019-10-14 | 2022-06-03 | 中国工程物理研究院化工材料研究所 | Method for regulating and controlling stress relaxation and reprocessing molding temperature of glass-like polymer material through dynamic bond content |
| CN113150277B (en) * | 2021-04-02 | 2023-01-13 | 天目湖先进储能技术研究院有限公司 | Self-healing polyimide conductive adhesive, preparation method, electrode plate and lithium battery |
| CN113956440B (en) * | 2021-11-19 | 2023-11-03 | 河南省科学院化学研究所有限公司 | High-density dynamic bond epoxy resin crosslinked network and preparation method thereof |
| CN114292384B (en) * | 2021-12-27 | 2023-09-01 | 西安隆基乐叶光伏科技有限公司 | Epoxy resin composition, cured epoxy resin composition, paste, method for preparing same, and electrode |
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