CN112920379A - Epoxy resin monomer and intermediate thereof, preparation method, epoxy resin and recovery method - Google Patents
Epoxy resin monomer and intermediate thereof, preparation method, epoxy resin and recovery method Download PDFInfo
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- CN112920379A CN112920379A CN202110331263.0A CN202110331263A CN112920379A CN 112920379 A CN112920379 A CN 112920379A CN 202110331263 A CN202110331263 A CN 202110331263A CN 112920379 A CN112920379 A CN 112920379A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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Abstract
本发明涉及高分子材料领域，特别涉及一种环氧树脂单体及其衍生物、该环氧树脂单体的中间体及其衍生物、它们的制备方法、由所述环氧树脂单体制备得到的环氧树脂，以及所述环氧树脂的回收方法。所述环氧树脂单体具有式(I)所示结构，其中，A1和A2各自独立地选自Z选自以下结构：Z1基团Z2基团Z3基团Z4基团本发明的环氧树脂单体能够得到的可回收型环氧树脂，能够在热条件下多次重复加工成型，并且能够在酸条件下充分降解，能够实现资源的回收利用，安全环保，具有广阔的应用前景。The invention relates to the field of polymer materials, in particular to an epoxy resin monomer and derivatives thereof, an intermediate of the epoxy resin monomer and derivatives thereof, their preparation methods, and preparation from the epoxy resin monomers The obtained epoxy resin, and the recovery method of the epoxy resin. The epoxy resin monomer has the structure shown in formula (I), wherein A 1 and A 2 are each independently selected from Z is selected from the following structures: Z1 group Z2 group Z3 group Z4 group The recyclable epoxy resin that can be obtained by the epoxy resin monomer of the present invention can be repeatedly processed and molded under thermal conditions, and can be fully degraded under acid conditions, can realize resource recycling, is safe and environmentally friendly, and has a wide range of application prospects.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to an epoxy resin monomer, an intermediate of the epoxy resin monomer, preparation methods of the epoxy resin monomer and the intermediate, an epoxy resin prepared from the epoxy resin monomer, and a recovery method of the epoxy resin.
Background
Epoxy resin is a thermosetting polymer material with a three-dimensional crosslinking structure, and is widely applied to the fields of coatings, adhesives, civil engineering and construction, microelectronic manufacturing, fiber reinforced composite materials and the like due to excellent mechanical properties, adhesive properties, dimensional stability, chemical corrosion resistance and electrical insulation. However, the three-dimensional cross-linked network structure of the current commercialized epoxy resin is constructed by irreversible covalent chemical bonds, so that the epoxy resin has the characteristics of insolubility and infusibility once being cured, and is difficult to recycle. With the rapid development of economic society, the increasing year by year of waste epoxy resin products poses a great challenge to ecological environment protection. The existing treatment modes for epoxy resin wastes mainly comprise land landfill, incineration, natural environment aging, thermal cracking, mechanical crushing, supercritical fluid degradation and the like, but the recovery methods not only cause resource waste, but also have the problems of long treatment period, environmental pollution, high energy consumption, high equipment cost and the like. The intrinsic recyclable epoxy resin is designed and developed, the problem of recycling of epoxy resin waste can be fundamentally solved, and the intrinsic recyclable epoxy resin has considerable economic value and important environmental protection significance.
At present, the introduction of dynamic covalent bonds with environmental stimulus responsiveness into the cross-linked structure of epoxy resin is an important approach for developing epoxy resin with recyclable function. Under the stimulation of specific environmental conditions (such as light, heat, a magnetic field, an electric field, a chemical solvent, pH value change and the like), the dynamic covalent bonds are subjected to reversible bond breaking-bonding or exchange reaction processes, so that the crosslinked structure of the epoxy resin is rearranged or degraded, and the epoxy resin has the characteristics of repeated processing and forming, degradability and the like on a macroscopic scale and can be recycled.
Based on the idea of dynamic covalent bond, polyamine curing agent containing imine dynamic covalent bond is found in the prior art, and epoxy resin is crosslinked and cured to obtain epoxy resin which can be repeatedly hot-pressed and repeatedly molded. However, the mechanical properties of the epoxy resin are remarkably reduced along with the increase of the times of repeated processing and molding, and the epoxy resin without use value after repeated processing and molding still faces the recycling problem.
In the prior art, the method for preparing the recyclable epoxy resin by using the body click chemical reaction is also used, and the intermediate with the end group of furan functional group is obtained by adopting the click reaction of polyfunctional epoxy resin and furfuryl mercaptan under the action of a tertiary amine catalyst; subsequently, reacting the intermediate with a crosslinking agent containing maleimide groups in a Diels-Alder (DA) reaction to form a reversibly crosslinked epoxy resin; by utilizing the reversible dynamic property of the DA addition structure, the epoxy resin can be subjected to decrosslinking at high temperature, so that the repeated recycling and secondary processing of the epoxy resin are realized. However, when the epoxy resin is heated, the epoxy resin loses mechanical properties due to the fact that the epoxy resin can generate a de-crosslinking reaction, so that the epoxy resin has potential safety hazards when being used under high-temperature conditions.
Although the epoxy resins with repeatable processing and forming and degradable characteristics are obtained based on dynamic covalent bonds in the prior art, the defects that the mechanical properties are remarkably reduced along with the increase of the processing and forming times and potential safety hazards exist at high temperature still exist, the application of the recyclable epoxy resins is greatly limited, and further research and improvement are urgently needed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an epoxy resin monomer, an intermediate of the epoxy resin monomer, preparation methods of the epoxy resin monomer and the intermediate, an epoxy resin prepared from the epoxy resin monomer, and a recovery method of the epoxy resin.
The recyclable epoxy resin obtained by the epoxy resin monomer can be repeatedly processed and molded under a hot condition, can be fully degraded under an acid condition, can realize the recycling of resources, is safe and environment-friendly, and has wide application prospect.
The invention provides an epoxy resin monomer, wherein the epoxy resin monomer has a structure shown in a formula (I),
wherein A is1And A2Each independently selected from
R1And R3Each independently selected from the group consisting of substituted or unsubstituted: - (CH)2)a-and a is an integer from 1 to 5, a saturated aliphatic branch of a binary to a seven-membered carbon;
R2and R4Each independently selected from one or more of H, methyl, ethyl and halogen;
z is selected from the following structures:
z1 radical
(Z11 group) or
(Z12 radical), wherein R5And R7Each independently selected from the group consisting of substituted or unsubstituted: - (CH)2)n-and n is an integer from 1 to 5, a saturated aliphatic branch of binary to seven-membered carbon; r6One or more selected from H, methyl and halogen;
z2 radical
Wherein R is8Selected from the following substituted or unsubstituted groups: - (CH)2)m-and m is an integer from 4-10, a saturated aliphatic branch of binary to seven-membered carbon;
z3 radical
Wherein R is9And R10Each independently selected from the group consisting of substituted or unsubstituted: - (CH)2)p-and p is an integer from 2-5, a saturated aliphatic branch of binary to seven-membered carbon;
z4 radical
And q is an integer of 2 to 5,
R11and R12Each independently selected from the group consisting of substituted or unsubstituted: - (CH)2)x-and x is an integer from 1 to 5, a saturated aliphatic branch from binary to quaternary carbon,
R13and R14Each independently selected from the group consisting of substituted or unsubstituted: H. - (CH)2)y-and y is an integer from 1 to 3, a saturated aliphatic branch from a binary carbon to a quaternary carbon.
In the present invention, in the group
Indicates the point of attachment of the group to the main structure.
In the formula (I), A1And A2May be the same or different and are each independently selected from
(A1 group) and
(A2 group).
In the A1 radical and the A2 radical, R1And R3Are radicals attached to the backbone structure of formula (I), each independently selected from the group consisting ofOr unsubstituted groups of: - (CH)2)aA is an integer from 1 to 5 (e.g. 1, 2, 3, 4, 5); saturated aliphatic branches of binary to seven-membered carbons (e.g., binary, ternary, quaternary, pentavalent, hexahydric, heptavalent) (the term "branched" as used herein also includes the case where the group itself is straight-chain, but forms a branch with the backbone structure). When these groups are substituted, the substituents may be selected from one or more of the halogens (F, Cl, Br, I).
In the A1 radical and the A2 radical, R2And R4On a carbocyclic ring, which may be H, meaning that the carbocyclic ring is unsubstituted; or each independently of the others may be other than H, meaning that the carbocyclic ring is substituted, and when the carbocyclic ring is substituted, R2And R4Each independently selected from one or more of methyl, ethyl, and halogen.
In the present invention, R is2And R4Exemplary carbocyclic ring substitutions, as shown by the groups a1 and a2, when the substitution site is drawn inside the carbocyclic ring, indicate that the position of the substitution is not limiting and can be any position on the carbocyclic ring; the number of substitutions is also not limited and may be one or more.
In the present invention, A1And A2The groups may each be independently selected from, but are not limited to, the following structures:
At the Z1 radical
The method comprises the following steps:
R5and R7Are groups attached to the backbone structure of formula (I), each of which is independently selected from the group consisting of substituted or unsubstituted: - (CH)2)nN is an integer from 1 to 5 (e.g. 1, 2, 3, 4, 5); binary carbonSaturated aliphatic branches to five-membered carbons (e.g., binary, ternary, quaternary, quinary). When these groups are substituted, the substituents are selected from one or more of the groups that may be halogen.
In the Z1 radical, R6Located on a carbocyclic ring, which may be H, meaning that the carbocyclic ring is unsubstituted; or may be other than H, represents a substituted carbocyclic ring, and when substituted, R6One or more selected from methyl, ethyl and halogen.
At the Z2 radical
The method comprises the following steps:
R8selected from the following substituted or unsubstituted groups: - (CH)2)m-, m is an integer from 4 to 10 (e.g. 4, 5, 6, 7, 8, 9, 10); saturated aliphatic branches of binary to seven-membered carbons (e.g., binary, ternary, quaternary, quinary, hexabasic, heptabasic). When these groups are substituted, the substituents may be selected from one or more of the halogens.
At the Z3 radical
The method comprises the following steps:
R9and R10Are groups attached to the backbone structure of formula (I), each of which is independently selected from the group consisting of substituted or unsubstituted: - (CH)2)pP is an integer from 2 to 5 (e.g. 2, 3, 4, 5); saturated aliphatic branches of binary to seven-membered carbons (e.g., binary, ternary, quaternary, quinary, hexabasic, heptabasic). When these groups are substituted, the substituents may be selected from one or more of the halogens.
At the Z4 radical
The method comprises the following steps:
q is an integer of 2 to 5 (e.g., 2, 3, 4, 5).
In the Z4 radical, R11And R12Each independently selected from the group consisting of substituted or unsubstituted: - (CH)2)x-x is an integer from 1 to 5 (e.g. 1, 2, 3, 4, 5); binary to quaternary carbon (e.g., binary, ternary, quaternary) saturated aliphatic branches. When these groups are substituted, the substituents may be selected from one or more of the halogens.
In the Z4 radical, R13And R14Each independently selected from the group consisting of substituted or unsubstituted: H. - (CH)2)y-y is an integer from 1 to 3 (e.g. 1, 2, 3); binary to quaternary carbon (e.g., binary, ternary, quaternary) saturated aliphatic branches. When these groups are substituted, the substituents may be selected from one or more of the halogens.
In the present invention, the Z group may be selected from, but is not limited to, the following structures:
According to a specific embodiment of the present invention, the structure of formula (I) is a centrosymmetric structure.
According to a specific embodiment of the present invention, the structure of formula (I) is an axisymmetric structure.
According to a specific embodiment of the present invention, the structure of formula (I) is a non-centrosymmetric structure.
Those skilled in the art will appreciate that various spatial structural variations that may exist in the structure shown in formula (I) are within the scope of the present invention.
The scope of the present invention also includes various derivatives of the compound of formula (I), and any modification of the epoxy resin monomer having the structure shown in formula (I) within the ability of those skilled in the art is within the scope of the present invention.
The epoxy resin prepared from the epoxy resin monomer with the structure shown in the formula (I) has excellent mechanical property and recovery property.
In a second aspect, the present invention provides an intermediate compound having a structure represented by formula (II),
wherein, B1And B2Each independently selected from
R1～R4Is as defined in the first aspect of the invention; the choice of Z is the same as defined in the first aspect of the invention. And will not be described in detail herein.
The intermediate compound of the second aspect of the present invention is the structure of the compound of formula (I) before the epoxidation reaction, i.e. the six-membered rings at both ends have a double bond structure.
In the invention, the intermediate compound with the structure of formula (II) can obtain the compound of formula (I) through epoxidation reaction.
In the present invention, B1And B2The group may be selected from, but is not limited to, the following structures:
In the present invention, the compound obtained when the epoxy group in the compound of the formula (I) is replaced by a double bond is included in the scope of the present invention.
In addition, the intermediate compounds of the second aspect of the present invention also include compounds which do not correspond exactly to the structure of formula (I): although the structure is different from that of the "compound obtained when the double bond is substituted for the epoxy group in the compound having the structure of the formula (I)", the reaction can be carried out simultaneously during the epoxidation reaction, and the compound having the structure of the formula (I) can be finally obtained.
In a third aspect, the present invention provides a process for the preparation of an intermediate compound according to the second aspect of the invention, said process comprising: carrying out an acetalization reaction on a compound with a structure shown in a formula (III-1) and/or a formula (III-2) and a compound with a structure shown in a formula (IV),
R1～R4is as defined in the first aspect of the invention; the choice of Z is the same as defined in the first aspect of the invention.
In the above-mentioned acetalization reaction, the double bond of the compound having the structure represented by the formula (IV) is opened, and the double bond is bonded to the alcohol group in the compound having the structure represented by the formula (III-1) and/or the compound having the structure represented by the formula (III-2) to form an acetal structure.
Taking the example that the structural compound shown in the formula (III-1) reacts with the structural compound shown in the formula (IV) to generate the structural compound shown in the formula (II-1), the reaction is shown by the following formula 1, formula 1:
in the present invention, the reaction conditions of the acetalization reaction may be performed in the manner of the acetalization reaction which is conventional in the art. For example, the acetalization reaction is carried out in an organic solvent, which may be selected from one or more of chloroform, dichloromethane, tetrahydrofuran, acetone, ethyl acetate, N dimethylformamide, N-methylpyrrolidone.
Preferably, the acetalization reaction is carried out in the presence of a catalyst.
Preferably, the catalyst is selected from one or more of p-toluenesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, trichloroacetic acid and p-nitrobenzenesulfonic acid.
Preferably, the molar ratio of the used amount of the catalyst to the used amount of the compound of the structure shown In (IV) is (0.02-0.2): 1, more preferably (0.05-0.15): 1.
in the aldolization reaction, the reaction molar number of the compound having the structure represented by the formula (IV) and the compound having the formula (III) (including the compound having the structure represented by the formula (III-1) and the compound having the structure represented by the formula (III-2)) is 1: 2; therefore, the molar ratio of the compound of the structure (IV) to the compound of the formula (III) used in the reaction may be adjusted to about 1:2, and one of them may be used in excess in order to sufficiently proceed the reaction, for example, the molar ratio of the compound of the structure (IV) to the compound of the formula (III) is 1: (2.0-3.0).
Preferably, the acetalization conditions include: the temperature is 0-40 ℃, preferably 0-25 ℃; the time is 4-10h, preferably 6-10 h.
In the present invention, in order to facilitate the continuation of the subsequent reaction, it is preferable to purify the obtained product after the acetalization reaction. For example, after the acetalization reaction is completed, it is washed to neutrality with deionized water, and then the organic solvent is distilled off under reduced pressure.
In a fourth aspect, the present invention provides an intermediate compound having a structure represented by formula (V),
wherein A is selected from A in the first aspect of the invention1And A2B is selected from B in the second aspect of the invention1And B2(ii) a The choice of Z is the same as in the first aspect of the invention.
When the epoxy resin monomer of the present invention is prepared by epoxidation of the intermediate compound represented by formula (II), the intermediate compound having the structure represented by formula (V) may be present in the environmental product due to the insufficiency of the epoxidizing agent or the insufficiency of the epoxidation, and the compound may be further reacted to obtain the epoxy resin monomer of the present invention. Therefore, the intermediate compound with the structure shown in the formula (V) also belongs to the protection scope of the invention.
In the fourth aspect of the present invention, the "structure represented by formula (V) is a structure in which one of two epoxy structures in the structure represented by formula (I) is replaced with a double bond".
In a fifth aspect, the present invention provides a method for preparing the epoxy resin monomer according to the first aspect, wherein the method comprises: subjecting an intermediate compound to an epoxidation reaction such that the double bond in the intermediate compound is opened and an oxygen atom is attached to form an epoxy structure; the intermediate compound is one or more of an intermediate compound prepared by the method of the third aspect, an intermediate compound of the second aspect and an intermediate compound of the fourth aspect.
The process of the fifth aspect of the present invention may be carried out by first performing the process of the third aspect of the present invention to prepare an intermediate compound having a structure represented by formula (II), or may be directly purchased as an intermediate compound having a structure represented by formula (II) of the second aspect of the present invention; in addition, although not usually, the epoxidation reaction may be carried out on the basis of an intermediate compound having a structure represented by the formula (V) described in the fourth aspect.
The epoxidation reaction of the present invention may be carried out in a manner conventional in the art, for example, the epoxidation reaction includes: and (c) contacting the intermediate compound with an epoxidation reagent selected from peroxides and monopersulfates in an organic solvent and carrying out an epoxidation reaction.
Preferably, the epoxidation reagent is selected from one or more of m-chloroperoxybenzoic acid, p-nitroperoxybenzoic acid, peracetic acid, peroxypropiolic acid, p-nitroperoxybenzoic acid, m-nitroperoxybenzoic acid, and potassium monopersulfate complex salts.
Preferably, the organic solvent is selected from one or more of chloroform, dichloromethane, carbon tetrachloride, tetrahydrofuran, N-dimethylformamide and N-methylpyrrolidone.
Preferably, the epoxidizing agent is used in an amount of 2 to 8 moles, preferably 4 to 6 moles, relative to 1 mole of the intermediate compound having a structure represented by formula (II).
Preferably, the contacting reaction is a slow contact, for example, a dropwise manner contact on a laboratory scale. After the completion of the dropwise addition, the epoxidation reaction was continued for a while.
Preferably, the epoxidation reaction conditions include: the temperature is-4 ℃ to 10 ℃, preferably 0 ℃ to 6 ℃; the time is 5-12h, preferably 8-10 h.
In the present invention, in order to facilitate the continuation of the subsequent reaction, it is preferable that the product is subjected to a subsequent treatment after the reaction is completed. For example: and after the reaction is finished, filtering the obtained mixture, washing the filtrate to the center by using deionized water, drying the filtrate by using anhydrous sodium sulfate, and removing the organic solvent by reduced pressure distillation to obtain the acetal structure-containing epoxy resin monomer.
In a sixth aspect, the present invention provides an epoxy resin, wherein the epoxy resin is obtained by a curing reaction of the epoxy resin monomer and/or the derivative thereof according to the first aspect of the present invention in the presence of a curing agent.
The curing agent of the present invention is not particularly limited, and a curing agent conventionally used in the art for preparing an epoxy resin from an epoxy resin monomer can be selected.
Preferably, the curing agent is an acid anhydride curing agent or a cationic curing agent.
When the curing agent is an acid anhydride curing agent, preferably, the acid anhydride curing agent is selected from one or more of methyl hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, and methyl nadic anhydride.
The operation and reaction conditions for curing the epoxy resin using the acid anhydride-based curing agent may be performed in a manner conventional in the art. Examples include: and (3) carrying out stepped heating curing on the mixed material of the anhydride curing agent, the accelerator and the epoxy resin in an oven to obtain an epoxy resin cured product.
The acid anhydride-based curing agent is preferably used in an amount of 1.4 to 2.4 mol, more preferably 1.7 to 2.0 mol, based on 1 mol of the epoxy resin monomer.
Preferably, the curing reaction is also carried out in the presence of an accelerator selected from the group consisting of 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole. Preferably, the accelerator is used in an amount of 0.02 to 0.12 parts by mole, more preferably 0.05 to 0.1 parts by mole, relative to 1 part by mole of the epoxy resin.
The step heating method includes, for example: a first time (e.g., 0.8-1.2h) at a first temperature (e.g., 95-110 ℃), a second time (e.g., 1.5-2.5h) at a second temperature (e.g., 130-.
When the curing agent is a cationic curing agent, preferably, the cationic curing agent is selected from one or more of triarylsulfonium salt curing agent, diaryliodonium salt curing agent, and ammonium blocked lewis acid salt curing agent.
The operating methods and reaction conditions for curing epoxy resins using cationic curing agents can be carried out in a manner conventional in the art. For example, the epoxy resin and the cationic curing agent are uniformly mixed and then cured by ultraviolet irradiation or heating.
Preferably, the cationic curing agent is used in an amount of 0.1 to 5.0 parts by weight, more preferably 0.5 to 3.0 parts by weight, relative to 100 parts by weight of the epoxy resin monomer.
A seventh aspect of the present invention provides the method for recycling an epoxy resin according to the sixth aspect of the present invention, comprising:
degrading the epoxy resin in an acid environment, or
And repeatedly processing and molding the epoxy resin in a hot environment.
The epoxy resin recovery mode comprises two modes of degradation and repeated processing and forming.
The degradation is recovered by placing the epoxy resin in an acid environment.
Preferably, the acid environment is an organic solution or an organic-aqueous mixed solution containing an acid, and the content of the acid is 0.1 to 5mol/L, more preferably 0.2 to 2 mol/L.
Preferably, the acid is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid.
Preferably, the organic solvent in the organic solution is selected from one or more of methanol, ethanol and acetone.
When the organic-water mixed solution is adopted, the volume of the organic solvent and the water is (4-8): 1.
preferably, the conditions for degradation in an acid environment include: the temperature is 0-80 ℃, and the time is 1-10 h.
The recycling mode of the repeated processing molding comprises the step of carrying out hot pressing on the epoxy resin.
Preferably, the conditions for repeating the machine-shaping include: the pressure is 0.5-2 MPa; the temperature is 140-200 ℃; the hot pressing time is 0.5-3 h.
Through the technical scheme, compared with the prior art, the invention at least has the following advantages:
(1) the epoxy resin monomer is in a liquid state at normal temperature, and has good processing property;
(2) the epoxy resin obtained after the epoxy resin monomer is cured has excellent mechanical property which is not inferior to that of the conventional epoxy resin;
(3) the epoxy resin can be recycled, so that the resource is saved, and the environment is protected;
(4) the epoxy resin can be repeatedly processed and molded under a hot pressing condition, and under a high temperature condition (for example, about 140 ℃), the epoxy resin does not have potential safety hazard caused by that bonds are completely opened to become liquid like epoxy resin obtained by Diels-Alder (DA) reaction; the epoxy resin is still solid under the high-temperature condition, and only has plasticity, so that the epoxy resin is relatively safe;
(5) the epoxy resin can be degraded under an acidic condition, so that the epoxy resin can be reused in a larger application range and has huge commercial value.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Detailed Description
The present invention will be described in detail below by way of examples. The described embodiments of the invention are only some, but not all embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, the reagents used are all commercially available analytical grade unless otherwise specified.
In the following examples, the reaction is carried out using only the compound of formula (IV) and the compound of formula (III-1), and since the structures and the reaction processes of the compound of formula (III-1) and the compound of formula (III-2) are very similar, and thus the reaction is carried out using only the compound of formula (IV) and the compound of formula (III-1) in this example to avoid excessive space, it is considered that the cases of the reaction with the compound of formula (III-2) and the reaction with the mixture of the compound of formula (III-1) and the compound of formula (III-2) have been confirmed, and the exemplified reactions do not limit the scope of the present invention.
Example 1
(1) Preparation of intermediate compounds
Dissolving 1, 4-cyclohexanedimethanol divinyl ether with the mole fraction of 1 and 3-cyclohexenyl-1-methanol with the mole fraction of 2 in chloroform in a reaction vessel at normal temperature, stirring for 15min, and adding p-toluenesulfonic acid with the mole fraction of 0.1. Then, the obtained mixture is reacted for 10 hours at 0 ℃ under rapid stirring, washed to neutrality by deionized water, and then the chloroform is removed by distillation under reduced pressure, so as to obtain the acetal structure-containing alicyclic olefin compound.
The reaction shown in equation 1 below occurs during this preparation:
equation 1:
(2) preparation of epoxy resin monomer
Dissolving m-chloroperoxybenzoic acid with the mole fraction of 4 in dichloromethane, dropwise adding alicyclic olefin containing an acetal structure with the mole fraction of 1 into a solution of an epoxidation reagent at 0 ℃, and after dropwise adding, continuously reacting for 8 hours at 4 ℃. And after the reaction is finished, filtering the obtained mixture, washing the filtrate to be neutral by using deionized water, drying the filtrate by using anhydrous sodium sulfate, and removing the organic solvent by reduced pressure distillation to obtain the acetal structure-containing epoxy resin monomer.
The reaction shown in equation 2 below occurs during this preparation:
equation 2:
structural characterization, viscosity and epoxy equivalent of epoxy resin monomer:
infrared Spectrum (Potassium bromide window, cm)-1)：2862-2985cm-1(C-H)，1220cm-1(C-O)，905cm-1(epoxy group);
1H NMR(DMSO-d6，ppm)：4.6(2H，O-CH-O)，3.2-3.5(12H，CH2-O, epoxy ring, -CH-), 1.1-2.2(30H, -CH)3Alicyclic rings of-CH-and-CH2-)；
Elemental analysis: c26H44O6；
Calculated values: 68.99 percent; h: 9.80 percent;
measured value: 68.96 percent; h: 9.82 percent.
(3) Preparation of epoxy resins
Stirring and uniformly mixing 1 mole fraction of acetal structure-containing epoxy resin monomer, 2 mole fraction of curing agent methyl hexahydrophthalic anhydride and 0.05 mole fraction of accelerator 2-ethyl-4-methylimidazole. The resulting epoxy resin mixture was introduced into a stainless steel mold, degassed under vacuum for 1h, cured at 100 ℃ for 1h, 140 ℃ for 2h, and 170 ℃ for 2 h. And cooling and demolding to obtain the recoverable epoxy resin containing the acetal structure.
Example 2
(1) Preparation of intermediate compounds
1, 4-cyclohexanedimethanol divinyl ether with the mole fraction of 1 and 3-cyclohexenyl-1-methanol with the mole fraction of 2.5 are dissolved in dichloromethane in a reaction vessel at normal temperature, stirred for 15min and added with p-toluenesulfonic acid with the mole fraction of 0.1. Subsequently, the resulting mixture was reacted at 25 ℃ with rapid stirring for 8 hours (the reaction of the foregoing equation 1 occurred), washed with deionized water to neutrality, and then distilled under reduced pressure to remove methylene chloride and excess 3-cyclohexenyl-1-methanol, to obtain an acetal structure-containing alicyclic olefin compound.
(2) Preparation of epoxy resin monomer
Dissolving peroxyacetic acid with the molar fraction of 6 in tetrahydrofuran, dropwise adding the acetal structure-containing alicyclic olefin with the molar fraction of 1 into the solution of the epoxidation reagent at 0 ℃, and after the dropwise addition is finished, continuing the reaction at 0 ℃ for 10 hours (the reaction of the equation 2 occurs). And after the reaction is finished, filtering the obtained mixture, washing the filtrate to the center by using deionized water, drying the filtrate by using anhydrous sodium sulfate, and removing the organic solvent by reduced pressure distillation to obtain the acetal structure-containing epoxy resin monomer.
Structural representation, viscosity and epoxy equivalent of an acetal structure-containing epoxy resin monomer:
infrared Spectrum (Potassium bromide window, cm)-1)：2860-2986cm-1(C-H)，1222cm-1(C-O)，906cm-1(epoxy group);
1H NMR(DMSO-d6，ppm)：4.5(2H，O-CH-O)，3.2-3.4(12H，CH2-O, epoxy ring, -CH-), 1.1-2.3(30H, -CH)3Alicyclic rings of-CH-and-CH2-)；
Elemental analysis: c26H44O6；
Calculated values: c: 68.99 percent; h: 9.80 percent;
measured value: c: 69.02 percent; h: 9.78 percent.
(3) Preparation of epoxy resins
Stirring and uniformly mixing 1 mole fraction of acetal structure-containing epoxy resin monomer, 1 mole fraction of curing agent methyl nadic anhydride and 0.07 mole fraction of accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole. The resulting epoxy resin mixture was introduced into a stainless steel mold, degassed under vacuum for 1h, cured at 100 ℃ for 1h, cured at 140 ℃ for 2h, and post-cured at 170 ℃ for 2 h. And cooling and demolding to obtain the recoverable epoxy resin containing the acetal structure.
Example 3
(1) Preparation of intermediate compounds
Dissolving 1, 4-cyclohexanedimethanol divinyl ether with the mole fraction of 1 and 3-cyclohexenyl-1-methanol with the mole fraction of 3 in tetrahydrofuran at normal temperature in a reaction vessel, stirring for 15min, and adding p-toluenesulfonic acid with the mole fraction of 0.15. Then, the resulting mixture was reacted at 40 ℃ with rapid stirring for 6 hours (the reaction of the foregoing equation 1 occurred), washed with deionized water to neutrality, and then tetrahydrofuran was distilled off under reduced pressure to obtain an acetal structure-containing alicyclic olefin compound.
(2) Preparation of epoxy resin monomer
P-nitroperoxybenzoic acid with the molar fraction of 5 is dissolved in N, N-dimethylformamide, acetal structure-containing alicyclic olefin with the molar fraction of 1 is dripped into the solution of the epoxidizing agent at 0 ℃, and after the dripping is finished, the reaction is continued for 9 hours at 0 ℃ (the reaction of the equation 2 occurs). And after the reaction is finished, filtering the obtained mixture, washing the filtrate to the center by using deionized water, drying the filtrate by using anhydrous sodium sulfate, and removing the organic solvent by reduced pressure distillation to obtain the acetal structure-containing epoxy resin monomer.
Structural representation, viscosity and epoxy equivalent of an acetal structure-containing epoxy resin monomer:
infrared Spectrum (Potassium bromide window, cm)-1)：2864-2988cm-1(C-H)，1219cm-1(C-O)，904cm-1(epoxy group);
1H NMR(DMSO-d6，ppm)：4.6(2H，O-CH-O)，3.1-3.4(12H，CH2-O, -CH-in the epoxy ring), 1.0-2.3(30H, -CH)3Alicyclic rings of-CH-and-CH2-)；
Elemental analysis: c26H44O6；
Calculated values: c: 68.99 percent; h: 9.80 percent;
measured value: c: 68.94 percent; h: 9.82 percent.
(3) Preparation of epoxy resins
100 parts by weight of acetal structure-containing epoxy resin monomer and 2 parts by weight of curing agent ammonium-blocked Lewis acid salt TC3632 (Shenzhen Kanji) are stirred and mixed uniformly. Introducing the obtained epoxy resin mixture into a stainless steel mold, degassing for 1h under vacuum condition, and curing at 100 ℃ for 0.5h to obtain the recoverable epoxy resin containing an acetal structure.
Example 4
The procedure was carried out in accordance with the procedure of example 1, except that, instead of the raw materials used in step (1), an intermediate compound represented by the formula (II-2), an epoxy resin monomer represented by the formula (I-2) were prepared in this order by the following reaction equation, and an epoxy resin was finally prepared.
The detection result of the obtained epoxy resin monomer is as follows:
infrared Spectrum (Potassium bromide window, cm)-1)：2862-2986cm-1(C-H)，1215cm-1(C-O)，910cm-1(epoxy group);
1H NMR(DMSO-d6，ppm)：4.7(2H，O-CH-O)，3.2-3.5(12H，CH2-O, -CH-in the epoxy ring), 1.0-2.3(24H, -CH)3Alicyclic rings of-CH-and-CH2-CH in the aliphatic chain2-)；。
Elemental analysis: c22H38O6；
Calculated values: c: 66.30 percent; h: 9.61 percent;
measured value: c: 66.28 percent; h: 9.58 percent.
Example 5
The procedure was carried out in accordance with the procedure of example 1, except that, instead of the raw materials used in step (1), an intermediate compound represented by the formula (II-3), an epoxy resin monomer represented by the formula (I-3) were prepared in this order by the following reaction equation, and an epoxy resin was finally prepared.
The detection result of the obtained epoxy resin monomer is as follows:
infrared Spectrum (Potassium bromide window, cm)-1)：2865-2990cm-1(C-H)，1218cm-1(C-O)，908cm-1(epoxy group); (ii) a
1H NMR(DMSO-d6，ppm)：4.6(2H，O-CH-O)，3.1-3.4(12H，CH2-O, -CH-in the epoxy ring), 0.9-2.4(28H, -CH)3Alicyclic rings of-CH-and-CH2-, fatsin-chain-CH2-)；。
Elemental analysis: c24H42O6；
Calculated values: c: 67.57 percent; h: 9.92 percent;
measured value: c: 67.59 percent; h: 9.90 percent.
Example 6
The procedure was carried out in accordance with the procedure of example 1, except that, instead of the raw materials used in step (1), an intermediate compound represented by the formula (II-4), an epoxy resin monomer represented by the formula (I-4) were prepared in this order by the following reaction equation, and finally an epoxy resin was prepared.
The detection result of the obtained epoxy resin monomer is as follows:
infrared Spectrum (Potassium bromide window, cm)-1)：2862-2988cm-1(C-H)，1216cm-1(C-O)，911cm-1(epoxy group);
1H NMR(DMSO-d6，ppm)：4.5(2H，O-CH-O)，3.0-3.5(16H，CH2-O, epoxy ring, -CH-), 0.9-2.4(20H, -CH)3Alicyclic rings of-CH-and-CH2-)；。
Elemental analysis: c22H38O7；
Calculated values: c: 63.74 percent; h: 9.24 percent;
measured value: c: 63.77 percent; h: 9.28 percent.
Example 7
The procedure was carried out in accordance with the procedure of example 1, except that, instead of the raw materials used in step (1), an intermediate compound represented by the formula (II-5), an epoxy resin monomer represented by the formula (I-5) were prepared in this order by the following reaction equation, and an epoxy resin was finally prepared.
The detection result of the obtained epoxy resin monomer is as follows:
infrared Spectrum (Potassium bromide window, cm)-1)：2860-2996cm-1(C-H)，1222cm-1(C-O)，909cm-1(epoxy group);
1H NMR(DMSO-d6，ppm)：4.6(2H，O-CH-O)，3.0-3.5(20H，CH2-O, epoxy ring, -CH-), 0.9-2.2(20H, -CH)3Alicyclic rings of-CH-and-CH2-)；。
Elemental analysis: c24H42O8；
Calculated values: c: 62.86 percent; h: 9.23 percent;
measured value: c: 62.79 percent; h: 9.17 percent.
Comparative example 1
The method for preparing the non-recyclable epoxy resin by curing the epoxy resin by the anhydride curing agent is conventional in the field and comprises the following specific steps:
12.6g of alicyclic epoxy resin TTA-21 (Jiangsutaer), 16.8g of curing agent methyl hexahydrophthalic anhydride and 0.3g of accelerator 2-ethyl-4-methylimidazole are stirred and mixed uniformly. The resulting epoxy resin mixture was introduced into a stainless steel mold, degassed under vacuum for 1h, cured at 100 ℃ for 1h, cured at 140 ℃ for 2h, and post-cured at 170 ℃ for 2 h. And (5) cooling and demolding to obtain the cured epoxy resin.
Comparative example 2
The non-recyclable epoxy resin is prepared according to a method for curing the epoxy resin by using a cationic curing agent, which is conventional in the field, and comprises the following specific steps:
20.0g of alicyclic epoxy resin TTA-21 (Jiangsutaert) and 0.3g of curing agent ammonium-blocked Lewis acid salt TC3632 (Shenzhen Kay) are stirred and mixed uniformly. The obtained epoxy resin mixture was introduced into a stainless steel mold, degassed under vacuum for 1 hour, and then cured at 100 ℃ for 0.5 hour to obtain a cured epoxy resin.
Comparative example 3
The preparation of the recyclable epoxy resin by a Diels-Alder (DA) reaction comprises the following specific steps:
(1) in a constant-temperature oil bath kettle at 20 ℃, 40g of novolac epoxy resin and 16g of furfuryl mercaptan are added into a 100mL three-neck round-bottom flask, and are stirred and mixed uniformly by a machine; then adding 1g N, N-dimethylbenzylamine, placing in a nitrogen protection atmosphere, and reacting for 3 hours to obtain an intermediate with a furan functional group as an end group, wherein the grafting rate reaches 99.9%;
(2) under the protection of nitrogen, the intermediate obtained by the reaction and 45g of N-N' - (4, 4-methylene diphenyl) bismaleimide are evenly stirred in a constant-temperature oil bath kettle at 160 ℃, fully reacted for 0.1 hour, poured into a polytetrafluoroethylene mould placed in an oven, and subjected to crosslinking reaction for 0.1 hour at 90 ℃ to obtain the yellow transparent epoxy resin.
Comparative example 4
The acetal epoxy resin is prepared according to the technical route of the following equation:
(1) under the condition of ice-water bath, 42.064g of 3-cyclohexene-1-methanol, 25g of 5A molecular sieve, 2.375g of p-toluenesulfonic acid monohydrate and 187.5ml of n-hexane are added into a 250ml three-neck flask with a mechanical stirrer and a thermometer, 14.021g of cyclohexylformaldehyde is added dropwise, the reaction is stopped after stirring and reacting for 6 hours, the product is washed by 15% NaOH aqueous solution firstly, then washed by deionized water to be neutral, dried by anhydrous magnesium sulfate, filtered, concentrated and distilled under reduced pressure to obtain an intermediate product.
(2) 45g of potassium hydrogen persulfate composite salt and 0.06g of ethylenediamine tetraacetic acid are dissolved by 240ml of deionized water to prepare an epoxidation reagent solution. Under the condition of ice-water bath, 10.515g of intermediate product, 0.9g of 18-crown ether-6, 90ml of dichloromethane and acetone are added into a 1000ml four-mouth bottle provided with a mechanical stirring, thermometer and constant pressure dropping funnel, the epoxidation reagent solution is added, alkali liquor is additionally taken during epoxidation to adjust the pH range of a system to be between 7 and 8, the reaction is stopped by continuously stirring for 6h, the water phase is extracted by dichloromethane after filtration, the organic phases are combined, the organic phase is washed by deionized water, and the anhydrous magnesium sulfate is used for drying, filtering and concentrating to obtain the final product.
Infrared spectrum (cm): 2979,2923,2852,1450,1435,1343,1259,1129,1078,1045,891,810,787. Nuclear magnetic resonance hydrogen spectrum (CDC13/TMS, ppm): 3.94(d, 1H, 0-CH-0), 2.89-3.36(m, 8H, 0-CH)2-，O-CH-on epoxide ring)，0.68-2.13(m，25H，-CH2-，-CH-).
(3) The epoxy resin was cured in the same manner as in step (3) of example 1.
Test example I-Performance testing
The epoxy resin monomer and the epoxy resin obtained above were subjected to the following performance tests, respectively:
(1) viscosity @25 deg.C (cps) of epoxy resin monomer
The viscosity (in cps) of the epoxy resin monomers at 25 ℃ was measured according to the method specified in GB 12007.4-89.
(2) Epoxy equivalent (g/eq) of epoxy resin monomer
The epoxy equivalent (unit g/eq) of the epoxy resin monomer was determined according to the method specified in GB/T4612-2008, respectively.
(3) Tensile Strength of epoxy resin (MPa)
The tensile strength (in MPa) of each epoxy resin was measured by the method specified in GB/T1040.3-2006.
(4) Tensile modulus (MPa) of epoxy resin
The tensile modulus (in MPa) of each epoxy resin was measured by the method specified in GB/T1040.3-2006.
The results obtained are reported in table 1.
TABLE 1
As can be seen from table 1, the epoxy resin monomer of the present invention has suitable viscosity and epoxy equivalent, and the prepared epoxy resin has comparable or even better mechanical properties than the conventional non-recycled epoxy resin.
Test example II recovery test
The epoxy resins obtained above were subjected to the following recovery tests, respectively:
(1) hot press repeated forming test
After the epoxy resin was pulverized by a grinder, the obtained resin powder was hot-pressed at 180 ℃ and a pressure of 0.5MPa for 0.5 hour to obtain a repeatedly molded epoxy resin, and the tensile strength (MPa) and tensile modulus (MPa) of the obtained epoxy resin were measured according to the above-mentioned property test methods.
According to this method, the molding was repeated 5 times, and the tensile strength (MPa) and tensile modulus (MPa) of the epoxy resin after the 5-time repeated molding were tested.
The molding was repeated 10 times, and the tensile strength (MPa) and tensile modulus (MPa) of the epoxy resin after the 10-time repeated molding were tested.
(2) Acid degradation test
5.0g of epoxy resin was placed in a 1.0M solution of hydrochloric acid/acetone (water to acetone volume ratio 1:6), allowed to stand at ambient temperature until the resin was completely degraded, and the time required for degradation was recorded.
The results obtained are reported in table 2.
TABLE 2
As can be seen from Table 2, the epoxy resin of the present invention can be repeatedly processed and molded at high temperature, and the mechanical properties of the epoxy resin after repeated molding are not significantly reduced; and can be sufficiently degraded in an acid environment. The epoxy resins of comparative example 1 and comparative example 2 are not degradable and have no recyclability. The epoxy resin prepared by DA reaction of comparative example 3 can be repeatedly molded only and is not degradable. The epoxy resin of comparative example 4, which was hot-press-repeatedly molded, had low tensile strength and long degradation time. And the mechanical properties of the epoxy resins of comparative examples 3 and 4 were significantly reduced after repeated molding for many times.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
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| CN117645584A (en) * | 2023-11-30 | 2024-03-05 | 广东能源集团科学技术研究院有限公司 | Alicyclic epoxy monomer containing acetal group dynamic covalent bond, and preparation method and application thereof |
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