CN115651165B - Recoverable epoxy resin, preparation method thereof and recovery method thereof - Google Patents
Recoverable epoxy resin, preparation method thereof and recovery 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, a preparation method thereof and a recycling method thereof. The recyclable epoxy resin comprises the following components in percentage by mass: 45-65% of epoxy resin raw materials, 35-55% of curing agent and 0.05-5% of catalyst. The preparation process comprises the following steps: the components are heated and mixed uniformly, degassed in a vacuum state, and then solidified, so that the recyclable epoxy resin with recycling performance is obtained. The method can dissolve the cured recyclable epoxy resin in the composite solvent under the heating condition, and then recycle the composite solvent and the epoxy resin with low molecular weight 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, a preparation method thereof and a recycling method thereof.
Background
The epoxy resin is a synthetic thermosetting polymer for preparing composite materials, and is widely applied to the fields of coating, composite materials, adhesives and the like due to excellent mechanical property, adhesive property and low curing shrinkage rate. However, since epoxy resins are thermoplastic linear structural monomers prior to curing, their application value is often manifested by crosslinking with curing agents and creating insoluble, insoluble crosslinked networks. So that the waste water can not be reprocessed or recycled, and the waste of resources is caused.
At present, the recyclable epoxy resins reported in the literature mainly focus on introducing dynamic covalent bonds with certain environmental stimuli responsivity into molecular structures, and dynamic covalent polymers with certain environmental stimuli responsivity have been used as sustainable alternative materials for thermosetting materials, also called glass-like polymers (Vitrimers), and have the dual advantages of thermosetting polymers and thermoplastic polymers. Such epoxy resins are known as covalently compliant networks, including ester linkages, disulfide linkages, imine linkages, hexahydro s-triazine structures, and the like. However, the imine bond curing process generates byproduct water in situ, which can adversely affect the performance of the cured resin and the industrial production; the preparation process of the molecule containing the disulfide bond and hexahydro-s-triazine structure is complex.
The Chinese patent CN114989562A discloses a recyclable metallographic mosaic material and a preparation method thereof, and aims at solving the problem that epoxy resin metallographic mosaic material cannot be reused after once mosaic, and the recyclable metallographic mosaic material is provided, and by adding dynamic chemical bonds into a thermosetting resin matrix, the thermosetting resin can realize the breaking and recombination of the chemical bonds under the stimulation of light, heat, acid, alkali and the like, thereby realizing the reprocessing of the resin. The method realizes recycling of the metallographic mosaic material and avoids waste of mosaic material after the mosaic. However, the recovery of the thermosetting epoxy resin in the method is mainly a low-end treatment mode such as pyrolysis and crushing, 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 recoverable 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 object of the invention is to overcome the defects of the prior art and provide a preparation method and a recovery process of the recyclable epoxy resin, so that the epoxy resin has excellent chemical recoverability and excellent mechanical properties.
The technical aim 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, wherein the epoxy resin raw materials comprise traditional epoxy resin and hyperbranched polyether type epoxy resin compounded according to a mass ratio of 100:3-20. The invention improves the crosslinking density of the end group of the epoxy resin raw material and the curing agent by controlling the proportion of the traditional epoxy resin and the hyperbranched polyether type epoxy resin, and ensures the viscosity and the rigidity of the recyclable epoxy resin.
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 type epoxy resin is between 0.42 and 0.51. The epoxy monomer in the range has lower viscosity, is suitable for low-viscosity operations such as vacuum pouring, pultrusion and the like, and if the epoxy equivalent is too small, the functionality of the traditional epoxy resin is too long, and the processing efficiency is affected.
Preferably, the hyperbranched polyether epoxy resin is glycidyl ether epoxy resin and is prepared by a proton transfer polymerization method. Wherein the preparation raw materials are bisphenol (phenolic hydroxyl) alcohol hydroxyl monomer or glycidyl ether monomer and triphenol hydroxyl (phenolic hydroxyl) monomer or glycidyl ether monomer, and the catalyst is prepared by proton transfer polymerization under the catalysis of tetrabutylammonium bromide or tetrabutylammonium chloride. In order to improve the crosslinking degree of the system, the glass transition temperature and the mechanical property of the recyclable epoxy resin are improved,
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 anhydride curing agent is one or more of linear aliphatic acid anhydride, aromatic anhydride and alicyclic anhydride. The epoxy resin monomer itself has various active groups such as epoxy group, hydroxyl group and ether group, so the curing agent capable of cross-linking reaction with the epoxy resin raw material has various types and mainly comprises an organic amine curing agent or an anhydride curing agent. The curing agent used varies, as does the curing temperature required. The curing temperature of the curing agent is higher than 90 ℃, so that the viscosity of the recyclable epoxy resin is controllable before curing. Generally, the organic amine curing agent can crosslink with the epoxy resin raw material at normal temperature, and the complete crosslinking reaction of the anhydride curing agent and the epoxy resin raw material can be completed at a higher temperature (> 150 ℃), and the temperature can be properly reduced by adding a catalyst.
Preferably, the catalyst is one or more of zinc acetylacetonate, zinc acetate, stannous isooctanoate, dibutyl tin dilaurate, dibutyl tin acetate, dodecylbenzene sulfonic acid, p-toluene sulfonic acid, methane sulfonic acid, trichloroacetic acid and trifluoroacetic acid.
Preferably, 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 reactive diluent is obtained by:
wherein, gamma 3 The method is characterized in that the method comprises the steps of calculating the theoretical viscosity of an epoxy resin raw material according to the compounding mass ratio of the traditional epoxy resin to the hyperbranched polyether type epoxy resin, wherein 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 X is less than M; q is the viscosity reduction rate of the reactive diluent;
to vacuumizeThe amount of change in pressure at that time; t is the vacuuming time.
Specifically, the method comprises the following steps; the calculation method of the reactive diluent comprises the following steps;
(1) Measuring viscosity gamma of hyperbranched polyether type epoxy resin by using RV-06 rotor at 25 ℃ and rotating speed of 20r/min by using a viscometer 1 Testing the viscosity gamma of conventional epoxy resins under the same conditions 2 Obtaining the theoretical viscosity gamma of the epoxy resin raw material 3 The method comprises the following steps:
wherein, gamma 1 In order to obtain the viscosity of the hyperbranched epoxy resin, gamma, by using a viscometer at 25 ℃ and with the rotation speed of 20r/min and using an RV-06 rotor 2 The viscosity of the traditional epoxy resin under the same conditions; mr 2 Is the relative molecular weight, mr, of the hyperbranched polyether epoxy resin 1 The relative molecular weight of the traditional epoxy resin, M 1 The mass of the epoxy resin is the mass of the traditional epoxy resin; m is M 2 Is the mass of the hyperbranched polyether type epoxy resin.
(2) Stirring M parts of epoxy resin raw material and X parts of reactive diluent to obtain theoretical viscosity gamma of the epoxy resin raw material 4 Is that;
(3) Adding W parts of curing agent into the recyclable epoxy resin system, and fully stirring until the mixture is uniformly mixed; vacuumizing for 10-20min at the constant temperature of 70-90 ℃ until bubbles are removed, wherein the theoretical viscosity gamma of the recoverable epoxy resin is as follows:
k is a viscosity correction coefficient, and gamma is a standard value (300-500 mpa.s) for ensuring that the viscosity of the recyclable epoxy resin reaches to be suitable for vacuum infusion and pultrusion under the minimum doping amount of the reactive diluent.
The amount X of reactive diluent is calculated from this.
The second object of the present invention is to provide a method for preparing a recyclable epoxy resin, which can prevent the premature reaction and degradation of part of epoxy groups by controlling the addition time of each component, thereby maximizing the synergistic effect.
The technical aim of the invention is realized by the following technical scheme:
a preparation method of recoverable 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 hyperbranched polyether type epoxy resin, stirring and mixing uniformly, and adding the reactive epoxy diluent to continue stirring after the traditional epoxy resin and the hyperbranched polyether type epoxy resin are mixed uniformly;
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: vacuumizing for 10-20min at the constant temperature of 70-90 ℃ until bubbles are removed, imitating oxygen to enter a system, and then pouring the system into a preheating die for stage heating and curing to obtain the recyclable epoxy resin.
According to the invention, the temperature rising and curing are adopted in the stage, wherein the reaction condition in the first stage is that the reaction is carried out for 1-2 hours at the temperature of 90-100 ℃, the reaction condition in the second stage is that the reaction is carried out for 1-2 hours at the temperature of 120-140 ℃, and the reaction condition in the third stage is that the reaction is carried out for 1-2 hours at the temperature of 150-170 ℃, so that the cured recyclable epoxy resin has better crosslinking density and mechanical property through slow reaction, compared with direct curing, the problem that the fixed network structure is formed at the initial stage of the reaction, and other molecules are difficult to react is avoided, and the reactivity of a cured product is improved.
The third object of the invention is to provide a method for recycling the recyclable epoxy resin, which is characterized in that the low-molecular epoxy resin is obtained through chemical recycling, and the stability of partial chemical bonds is maintained while the ester bonds are dynamically exchanged, so that the epoxy resin has good shape remolding performance.
The technical aim of the invention is realized by the following technical scheme:
a method for recovering recoverable epoxy resin comprises the steps of fully soaking the recoverable epoxy resin prepared by the preparation method in a composite solvent in a sealed state, stirring for 2-10 hours at 70-200 ℃ until the recoverable epoxy resin is fully dissolved, and then distilling under reduced pressure to obtain a recovered solvent and low-molecular epoxy resin.
Preferably, the compound 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. In the invention, the composite solvent is of a small molecular structure, the recyclable epoxy resin condensate is of a crosslinked network structure, and when the recyclable epoxy resin is completely soaked in the composite solvent, the small molecules of the composite solvent penetrate through the crosslinked network and act on dynamic chemical bonds (ester bonds) to completely dissolve the recyclable epoxy resin, so that the low-molecular epoxy resin is obtained.
In summary, 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 ether bonds in hyperbranched molecules is higher, so that the material maintains the stability of part of chemical bonds while dynamic chemical bonds (ester bonds) are dynamically exchanged. 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, by accurately controlling the doping amount of the reactive diluent, the viscosity of the recyclable epoxy resin is ensured to reach the standard value (300-500 mpa.s) suitable for vacuum infusion and pultrusion under the lowest doping amount of the reactive diluent, the number of dynamic bonds in the recyclable epoxy resin is ensured to be maximized under the same quality, and the recovery rate of the recyclable epoxy resin is further improved; and the waste of the cured epoxy resin is avoided. The recyclable epoxy resin prepared by the invention solves the difficult problem that the 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 cost of raw materials is low, and the method is suitable for industrial production; the recovery method of the recoverable epoxy resin has simple process and low operating pressure, and no waste water and waste liquid are produced in the recovery process. The process of recycling the epoxy resin material by using the recyclable epoxy resin provided by the invention can not generate secondary pollution sources to the environment, and excessive raw materials and reagents can be recycled, so that the method is an economically feasible industrial production route. Compared with the low-end treatment modes such as pyrolysis, crushing and the like, the invention ensures the stability of the molecular structure, so that the epoxy resin can be recovered for multiple times, and has important economic value and environmental protection significance.
Detailed Description
In order to further describe the technical means and effects adopted by the invention to achieve the preset aim, the specific implementation, the characteristics and the effects of the recyclable epoxy resin and the preparation method provided by the invention are described in detail below.
The sources of the raw materials used in the examples:
example 1
The recyclable epoxy resin comprises, by mass, 100g of a traditional epoxy resin E51, 5g of a hyperbranched polyether type epoxy resin, 43g of a curing agent glutaric anhydride, 22g of a reactive diluent phenyl glycidyl ether and 0.067g of a catalyst zinc acetylacetonate.
In this example, the viscosity gamma of the hyperbranched polyether epoxy resin was determined by means of a viscometer at 25℃and a rotational speed of 20r/min using an RV-06 spindle 1 352mpa.s, testing the viscosity gamma of the conventional epoxy resin under the same conditions 2 Relative molecular weight mr of hyperbranched polyether epoxy resin of 12940mpa.s 2 For 14532, the relative molecular weight mr of the conventional epoxy resin 1 380, the theoretical viscosity gamma of the epoxy resin raw material can be obtained according to the following formula 3 4246.20mpa.s;
meanwhile, the dilution rate of the obtained active diluent is 75%, the variation of the pressure during vacuumizing is 2mpa, and the vacuumizing time is 600s, so that the content X of the active diluent is 22g according to the following formula.
A preparation method of recoverable 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 hyperbranched polyether type epoxy resin, stirring and mixing uniformly, and adding the reactive epoxy diluent to continue stirring after the traditional epoxy resin and the hyperbranched polyether type epoxy resin are mixed uniformly;
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 for 10min at the constant temperature of 90 ℃ until bubbles are removed, and then pouring the mixture into a preheating mould to perform stage heating and solidification according to the processes of 100 ℃/1h,130 ℃/2h and 160 ℃/2h, so as to obtain the recyclable epoxy resin.
A method for recovering recoverable epoxy resin includes such steps as immersing the recoverable epoxy resin prepared by said method in 1, 2-propanediol, stirring at 160 deg.C for 2 hr until it is completely dissolved, and vacuum distilling to obtain recovered solvent and low-molecular epoxy resin.
Example 2
The recyclable epoxy resin comprises, by mass, 100g of a traditional epoxy resin E54, 4g of a hyperbranched polyether type epoxy resin, 45g of a curing agent succinic anhydride, 18.32g of an active diluent o-cresol glycidyl ether and 0.067g of a catalyst zinc acetylacetonate.
In this example, the viscosity gamma of the hyperbranched polyether epoxy resin was determined by means of a viscometer at 25℃and a rotational speed of 20r/min using an RV-06 spindle 1 The viscosity gamma of the conventional epoxy resin under the same conditions was tested at 352mpa.s 2 Relative molecular weight mr of hyperbranched polyether epoxy resin of 12940mpa.s 2 For 14532, the relative molecular weight mr of the 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, the dilution rate of the obtained active diluent is 90%, the variation of the pressure during vacuumizing is 2mpa, and the vacuumizing time is 600s, so that the content X of the active diluent is 18.32g according to the following formula.
A preparation method of recoverable 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 hyperbranched polyether type epoxy resin, stirring and mixing uniformly, and adding the reactive epoxy diluent to continue stirring after the traditional epoxy resin and the hyperbranched polyether type epoxy resin are mixed uniformly;
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 for 10min at the constant temperature of 90 ℃ until bubbles are removed, and then pouring the mixture into a preheating mould to perform stage heating and solidification according to the processes of 100 ℃/1h,140 ℃/2h and 170 ℃/2h, so as to obtain the recyclable epoxy resin.
A method for recovering recoverable epoxy resin includes such steps as immersing the recoverable epoxy resin prepared by said method in 1, 2-propanediol, stirring at 160 deg.C for 2 hr until it is completely dissolved, and vacuum distilling to obtain recovered solvent and low-molecular epoxy resin.
Example 3
The recyclable epoxy resin comprises, by mass, 100g of a traditional epoxy resin E51, 6g of a hyperbranched polyether type epoxy resin, 45g of a curing agent 4,4' -diaminodiphenylmethane, 17.95g of an active diluent o-cresol glycidyl ether and 0.067g of a catalyst zinc acetate.
In this example, the viscosity gamma of the hyperbranched polyether epoxy resin was determined by means of a viscometer at 25℃and a rotational speed of 20r/min using an RV-06 spindle 1 The viscosity gamma of the conventional epoxy resin under the same conditions was tested at 352mpa.s 2 Relative molecular weight mr of the hyperbranched polyether epoxy resin of 9893mpa.s 2 For 14532, the relative molecular weight mr of the conventional epoxy resin 1 405, the theoretical viscosity gamma of the epoxy resin raw material can be obtained according to the following formula 3 3719.28mpa.s;
meanwhile, the dilution rate of the obtained active diluent is 90%, the variation of the pressure during vacuumizing is 2mpa, and the vacuumizing time is 600s, so that the content X of the active diluent is 17.95g according to the following formula.
A preparation method of recoverable 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 hyperbranched polyether type epoxy resin, stirring and mixing uniformly, and adding the reactive epoxy diluent to continue stirring after the traditional epoxy resin and the hyperbranched polyether type epoxy resin are mixed uniformly;
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 for 10min at the constant temperature of 90 ℃ until bubbles are removed, and then pouring the mixture into a preheating mould to perform stage heating and solidification according to the processes of 100 ℃/1h,130 ℃/2h and 150 ℃/2h, so as to obtain the recyclable epoxy resin.
A method for recovering the recoverable epoxy resin includes such steps as immersing the recoverable epoxy resin in ethylene glycol, stirring at 160 deg.C for 2 hr until it is completely dissolved, and vacuum distilling.
Example 4
The recyclable epoxy resin comprises, by mass, 100g of a traditional epoxy resin BPF, 4g of a hyperbranched polyether type epoxy resin, 43g of a curing agent glutaric anhydride, 15g of an active diluent o-cresol glycidyl ether and 0.067g of a catalyst zinc acetylacetonate.
In this example, the viscosity gamma of the hyperbranched polyether epoxy resin was determined by means of a viscometer at 25℃and a rotational speed of 20r/min using an RV-06 spindle 1 The viscosity gamma of the conventional epoxy resin under the same conditions was tested at 352mpa.s 2 Relative molecular weight mr of hyperbranched polyether epoxy resin at 5664mpa.s 2 For 14532, the relative molecular weight mr of the conventional epoxy resin 1 425, the theoretical viscosity gamma of the epoxy resin raw material can be obtained according to the following formula 3 2308mpa.s;
meanwhile, the dilution rate of the obtained active diluent is 90%, the variation of the pressure during vacuumizing is 1.5mpa, and the vacuumizing time is 600s, and the content X of the active diluent is 15g according to the following formula.
A preparation method of recoverable 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 hyperbranched polyether type epoxy resin, stirring and mixing uniformly, and adding the reactive epoxy diluent to continue stirring after the traditional epoxy resin and the hyperbranched polyether type epoxy resin are mixed uniformly;
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 for 10min at the constant temperature of 90 ℃ until bubbles are removed, and then pouring the mixture into a preheating mould to perform stage heating and solidification according to the processes of 100 ℃/1h,130 ℃/2h and 160 ℃/2h, so as to obtain the recyclable epoxy resin.
A method for recovering recoverable epoxy resin includes such steps as immersing the recoverable epoxy resin prepared by said method in 1, 2-propanediol, stirring at 160 deg.C for 2 hr until it is completely dissolved, and vacuum distilling to obtain recovered solvent and low-molecular epoxy resin.
Example 5
The recyclable epoxy resin comprises, by mass, 100g of a traditional epoxy resin E51, 8g of a hyperbranched polyether type epoxy resin, 50g of a curing agent glutaric anhydride, 21g of an active diluent o-cresol glycidyl ether and 0.067g of a catalyst zinc acetylacetonate.
In the present embodiment of the present invention, in the present embodiment,measuring viscosity gamma of hyperbranched polyether type epoxy resin by using RV-06 rotor at 25 ℃ and rotating speed of 20r/min by using a viscometer 1 The viscosity gamma of the conventional epoxy resin under the same conditions was tested at 352mpa.s 2 Relative molecular weight mr of hyperbranched polyether epoxy resin of 12940mpa.s 2 For 14532, the relative molecular weight mr of the conventional epoxy resin 1 380, the theoretical viscosity gamma of the epoxy resin raw material can be obtained according to the following formula 3 2971.21mpa.s;
meanwhile, the dilution rate of the obtained active diluent is 75%, the variation of the pressure during vacuumizing is 2mpa, and the vacuumizing time is 600s, so that the content X of the active diluent is 21g according to the following formula.
A preparation method of recoverable 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 hyperbranched polyether type epoxy resin, stirring and mixing uniformly, and adding the reactive epoxy diluent to continue stirring after the traditional epoxy resin and the hyperbranched polyether type epoxy resin are mixed uniformly;
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 for 20min at the constant temperature of 90 ℃ until bubbles are removed, and then pouring the mixture into a preheating mould to perform stage heating and solidification according to the processes of 95 ℃/1h,120 ℃/2h and 160 ℃/2h, so as to obtain the recyclable epoxy resin.
A method for recovering recoverable epoxy resin includes such steps as immersing the recoverable epoxy resin prepared by said method in 1, 2-propanediol, stirring at 160 deg.C for 2 hr until it is completely dissolved, and vacuum distilling to obtain recovered solvent and low-molecular epoxy resin.
Comparative example 1
A recyclable epoxy resin comprises, by mass, 100g of a conventional epoxy resin E51, 43g of a curing agent glutaric anhydride, 45g of a reactive diluent phenyl glycidyl ether and 0.067g of a catalyst zinc acetylacetonate.
A preparation method of recoverable 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 an active 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 for 10min at the constant temperature of 90 ℃ until bubbles are removed, and then pouring the mixture into a preheating mould to perform stage heating and solidification according to the processes of 100 ℃/1h,130 ℃/2h and 160 ℃/2h, so as to obtain the recyclable epoxy resin.
A method for recovering recoverable epoxy resin includes such steps as immersing the recoverable epoxy resin prepared by said method in 1, 2-propanediol, stirring at 160 deg.C for 2 hr until it is completely dissolved, and vacuum distilling to obtain recovered solvent and low-molecular epoxy resin.
Comparative example 2
The recyclable epoxy resin comprises, by mass, 100g of a traditional epoxy resin E51, 1g of a hyperbranched polyether type epoxy resin, 43g of a curing agent glutaric anhydride, 36g of a reactive diluent phenyl glycidyl ether and 0.067g of a catalyst zinc acetylacetonate.
A preparation method of recoverable 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 hyperbranched polyether type epoxy resin, stirring and mixing uniformly, and adding the reactive epoxy diluent to continue stirring after the traditional epoxy resin and the hyperbranched polyether type epoxy resin are mixed uniformly;
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 for 10min at the constant temperature of 90 ℃ until bubbles are removed, and then pouring the mixture into a preheating mould to perform stage heating and solidification according to the processes of 100 ℃/1h,130 ℃/2h and 160 ℃/2h, so as to obtain the recyclable epoxy resin.
A method for recovering recoverable epoxy resin includes such steps as immersing the recoverable epoxy resin prepared by said method in 1, 2-propanediol, stirring at 160 deg.C for 2 hr until it is completely dissolved, and vacuum distilling to obtain recovered solvent and low-molecular epoxy resin.
Comparative example 3
The recyclable epoxy resin comprises, by mass, 70g of a traditional epoxy resin E51, 30g of a hyperbranched polyether type epoxy resin, 43g of a curing agent glutaric anhydride and 0.067g of a catalyst zinc acetylacetonate.
A preparation method of recoverable 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 hyperbranched polyether type epoxy resin, stirring and mixing uniformly, and adding the reactive epoxy diluent to continue stirring after the traditional epoxy resin and the hyperbranched polyether type epoxy resin are mixed uniformly;
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 for 10min at the constant temperature of 90 ℃ until bubbles are removed, and then pouring the mixture into a preheating mould to perform stage heating and solidification according to the processes of 100 ℃/1h,130 ℃/2h and 160 ℃/2h, so as to obtain the recyclable epoxy resin.
A method for recovering recoverable epoxy resin includes such steps as immersing the recoverable epoxy resin prepared by said method in 1, 2-propanediol, stirring at 160 deg.C for 2 hr until it is completely dissolved, and vacuum distilling to obtain recovered solvent and low-molecular epoxy resin.
Performance test:
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 testing was performed according to the test methods of ASTM D638 and ASTM D790, respectively.
Comparative example 1 compared with example 1, the hyperbranched polyether type epoxy resin is not used, and a large amount of reactive diluent is used for diluting the epoxy resin raw material, and as can be seen from the data, the glass transition temperature Tg is reduced by 14.9 ℃, and the recovery rate of the epoxy resin is reduced by 13 percent, because the glycidyl ether hyperbranched polymer introduced by the invention ensures that the material dynamically exchanges dynamic chemical bonds (ester bonds), simultaneously maintains the stability of part of the chemical bonds, and improves the recovery rate of the recyclable epoxy resin.
Comparative example 2 uses only a small amount of hyperbranched polyether type epoxy resin as compared with example 1, and it is found that the larger the content of the reactive diluent in the system, the less dynamic chemical bonds (ester bonds) in the recoverable epoxy resin under the same mass, thereby affecting the recovery rate of the epoxy resin.
Comparative example 3 in order to ensure that the viscosity of the recyclable epoxy resin reaches the standard value suitable for vacuum infusion and pultrusion, compared with example 1, an excessive hyperbranched polyether type epoxy resin is used, and in comparative example 3, a reactive diluent is not used, and as can be seen from the data, 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 type epoxy resin increases the relative molecular weight of the epoxy resin raw material, the curing density of the epoxy resin is increased, the tensile modulus and the flexural modulus are further influenced, and the small molecular structure of the composite solvent cannot fully act on dynamic chemical bonds during recovery due to the excessive crosslinking density of the cured product, so that the recovery rate of the recyclable epoxy resin is reduced.
It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (6)
1. A method for recycling recyclable epoxy resin is characterized in that in a sealing state, the recyclable epoxy resin is soaked in a composite solvent, stirred for 2-10 hours at 70-200 ℃ until the recyclable epoxy resin is completely dissolved, and then reduced pressure distillation is carried out to obtain a recycled solvent and low-molecular epoxy resin; the low molecular epoxy resin is obtained through chemical recovery, and the stability of partial chemical bonds is maintained while the ester bonds are dynamically exchanged;
according to the mass portion, the recyclable epoxy resin comprises 45% -65% of epoxy resin raw materials, 35% -55% of curing agent and 0.05% -5% of catalyst, wherein the epoxy resin raw materials comprise traditional epoxy resin and hyperbranched polyether type epoxy resin which are compounded according to the mass ratio of 100:3-20; the recyclable epoxy resin is suitable for vacuum infusion and pultrusion, and the viscosity of the recyclable epoxy resin is 300-500 mpa.s;
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 way:
wherein, gamma 3 The theoretical viscosity of the epoxy resin raw material is calculated by the compounding 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 the 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 X is less than M; q is the viscosity reduction rate of the reactive diluent;
the pressure variation is used for vacuumizing; t is vacuumizing time;
the compound 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.
2. The method of claim 1, wherein 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.
3. The method for recycling recoverable epoxy resin according to claim 1, wherein the hyperbranched polyether type epoxy resin is prepared from glycidyl ether type epoxy resin by a proton transfer polymerization method.
4. The method for recycling epoxy resin according to 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 linear aliphatic acid anhydride, aromatic anhydride and alicyclic anhydride.
5. The method for recycling a recyclable epoxy resin according to 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 method for recycling epoxy resin according to any one of claims 1 to 5, wherein the method for preparing the recyclable epoxy resin comprises the following steps:
s1: weighing the components according to the mass ratio;
s2: adding the traditional epoxy resin into a reaction container, adding the hyperbranched polyether type epoxy resin, stirring and mixing uniformly, and adding the reactive epoxy diluent to continue stirring after the traditional epoxy resin and the hyperbranched polyether type epoxy resin are mixed uniformly;
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: vacuumizing for 10-20min at the constant temperature of 70-90 ℃ until bubbles are removed, and then pouring into a preheating die for stage heating and curing to obtain the recyclable epoxy resin.
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| CN114752109A (en) * | 2022-05-07 | 2022-07-15 | 浙江大学 | Upgrading recycling method of resin containing ester bonds |
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