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CN-122011363-A - Hyperbranched polyether-ether-ketone for toughening epoxy resin and preparation method and application thereof

CN122011363ACN 122011363 ACN122011363 ACN 122011363ACN-122011363-A

Abstract

The invention relates to novel hyperbranched polyether-ether-ketone and application thereof in toughening modification of epoxy resin. The HPEEK has a unique structure, comprises a rigid polyether-ether-ketone skeleton and a reactive end group, and can realize the comprehensive mechanical property improvement of 'toughening without damaging strong' when being used as a toughening agent in epoxy resin. Specifically, after a proper amount of HPEEK toughening agent is added, the impact strength, tensile strength and bending strength of the epoxy resin are obviously enhanced, meanwhile, excellent thermal stability is maintained, and the glass transition temperature can be increased by 15-20 ℃ to be more than 160 ℃. In addition, the toughening system has good high temperature resistance, and is suitable for high-performance composite materials, packaging materials, structural members, wear-resistant components and the like in the fields of aerospace, electronics, electrical, mechanical manufacturing and civil use.

Inventors

  • PENG XIAOJUN
  • FAN YUTAO
  • FAN JIANGLI
  • DU JIANJUN
  • CHEN PENGZHONG
  • WANG DONGPING

Assignees

  • 大连理工大学

Dates

Publication Date
20260512
Application Date
20260317

Claims (10)

  1. 1. The hyperbranched polyether-ether-ketone used for toughening and modifying the epoxy resin is characterized by having a structure shown in a general formula I; I Wherein n is selected from any integer from 1 to 25; r 1 is substituent CH 3 or CF 3 ; R 2 is hydroxy or epoxy methoxy.
  2. 2. The method for preparing the epoxy resin toughened and modified hyperbranched polyetheretherketone according to claim 1, comprising the following steps: Step 1, adding a triphenol compound, difluorobenzophenone (DFK), a catalyst potassium carbonate, solvent sulfolane and water-carrying agent toluene into a reaction container, carrying out staged heating reaction for 8-12 hours at 120-190 ℃ under inert conditions, carrying out precipitation, washing, hot filtration and reprecipitation purification on reaction liquid to obtain hydroxyl-terminated hyperbranched polyether ether ketone (HPEEK-OH), wherein the mol ratio of the triphenol compound to the difluorobenzophenone is 1 (0.5-1), the mass ratio of the triphenol compound to the potassium carbonate is 1 (1.5-2.2), the solvent sulfolane is used for completely dissolving all reactants, and the water-carrying agent toluene is 40-50% of the solvent sulfolane; Sequentially adding HPEEK-OH, epichlorohydrin, sodium hydroxide, tetrabutylammonium bromide and N-methylpyrrolidone (NMP) into a reaction container, reacting at a constant temperature of 85-95 ℃ for 8-12 h under an inert atmosphere, precipitating, washing, filtering, removing impurities, reprecipitating and purifying the reaction solution to obtain epoxy group-terminated hyperbranched polyether ether ketone (HPEEK-EO), wherein the ratio of the substances of hydroxyl, epichlorohydrin and sodium hydroxide in HPEEK-OH is 1 (10-20) (1.5-2.5), the addition amount of tetrabutylammonium bromide is 0.05-0.15% of the total mass of the reaction system, and the NMP is taken as a reaction solvent, and the use amount of the NMP is based on that all reactants in the reaction system can be completely dissolved.
  3. 3. The method according to claim 2, wherein the trisphenol compound in step 1 is one of TPE, THPE, TFPE.
  4. 4. A modified epoxy toughening system utilizing the hyperbranched polyetheretherketone of claim 1, comprising the following components: 95-110 parts by weight of epoxy resin, 1-5 Parts by weight of hyperbranched polyether-ether-ketone toughening agent, A curing agent; wherein the ratio of the total moles of active hydrogen in the curing agent to the total moles of epoxy groups in the epoxy resin is 0.9:1 to 1.1:1.
  5. 5. The system of claim 4, wherein a solvent is added in an amount of 40-50% by mass of the epoxy resin during the mixing process to promote the mixing, wherein the solvent is one selected from cyclopentanone and n-butanol, and is removed in a subsequent defoaming process.
  6. 6. The system according to claim 4, wherein the epoxy resin is at least one selected from the group consisting of glycidyl ether type epoxy resins, and the curing agent is at least one selected from the group consisting of aliphatic amines.
  7. 7. The system according to claim 4, wherein the glycidyl ether type epoxy resin is at least one of bisphenol A type epoxy resin and bisphenol F type epoxy resin, and the aliphatic amine is at least one selected from 4,4' -diaminodicyclohexylmethane, isophoronediamine and cyclohexanediamine.
  8. 8. A method of preparing the modified epoxy toughening system of claim 4 comprising the steps of: Step 1, adding a toughening agent and a solvent in proportion, heating and stirring until the toughening agent and the solvent are uniform; Step 2, after the epoxy resin is fully preheated to be in a flowing state, adding the mixed solution in the step 1, heating and stirring until the mixed solution is uniform, stopping heating and stirring, and cooling the mixed solution; And 3, adding a curing agent into the mixed system in the step 2 in proportion at normal temperature, stirring until the mixture is uniform, and defoaming to obtain a final product.
  9. 9. The method according to claim 8, wherein: the heating temperature in the step 1 is 40-100 ℃, the stirring rotation speed is 500-1500 rpm, and the stirring time is 15-60 min; The preheating temperature in the step 2 is 40-100 ℃ and the preheating time is 10-30 min; the heating temperature in the step 2 is 40-100 ℃, the stirring rotation speed is 500-1500 rpm, and the stirring time is 15-60 min; in the step 3, the stirring rotation speed is 500-1500 rpm, and the stirring time is 30-60 min; In the step 3, the vacuum degree of the vacuum drying oven ranges from-0.095 to-0.099 MPa, the temperature ranges from 30 ℃ to 60 ℃ and the defoaming time ranges from 5 minutes to 20 minutes.
  10. 10. The application of the hyperbranched polyether-ether-ketone modified epoxy resin toughening system as claimed in claim 4, wherein the application comprises the preparation of composite materials for aerospace, packaging materials and insulating parts in the field of electronics and electrical, structural parts and wear-resistant parts in the field of mechanical manufacturing, and high-performance adhesive and anti-corrosion coating products in the civil field.

Description

Hyperbranched polyether-ether-ketone for toughening epoxy resin and preparation method and application thereof Technical Field The invention belongs to the technical field of high polymer material modification, and particularly relates to a hyperbranched polyether-ether-ketone modified epoxy resin toughening system and a preparation method thereof. Background Epoxy resin is used as high-performance thermosetting resin, and is widely applied to the high-end engineering fields of aerospace, electronic and electric, transportation, civil engineering and the like by virtue of excellent mechanical strength, adhesion, thermal stability and chemical inertness. However, epoxy resin and curing agents such as amines, anhydrides and the like are crosslinked to form a highly compact three-dimensional crosslinked network structure, and the inherent defects of high brittleness and poor impact resistance exist, so that the application of the epoxy resin in a high impact load scene is limited. The development of the efficient toughening strategy realizes the cooperative optimization of toughness, strength and modulus, and is the core direction of the high-performance modification of the epoxy resin. The traditional toughening agent (rubber, nano particles and the like) is easy to cause the problem of toughening loss and strength, while the traditional hyperbranched toughening agent is mostly aliphatic, the glass transition temperature (Tg) of the flexible chain segment can be reduced, the applicability of high-temperature service is restricted, and the high-performance expansion of the epoxy resin is seriously hindered. Notably, although aromatic Polyetheretherketone (PEEK) has a high Tg and a rigid backbone, its linear structure is difficult to introduce into hyperbranched topologies and lacks reactive end groups that can participate in epoxy curing, and no report has been made of PEEK building blocks for the construction of reactive hyperbranched tougheners, resulting in a long-term blank of the "rigid backbone toughening" path in epoxy systems. Therefore, developing an epoxy resin toughening agent which has excellent toughening effect and high-temperature stability and can realize 'toughening without damaging strong' becomes a technical problem to be solved in the current field. Disclosure of Invention Aiming at the problems that the epoxy resin in the prior art is large in brittleness, the traditional toughening agent is easy to cause the deterioration of strength and thermal performance, and the existing aliphatic hyperbranched toughening agent is poor in high-temperature stability, the invention provides hyperbranched polyether-ether-ketone and a preparation method thereof. The first aspect of the invention provides hyperbranched polyether-ether-ketone which can be used for toughening and modifying epoxy resin, and has a structure shown in a general formula I; I wherein n is selected from any integer from 1 to 25, preferably from any integer from 5 to 15; R 1 is a substituent CH 3 or CF 3, preferably CF 3;R2 is hydroxy or epoxy methoxy, preferably epoxy methoxy; the most preferred structural formula of formula I is shown below as II: Structure II According to a second aspect of the invention, the preparation method of the epoxy resin toughened and modified hyperbranched polyether ether ketone comprises the following steps: The preparation method comprises the steps of 1, adding a triphenol compound, difluorobenzophenone (DFK), a catalyst potassium carbonate, solvent sulfolane and water-carrying agent toluene into a reaction container, carrying out staged heating reaction for 8-12 hours at 120-190 ℃ under inert conditions, carrying out precipitation, washing, hot filtering and reprecipitation purification on a reaction solution to obtain hydroxyl-terminated hyperbranched polyether-ether-ketone (HPEEK-OH), wherein the molar ratio of the triphenol compound to the difluorobenzophenone is 1 (0.5-1), more preferably 1 (0.7-0.8), the mass ratio of the triphenol compound to the potassium carbonate is 1 (1.5-2.2), more preferably 1.8-1.9), the dosage of the solvent sulfolane is 60% -70% of the total mass of the reaction system so as to completely dissolve all reactants and ensure that the reaction is uniformly carried out, and the dosage of the solvent sulfolane is 40-50% of the total mass of the solvent sulfolane. Sequentially adding HPEEK-OH, epichlorohydrin, sodium hydroxide, tetrabutylammonium bromide and N-methylpyrrolidone (NMP) into a reaction container, reacting at a constant temperature of 85-95 ℃ for 8-12 h under an inert atmosphere, precipitating, washing, filtering, removing impurities, reprecipitating and purifying the reaction solution to obtain epoxy group-terminated hyperbranched polyether ether ketone (HPEEK-EO), wherein the ratio of the substances of hydroxyl, epichlorohydrin and sodium hydroxide in HPEEK-OH is 1 (10-20): 1.5-2.5), the preferable range is 1 (14-16): 1.9-2.1), tetrabutylammonium bromide is us