CN115651165A - Recyclable epoxy resin and preparation method and recycling method thereof - Google Patents
Recyclable epoxy resin and preparation method and recycling method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of recyclable epoxy resin, and relates to a recyclable epoxy resin, and a preparation method and a recycling method thereof. The recyclable epoxy resin comprises the following components in percentage by mass: 45-65% of epoxy resin raw material, 35-55% of curing agent and 0.05-5% of catalyst. The preparation method comprises the following specific steps: the components are heated and mixed uniformly, degassed in a vacuum state and then cured to obtain the recyclable epoxy resin with the recycling performance. The invention can dissolve the cured recyclable epoxy resin in the composite solvent under the heating condition, and then recover the composite solvent and the low molecular weight epoxy resin by using a reduced pressure distillation mode. The invention has simple preparation and recovery process, can be used in the fields of epoxy pavements and fan blades, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of recyclable epoxy resin, and particularly relates to a recyclable epoxy resin, and a preparation method and a recycling method thereof.
Background
Epoxy resin is a synthetic thermosetting polymer for preparing composite materials, and is widely applied to the fields of coatings, composite materials, adhesives and the like due to excellent mechanical property, bonding property and low curing shrinkage rate. However, since the epoxy resin is a thermoplastic linear structural monomer before being cured, the application value of the epoxy resin is often embodied only by crosslinking with a curing agent and generating an infusible and insoluble crosslinked network. So that the waste of resources is caused because the waste can not be reprocessed or recycled.
At present, the recyclable epoxy resins reported in the literature mainly focus on introducing dynamic covalent bonds with certain environmental stimulus responsiveness into the molecular structure, and the dynamic covalent polymers with certain environmental stimulus responsiveness have been used as a sustainable alternative material of thermosetting materials, also called glass-like polymers (vitrimers), which have the dual advantages of both thermosetting polymers and thermoplastic polymers. Such epoxy resins are known as covalently compliant networks, and include ester, disulfide, imine, and hexahydro-s-triazine structures, among others. However, the imine bond curing process generates byproduct water in situ, which can cause adverse effects on the performance of the cured resin and industrial production; the preparation process of the molecule containing the disulfide bond and the hexahydro-s-triazine structure is complex.
Chinese patent CN114989562A discloses a recyclable metallographic phase embedding material and a preparation method thereof, and aims at solving the problem that an epoxy resin metallographic phase embedding material cannot be recycled after being embedded once, the recyclable metallographic phase embedding material is provided, and by adding a dynamic chemical bond into a thermosetting resin matrix, the thermosetting resin can be cracked and recombined under the stimulation of light, heat, acid, alkali and the like, so that the reprocessing of the resin is realized. The method realizes the recycling of the metallographic phase embedding material and avoids the waste of the embedding material after the sample embedding. However, the method mainly adopts low-end treatment methods such as pyrolysis and crushing for the recovery of the thermosetting epoxy resin, and the recovery methods have high energy consumption and pollute the environment. And the stability of the molecular structure is reduced, so that the recovery rate of the epoxy resin is reduced, and therefore, the development of the recyclable epoxy resin with high recovery rate has important economic value and environmental protection significance.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art that is known to a person skilled in the art.
Disclosure of Invention
The first purpose of the present invention is to overcome the defects of the prior art and provide a preparation method and a recycling process of recyclable epoxy resin, so that the epoxy resin has excellent chemical recycling performance and excellent mechanical properties.
The technical purpose of the invention is realized by the following technical scheme:
the recyclable epoxy resin comprises, by mass, 45-65% of epoxy resin raw materials, 35-55% of curing agents and 0.05-5% of catalysts, and the epoxy resin raw materials comprise traditional epoxy resin and hyperbranched polyether epoxy resin which are compounded according to a mass ratio of 100-20. According to the invention, the cross-linking density of the terminal group of the epoxy resin raw material and the curing agent is improved by controlling the proportion of the traditional epoxy resin and the hyperbranched polyether type epoxy resin, and the viscosity and rigidity of the recyclable epoxy resin are ensured.
Preferably, the conventional epoxy resin is one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and hydrogenated bisphenol a type epoxy resin. Wherein the bisphenol A type epoxy resin is at least one of the following epoxy monomers: CYD-128 (E-51), CYD-127 (E-54), CYD-115, E-44 (6101), E-42. The epoxy value of the bisphenol A epoxy resin is between 0.42 and 0.51. The epoxy monomer in the range has low viscosity, is suitable for low-viscosity operations such as vacuum infusion, pultrusion and the like, and if the epoxy equivalent is too small, the functionality of the traditional epoxy resin is too long, so that the processing efficiency is influenced.
Preferably, the hyperbranched polyether type epoxy resin is glycidyl ether type epoxy resin which is prepared by a proton transfer polymerization method. Wherein the preparation raw materials are bis (phenolic hydroxyl) alcoholic hydroxyl monomer or glycidyl ether monomer and triphenol hydroxyl (alcoholic hydroxyl) monomer or glycidyl ether monomer, and the preparation is carried out by proton transfer polymerization reaction under the catalysis of tetrabutylammonium bromide or tetrabutylammonium chloride. In order to improve the crosslinking degree of the system and improve the glass transition temperature and the mechanical property of the recyclable epoxy resin,
preferably, the curing agent is an organic amine curing agent or an acid anhydride curing agent; the organic amine curing agent is one or more of aromatic amine and alicyclic amine; the acid anhydride curing agent is one or more of straight-chain aliphatic acid anhydride, aromatic acid anhydride and alicyclic acid anhydride. Epoxy resin monomers have various active groups such as epoxy groups, hydroxyl groups and ether groups, so that various curing agents capable of performing a crosslinking reaction with epoxy resin raw materials are available, and the curing agents mainly include organic amine curing agents or acid anhydride curing agents. The curing agents used differ, as do the desired curing temperatures. The curing temperature of the curing agent is more than 90 ℃, so that the viscosity of the recyclable epoxy resin before curing is controllable. Generally, the organic amine curing agent can crosslink with the epoxy resin raw material at normal temperature, while the anhydride curing agent can complete the crosslinking reaction with the epoxy resin raw material at higher temperature (> 150 ℃), and the temperature can be properly reduced by adding the catalyst.
Preferably, the catalyst is one or more of zinc acetylacetonate, zinc acetate, stannous isooctanoate, dibutyltin dilaurate, dibutyltin acetate, dodecylbenzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, trichloroacetic acid and trifluoroacetic acid.
Preferably, the reactive diluent also comprises a reactive diluent, and the reactive diluent is one or more of phenyl glycidyl ether, o-cresol glycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether and trimethylolpropane triglycidyl ether.
The content of the reactive diluent is obtained by the following method:
wherein, γ 3 The theoretical viscosity of the epoxy resin raw material is calculated by the compound mass ratio of the traditional epoxy resin and the hyperbranched polyether type epoxy resin, gamma is the theoretical viscosity of the recoverable epoxy resin after air bubbles are removed, and M is the mass of the epoxy resin raw material; w is the mass of the curing agent; r is the mass of the catalyst; x is the mass of the active diluent and is less than M; q is the viscosity reduction rate of the active diluent;
the variable quantity of the pressure during the vacuum pumping; t is vacuumizing time.
Specifically; the calculation method of the reactive diluent comprises the following steps;
(1) The viscosity gamma of the hyperbranched polyether epoxy resin is measured by an RV-06 rotor at the temperature of 25 ℃ and the rotating speed of 20r/min by using a viscometer 1 The viscosity gamma of a conventional epoxy resin under the same conditions was measured 2 The theoretical viscosity gamma of the epoxy resin raw material can be obtained 3 Comprises the following steps:
wherein, γ 1 The viscosity, gamma, of the hyperbranched epoxy resin is measured by an RV-06 rotor at the temperature of 25 ℃ and the rotating speed of 20r/min by using a viscometer 2 The viscosity of the traditional epoxy resin under the same conditions; mr is 2 Is the relative molecular weight, mr, of the hyperbranched polyether type epoxy resin 1 Relative molecular weight of conventional epoxy resins, M 1 Is the quality of the traditional epoxy resin; m is a group of 2 Is hyperbranched polyQuality of ether type epoxy resin.
(2) Stirring M parts of epoxy resin raw material and X parts of reactive diluent to obtain the theoretical viscosity gamma of the epoxy resin raw material 4 Is as follows;
(3) Adding W parts of curing agent into a recyclable epoxy resin system, and fully stirring until the mixture is uniformly mixed; vacuumizing at the constant temperature of 70-90 ℃ for 10-20min until bubbles are pumped out, wherein the theoretical viscosity gamma of the recyclable epoxy resin is as follows:
wherein K is a viscosity correction coefficient, and gamma is a standard value (300 to 500mpa.s) for ensuring that the viscosity of the recyclable epoxy resin reaches a standard value suitable for vacuum infusion and pultrusion under the lowest mixing amount of the reactive diluent.
The doping amount X of the reactive diluent is calculated.
The second purpose of the invention is to provide a preparation method of the recyclable epoxy resin, which can prevent partial epoxy groups from being degraded in advance by controlling the adding time of each component so as to achieve the maximum effect of the synergistic effect.
The technical purpose of the invention is realized by the following technical scheme:
a preparation method of recyclable epoxy resin comprises the following operation steps:
s1: weighing the components according to the mass ratio;
s2: adding the traditional epoxy resin into a reaction container, then adding the hyperbranched polyether type epoxy resin, uniformly stirring, and adding the active epoxy diluent for continuously stirring after uniformly mixing the traditional epoxy resin and the hyperbranched polyether type epoxy resin;
s3: adding a catalyst into the mixture obtained in the step S2, fully stirring at 120-160 ℃ until the catalyst is completely dissolved, cooling to 50-80 ℃, adding a curing agent, and fully stirring until the mixture is uniformly mixed;
s4: and vacuumizing at the constant temperature of 70-90 ℃ for 10-20min until air bubbles are exhausted, enabling imitation oxygen to enter a system, and pouring into a preheating mould to perform staged heating curing to obtain the recyclable epoxy resin.
The method adopts temperature rise curing in stages, wherein the reaction conditions in the first stage are 90-100 ℃ for 1-2h, the reaction conditions in the second stage are 120-140 ℃ for 1-2h, and the reaction conditions in the third stage are 150-170 ℃ for 1-2h, so that the cured recyclable epoxy resin has better cross-linking density and mechanical property, compared with direct curing, a fixed network structure is prevented from being formed in the initial stage of the reaction, the rest molecules are difficult to react, and the reactivity of a cured product is improved.
The third purpose of the invention is to provide a recycling method of recyclable epoxy resin, which obtains low molecular epoxy resin through chemical recycling, and maintains the stability of partial chemical bonds while ester bonds are dynamically exchanged, so that the epoxy resin has good shape remolding performance.
The technical purpose of the invention is realized by the following technical scheme:
a method for recovering recyclable epoxy resin comprises the steps of completely soaking the recyclable epoxy resin prepared by the preparation method in a composite solvent in a sealed state, stirring for 2-10 h at 70-200 ℃, and distilling under reduced pressure to obtain a recovered solvent and low-molecular epoxy resin after the recyclable epoxy resin is completely dissolved.
Preferably, the composite solvent is one or more of acetic acid, ethanol, methanol, propanol, butanol, ethylene glycol, 1,2 propylene glycol, acetic acid, acetone, tetrahydrofuran, 1,4 dioxane, and acetone. The composite solvent is in a micromolecular structure, the condensate of the recyclable epoxy resin is in a cross-linked network structure, and when the recyclable epoxy resin is completely soaked in the composite solvent, micromolecules of the composite solvent penetrate through the cross-linked network and act on dynamic chemical bonds (ester bonds), so that the recyclable epoxy resin is completely dissolved, and the low-molecular epoxy resin is obtained.
In conclusion, the invention has the following beneficial effects:
(1) According to the invention, the glycidyl ether hyperbranched polymer is introduced into the epoxy resin component, and the thermal stability of an ether bond in a hyperbranched molecule is higher, so that the stability of part of chemical bonds is maintained while dynamic exchange of dynamic chemical bonds (ester bonds) is carried out on the material. By virtue of the advantages of the hyperbranched polyether type epoxy resin, the viscosity of the system can be reduced, and the crosslinking density of the system can be increased, so that the epoxy resin has good shape remolding performance.
(2) According to the invention, the mixing amount of the reactive diluent is accurately controlled, the viscosity of the recyclable epoxy resin is ensured to reach a standard value (300 to 500mpa.s) suitable for vacuum infusion and pultrusion under the lowest mixing amount of the reactive diluent, the quantity of dynamic bonds in the recyclable epoxy resin under the same quality is ensured to be maximized, and the recovery rate of the recyclable epoxy resin is further improved; the waste of the cured epoxy resin is avoided. The recyclable epoxy resin prepared by the invention solves the problem that thermosetting epoxy resin is difficult to recycle, effectively saves resources, and has practical application value under the sustainable development concept.
(3) The preparation process of the recyclable epoxy resin is simple, the raw material cost is low, and the method is suitable for industrial production; the method for recovering the recyclable epoxy resin has the advantages of simple process, low operation pressure and no waste water and liquid generated in the recovery process. The process of recycling and reusing the epoxy resin material by using the recyclable epoxy resin in the invention does not generate secondary pollution sources to the environment, and the excessive raw materials and reagents can be recycled, thereby being an economical and feasible industrial production route. Compared with the low-end treatment modes such as pyrolysis, crushing and the like, the method ensures the stability of the molecular structure, so that the epoxy resin can be recycled for multiple times, and has important economic value and environmental protection significance.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the embodiments, features and effects of the recyclable epoxy resin and the preparation method according to the present invention are described in detail below.
Sources of raw materials used in the examples:
example 1
The recyclable epoxy resin comprises, by mass, 100g of conventional epoxy resin E51, 5g of hyperbranched polyether epoxy resin, 43g of curing agent glutaric anhydride, 22g of reactive diluent phenyl glycidyl ether and 0.067g of catalyst zinc acetylacetonate.
In this example, the viscosity γ of the hyperbranched polyether epoxy resin was measured with an RV-06 rotor at 25 ℃ and 20r/min using a viscometer 1 352mpa.s, the viscosity γ of a conventional epoxy resin under the same conditions was measured 2 12940mpa.s, relative molecular weight mr of hyperbranched polyether epoxy resin 2 14532, the relative molecular weight mr of a conventional epoxy resin 1 380, the theoretical viscosity γ of the epoxy resin raw material can be obtained according to the following formula 3 4246.20mpa.s;
meanwhile, when the dilution rate of the obtained reactive diluent is 75%, the variation of the pressure during vacuumizing is 2mpa, and the vacuumizing time is 600s, the content X of the reactive diluent is 22g calculated according to the following formula.
A preparation method of recyclable epoxy resin comprises the following operation steps:
s1: weighing the components according to the mass ratio;
s2: adding the traditional epoxy resin into a reaction container, then adding the hyperbranched polyether type epoxy resin, uniformly stirring, and adding the active epoxy diluent for continuously stirring after uniformly mixing the traditional epoxy resin and the hyperbranched polyether type epoxy resin;
s3: adding zinc acetylacetonate into the mixture obtained in the step S2, fully stirring at 120 ℃ until the catalyst is completely dissolved, cooling to 60 ℃, adding a curing agent, and fully stirring until the mixture is uniformly mixed;
s4: vacuumizing at the constant temperature of 90 ℃ for 10min until bubbles are removed, and then pouring into a preheating mould for staged temperature rise curing according to the processes of 100 ℃/1h,130 ℃/2h and 160 ℃/2h to obtain the recyclable epoxy resin.
A method for recovering recoverable epoxy resin comprises the steps of soaking the recoverable epoxy resin prepared by the preparation method in 1,2 propylene glycol in a sealed state, stirring for 2 hours at 160 ℃ until the recoverable epoxy resin is completely dissolved, and distilling under reduced pressure to obtain a recovered solvent and low-molecular epoxy resin.
Example 2
The recyclable epoxy resin comprises, by mass, 100g of conventional epoxy resin E54, 4g of hyperbranched polyether epoxy resin, 45g of curing agent succinic anhydride, 18.32g of reactive diluent o-cresol glycidyl ether and 0.067g of catalyst zinc acetylacetonate.
In this example, the viscosity γ of the hyperbranched polyether epoxy resin was measured with an RV-06 rotor at 25 ℃ and 20r/min using a viscometer 1 352mpa.s, the viscosity γ of a conventional epoxy resin under the same conditions was measured 2 12940mpa.s, relative molecular weight mr of hyperbranched polyether epoxy resin 2 14532, the relative molecular weight mr of a conventional epoxy resin 1 380, the theoretical viscosity gamma of the epoxy resin raw material can be obtained according to the following formula 3 3914.13mpa.s;
meanwhile, when the dilution rate of the obtained reactive diluent is 90%, the variation of the pressure during vacuumizing is 2mpa, and the vacuumizing time is 600s, the content X of the reactive diluent is 18.32g calculated according to the following formula.
A preparation method of recyclable epoxy resin comprises the following operation steps:
s1: weighing the components according to the mass ratio;
s2: adding the traditional epoxy resin into a reaction container, then adding the hyperbranched polyether type epoxy resin, uniformly stirring, and adding the active epoxy diluent for continuously stirring after uniformly mixing the traditional epoxy resin and the hyperbranched polyether type epoxy resin;
s3: adding zinc acetylacetonate into the mixture obtained in the step S2, fully stirring at 120 ℃ until the catalyst is completely dissolved, cooling to 60 ℃, adding a curing agent, and fully stirring until the mixture is uniformly mixed;
s4: vacuumizing at the constant temperature of 90 ℃ for 10min until bubbles are removed, pouring into a preheating mould, and carrying out stage heating curing according to the processes of 100 ℃/1h,140 ℃/2h and 170 ℃/2h to obtain the recyclable epoxy resin.
A method for recovering recoverable epoxy resin comprises the steps of soaking the recoverable epoxy resin prepared by the preparation method in 1,2 propylene glycol in a sealed state, stirring for 2 hours at 160 ℃ until the recoverable epoxy resin is completely dissolved, and distilling under reduced pressure to obtain a recovered solvent and low-molecular epoxy resin.
Example 3
The recyclable epoxy resin comprises, by mass, 100g of conventional epoxy resin E51, 6g of hyperbranched polyether epoxy resin, 45g of curing agent 4,4' -diaminodiphenylmethane, 17.95g of active diluent o-cresol glycidyl ether and 0.067g of catalyst zinc acetate.
In this example, the viscosity γ of the hyperbranched polyether epoxy resin was measured with an RV-06 rotor at 25 ℃ and 20r/min using a viscometer 1 352mpa.s, the viscosity γ of a conventional epoxy resin under the same conditions was measured 2 The signal is 9893mpa.s,relative molecular weight mr of hyperbranched polyether type epoxy resin 2 14532, the relative molecular weight mr of a conventional epoxy resin 1 405, the theoretical viscosity γ of the epoxy resin raw material can be obtained according to the following formula 3 3719.28mpa.s;
meanwhile, when the dilution rate of the obtained reactive diluent is 90%, the pressure change amount during vacuumizing is 2mpa, and the vacuumizing time is 600s, the content X of the reactive diluent is 17.95g calculated according to the following formula.
A preparation method of recyclable epoxy resin comprises the following operation steps:
s1: weighing the components according to the mass ratio;
s2: adding the traditional epoxy resin into a reaction container, then adding the hyperbranched polyether type epoxy resin, uniformly stirring, and adding the active epoxy diluent for continuously stirring after uniformly mixing the traditional epoxy resin and the hyperbranched polyether type epoxy resin;
s3: adding zinc acetylacetonate into the mixture obtained in the step S2, fully stirring at 120 ℃ until the catalyst is completely dissolved, cooling to 60 ℃, adding a curing agent, and fully stirring until the mixture is uniformly mixed;
s4: vacuumizing at the constant temperature of 90 ℃ for 10min until bubbles are removed, pouring into a preheating mould, and carrying out stage heating curing according to the processes of 100 ℃/1h,130 ℃/2h and 150 ℃/2h to obtain the recyclable epoxy resin.
A method for recovering recoverable epoxy resin comprises soaking the recoverable epoxy resin prepared by the above preparation method in ethylene glycol under sealed condition, stirring at 160 deg.C for 2h until the recoverable epoxy resin is completely dissolved, and distilling under reduced pressure to obtain recovered solvent and low molecular epoxy resin.
Example 4
The recyclable epoxy resin comprises, by mass, 100g of traditional epoxy resin BPF, 4g of hyperbranched polyether epoxy resin, 43g of curing agent glutaric anhydride, 15g of reactive diluent o-cresol glycidyl ether and 0.067g of catalyst zinc acetylacetonate.
In this example, the viscosity γ of the hyperbranched polyether epoxy resin was measured using a viscometer at 25 ℃ and 20r/min using an RV-06 rotor 1 352mpa.s, the viscosity γ of a conventional epoxy resin under the same conditions was measured 2 5664mpa.s, relative molecular weight mr of hyperbranched polyether epoxy resin 2 14532, the relative molecular weight mr of conventional epoxy resins 1 At 425, the theoretical viscosity γ of the epoxy resin raw material can be obtained according to the following formula 3 2308mpa.s;
meanwhile, when the dilution rate of the obtained reactive diluent is 90%, the variation of the pressure during vacuumizing is 1.5mpa, and the vacuumizing time is 600s, the content X of the reactive diluent is 15g calculated according to the following formula.
A preparation method of recyclable epoxy resin comprises the following operation steps:
s1: weighing the components according to the mass ratio;
s2: adding the traditional epoxy resin into a reaction container, then adding the hyperbranched polyether type epoxy resin, uniformly stirring, and adding the active epoxy diluent for continuously stirring after uniformly mixing the traditional epoxy resin and the hyperbranched polyether type epoxy resin;
s3: adding zinc acetylacetonate into the mixture obtained in the step S2, fully stirring at 120 ℃ until the catalyst is completely dissolved, cooling to 60 ℃, adding a curing agent, and fully stirring until the mixture is uniformly mixed;
s4: vacuumizing at the constant temperature of 90 ℃ for 10min until bubbles are removed, and then pouring into a preheating mould for staged temperature rise curing according to the processes of 100 ℃/1h,130 ℃/2h and 160 ℃/2h to obtain the recyclable epoxy resin.
A method for recovering recoverable epoxy resin comprises the steps of soaking the recoverable epoxy resin prepared by the preparation method in 1,2 propylene glycol in a sealed state, stirring for 2 hours at 160 ℃ until the recoverable epoxy resin is completely dissolved, and distilling under reduced pressure to obtain a recovered solvent and low-molecular epoxy resin.
Example 5
The recyclable epoxy resin comprises, by mass, 100g of conventional epoxy resin E51, 8g of hyperbranched polyether epoxy resin, 50g of curing agent glutaric anhydride, 21g of reactive diluent o-cresol glycidyl ether and 0.067g of catalyst zinc acetylacetonate.
In this example, the viscosity γ of the hyperbranched polyether epoxy resin was measured with an RV-06 rotor at 25 ℃ and 20r/min using a viscometer 1 352mpa.s, the viscosity γ of a conventional epoxy resin under the same conditions was measured 2 12940mpa.s, relative molecular weight mr of hyperbranched polyether epoxy resin 2 14532, the relative molecular weight mr of a conventional epoxy resin 1 380, the theoretical viscosity γ of the epoxy resin raw material can be obtained according to the following formula 3 2971.21mpa.s;
meanwhile, when the dilution rate of the obtained reactive diluent is 75%, the variation of the pressure during vacuumizing is 2mpa, and the vacuumizing time is 600s, the content X of the reactive diluent is 21g calculated according to the following formula.
A preparation method of recyclable epoxy resin comprises the following operation steps:
s1: weighing the components according to the mass ratio;
s2: adding the traditional epoxy resin into a reaction container, then adding the hyperbranched polyether type epoxy resin, uniformly stirring, and adding the active epoxy diluent for continuously stirring after uniformly mixing the traditional epoxy resin and the hyperbranched polyether type epoxy resin;
s3: adding zinc acetylacetonate into the mixture obtained in the step S2, fully stirring at 120 ℃ until the catalyst is completely dissolved, cooling to 60 ℃, adding a curing agent, and fully stirring until the mixture is uniformly mixed;
s4: vacuumizing at the constant temperature of 90 ℃ for 20min until bubbles are removed, and then pouring into a preheating mould for staged temperature rise curing according to the processes of 95 ℃/1h,120 ℃/2h and 160 ℃/2h to obtain the recyclable epoxy resin.
A method for recovering recoverable epoxy resin comprises the steps of soaking the recoverable epoxy resin prepared by the preparation method in 1,2 propylene glycol in a sealed state, stirring for 2 hours at 160 ℃ until the recoverable epoxy resin is completely dissolved, and distilling under reduced pressure to obtain a recovered solvent and low-molecular epoxy resin.
Comparative example 1
The recyclable epoxy resin comprises, by mass, 100g of conventional epoxy resin E51, 43g of curing agent glutaric anhydride, 45g of reactive diluent phenyl glycidyl ether and 0.067g of catalyst zinc acetylacetonate.
A preparation method of recyclable epoxy resin comprises the following operation steps:
s1: weighing the components according to the mass ratio;
s2: adding the traditional epoxy resin into a reaction container, adding the reactive epoxy diluent, and continuously stirring;
s3: adding zinc acetylacetonate into the mixture obtained in the step S2, fully stirring at 120 ℃ until the catalyst is completely dissolved, cooling to 60 ℃, adding a curing agent, and fully stirring until the mixture is uniformly mixed;
s4: vacuumizing at the constant temperature of 90 ℃ for 10min until bubbles are removed, pouring into a preheating mould, and carrying out stage heating curing according to the processes of 100 ℃/1h,130 ℃/2h and 160 ℃/2h to obtain the recyclable epoxy resin.
A method for recovering recoverable epoxy resin comprises the steps of soaking the recoverable epoxy resin prepared by the preparation method in 1,2 propylene glycol in a sealed state, stirring for 2 hours at 160 ℃ until the recoverable epoxy resin is completely dissolved, and distilling under reduced pressure to obtain a recovered solvent and low-molecular epoxy resin.
Comparative example 2
The recyclable epoxy resin comprises, by mass, 100g of conventional epoxy resin E51, 1g of hyperbranched polyether epoxy resin, 43g of curing agent glutaric anhydride, 36g of reactive diluent phenyl glycidyl ether and 0.067g of catalyst zinc acetylacetonate.
A preparation method of recyclable epoxy resin comprises the following operation steps:
s1: weighing the components according to the mass ratio;
s2: adding the traditional epoxy resin into a reaction container, then adding the hyperbranched polyether type epoxy resin, uniformly stirring, adding the active epoxy diluent, and continuously stirring after uniformly mixing the traditional epoxy resin with the hyperbranched polyether type epoxy resin;
s3: adding zinc acetylacetonate into the mixture obtained in the step S2, fully stirring at 120 ℃ until the catalyst is completely dissolved, cooling to 60 ℃, adding a curing agent, and fully stirring until the mixture is uniformly mixed;
s4: vacuumizing at the constant temperature of 90 ℃ for 10min until bubbles are removed, pouring into a preheating mould, and carrying out stage heating curing according to the processes of 100 ℃/1h,130 ℃/2h and 160 ℃/2h to obtain the recyclable epoxy resin.
A method for recovering recoverable epoxy resin comprises the steps of soaking the recoverable epoxy resin prepared by the preparation method in 1,2 propylene glycol in a sealed state, stirring for 2 hours at 160 ℃ until the recoverable epoxy resin is completely dissolved, and distilling under reduced pressure to obtain a recovered solvent and low-molecular epoxy resin.
Comparative example 3
The recyclable epoxy resin comprises, by mass, 70g of conventional epoxy resin E51, 30g of hyperbranched polyether epoxy resin, 43g of curing agent glutaric anhydride and 0.067g of catalyst zinc acetylacetonate.
A preparation method of recyclable epoxy resin comprises the following operation steps:
s1: weighing the components according to the mass ratio;
s2: adding the traditional epoxy resin into a reaction container, then adding the hyperbranched polyether type epoxy resin, uniformly stirring, and adding the active epoxy diluent for continuously stirring after uniformly mixing the traditional epoxy resin and the hyperbranched polyether type epoxy resin;
s3: adding zinc acetylacetonate into the mixture obtained in the step S2, fully stirring at 120 ℃ until the catalyst is completely dissolved, cooling to 60 ℃, adding a curing agent, and fully stirring until the mixture is uniformly mixed;
s4: vacuumizing at the constant temperature of 90 ℃ for 10min until bubbles are removed, pouring into a preheating mould, and carrying out stage heating curing according to the processes of 100 ℃/1h,130 ℃/2h and 160 ℃/2h to obtain the recyclable epoxy resin.
A method for recovering recoverable epoxy resin comprises the steps of soaking the recoverable epoxy resin prepared by the preparation method in 1,2 propylene glycol in a sealed state, stirring for 2 hours at 160 ℃ until the recoverable epoxy resin is completely dissolved, and distilling under reduced pressure to obtain a recovered solvent and low-molecular epoxy resin.
And (3) performance testing:
the recyclable resins prepared in examples 1-5 and comparative examples 1-3 were subjected to the following performance tests:
dynamic Mechanical Analysis (DMA) (ASTM D4065) was performed to determine the glass transition temperature Tg of the cured resin;
tensile and flexural tests were performed according to the test methods of ASTM D638 and ASTM D790, respectively.
Comparative example 1 compared with example 1, no hyperbranched polyether epoxy resin was used, and a large amount of reactive diluent was used to dilute the epoxy resin raw material, as can be seen from the data, the glass transition temperature Tg was reduced by 14.9 ℃, and the recovery rate of the epoxy resin was reduced by 13%, because the glycidyl ether hyperbranched polymer introduced in the present invention allows the material to maintain the stability of part of the chemical bonds while the dynamic chemical bonds (ester bonds) are exchanged, and the recovery rate of the recyclable epoxy resin is improved.
Comparative example 2 compared to example 1, only a small amount of hyperbranched polyether epoxy resin was used, and it can be seen from the combination of comparative example 1 that the larger the content of the reactive diluent in the system, the less the dynamic chemical bonds (ester bonds) in the recyclable epoxy resin under the same mass, and further the recovery rate of the epoxy resin was affected.
Compared with the embodiment 1, the comparative example 3 uses excessive hyperbranched polyether epoxy resin, in order to ensure that the viscosity of the recyclable epoxy resin reaches a standard value suitable for vacuum infusion and pultrusion, the comparative example 3 does not use a reactive diluent, and the data show that the glass transition temperature Tg is reduced by 13.2 ℃, the recovery rate of the epoxy resin is reduced by 18%, the tensile modulus is improved by 3070MPa, and the flexural modulus is improved by 2030MPa, because the excessive hyperbranched polyether epoxy resin increases the relative molecular weight of the epoxy resin raw material, increases the curing density of the epoxy resin, and further influences the tensile modulus and the flexural modulus, and because the crosslinking density of the cured product is too large, the small molecular structure of the composite solvent cannot completely and dynamically act on a chemical bond during recycling, and further reduces the recovery rate of the recyclable epoxy resin.
It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The recyclable epoxy resin is characterized by comprising, by mass, 45-65% of epoxy resin raw materials, 35-55% of curing agents and 0.05-5% of catalysts, wherein the epoxy resin raw materials comprise traditional epoxy resin and hyperbranched polyether epoxy resin which are compounded according to a mass ratio of 100-20.
2. The recyclable epoxy resin as described in claim 1, wherein the conventional epoxy resin is one or more of bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and hydrogenated bisphenol a epoxy resin.
3. The recyclable epoxy resin as described in claim 1, wherein the hyperbranched polyether epoxy resin is a glycidyl ether epoxy resin prepared by proton transfer polymerization.
4. The recyclable epoxy resin as described in claim 1, wherein the curing agent is an organic amine curing agent or an acid anhydride curing agent;
the organic amine curing agent is one or more of aromatic amine and alicyclic amine;
the anhydride curing agent is one or more of straight-chain aliphatic anhydride, aromatic anhydride and alicyclic anhydride.
5. The recyclable epoxy resin as described in claim 1, wherein the catalyst is one or more of zinc acetylacetonate, zinc acetate, stannous isooctanoate, dibutyltin dilaurate, dibutyltin acetate, dodecylbenzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid, trichloroacetic acid, and trifluoroacetic acid.
6. The recyclable epoxy resin as described in claim 1, further comprising a reactive diluent, wherein the reactive diluent is one or more of phenyl glycidyl ether, o-cresol glycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, and trimethylolpropane triglycidyl ether.
7. The recyclable epoxy resin according to claim 6, wherein the reactive diluent is obtained by the following method in parts by weight:
wherein, γ 3 The theoretical viscosity of the epoxy resin raw material is calculated according to the compounding mass ratio of the traditional epoxy resin and the hyperbranched polyether type epoxy resin; gamma is the theoretical viscosity of the recyclable epoxy resin after air bubbles are removed, and M is the mass of the epoxy resin raw material; w is the mass of the curing agent; r is the mass of the catalyst; x is the mass of the active diluent and is less than M; q is the viscosity reduction rate of the active diluent;
the variable quantity of the pressure during the vacuum pumping; t is the vacuumizing time.
8. The process for the preparation of a recyclable epoxy resin according to any of the claims 1 to 7, characterized in that it comprises the following operative steps:
s1: weighing the components according to the mass ratio;
s2: adding the traditional epoxy resin into a reaction container, then adding the hyperbranched polyether type epoxy resin, uniformly stirring, and adding the active epoxy diluent for continuously stirring after uniformly mixing the traditional epoxy resin and the hyperbranched polyether type epoxy resin;
s3: adding a catalyst into the mixture obtained in the step S2, fully stirring at 120-160 ℃ until the catalyst is completely dissolved, cooling to 50-80 ℃, adding a curing agent, and fully stirring until the mixture is uniformly mixed;
s4: and (3) vacuumizing for 10 to 20min at the constant temperature of 70 to 90 ℃ until air bubbles are exhausted, and pouring the air bubbles into a preheating mould to perform staged heating curing to obtain the recyclable epoxy resin.
9. A method for recovering recyclable epoxy resin, characterized in that the recyclable epoxy resin prepared by the preparation method of claim 8 is soaked in a composite solvent in a sealed state, stirred at 70-200 ℃ for 2-10 h until the recyclable epoxy resin is completely dissolved, and then distilled under reduced pressure to obtain a recovered solvent and low molecular weight epoxy resin.
10. The method of claim 9, wherein the composite solvent is one or more of acetic acid, ethanol, methanol, propanol, butanol, ethylene glycol, 1,2 propylene glycol, acetic acid, acetone, tetrahydrofuran, 1,4 dioxane, and acetone.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115960337A (en) * | 2023-02-17 | 2023-04-14 | 南京海拓复合材料有限责任公司 | Epoxy resin curing agent for pultrusion of composite material and preparation method thereof |
| CN116731288A (en) * | 2023-07-19 | 2023-09-12 | 武汉纺织大学 | Epoxy glass polymer containing dynamic ester bonds, glass fiber cloth laminated board and preparation method and application thereof |
| CN117820816A (en) * | 2024-01-02 | 2024-04-05 | 中国科学院宁波材料技术与工程研究所 | Flame-retardant and easily-degradable epoxy resin precursor, cured product, preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924690A (en) * | 2012-11-07 | 2013-02-13 | 北京化工大学 | Epoxy resin material used for toughening and reinforcing of hyperbranched polyether type epoxy resin and preparation method thereof |
| CN114752109A (en) * | 2022-05-07 | 2022-07-15 | 浙江大学 | Upgrading recycling method of resin containing ester bonds |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102924690A (en) * | 2012-11-07 | 2013-02-13 | 北京化工大学 | Epoxy resin material used for toughening and reinforcing of hyperbranched polyether type epoxy resin and preparation method thereof |
| CN114752109A (en) * | 2022-05-07 | 2022-07-15 | 浙江大学 | Upgrading recycling method of resin containing ester bonds |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115960337A (en) * | 2023-02-17 | 2023-04-14 | 南京海拓复合材料有限责任公司 | Epoxy resin curing agent for pultrusion of composite material and preparation method thereof |
| CN115960337B (en) * | 2023-02-17 | 2023-12-26 | 南京海拓复合材料有限责任公司 | Epoxy resin curing agent for composite material pultrusion and preparation method thereof |
| CN116731288A (en) * | 2023-07-19 | 2023-09-12 | 武汉纺织大学 | Epoxy glass polymer containing dynamic ester bonds, glass fiber cloth laminated board and preparation method and application thereof |
| CN117820816A (en) * | 2024-01-02 | 2024-04-05 | 中国科学院宁波材料技术与工程研究所 | Flame-retardant and easily-degradable epoxy resin precursor, cured product, preparation method and application |
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