Degradable epoxy resin composition, cured product and application thereof

Abstract

The invention provides a degradable epoxy resin composition, a cured product and application thereof. The degradable epoxy resin composition comprises acetal polyester glycol, epoxy resin containing ester bonds and a cationic initiator, wherein the mass ratio of the acetal polyester glycol to the epoxy resin containing ester bonds to the cationic initiator is (20-50): (50-80): (5-10); the structure of the acetal polyester diol is shown as a formula I, in which R1 comprises a group containing an acetal structure, and R2 comprises an aliphatic chain group or an aliphatic ring group. A cured product formed by the degradable epoxy resin composition has good degradability and mechanical properties, and the degradation rate of the cured product in an acid solution can reach 99% or above.

Description

Technical Field

[0001] The present invention belongs to the technical field of thermosetting resins, and in particular relates to a degradable epoxy resin composition, a cured product and applications thereof. Background Art

[0002] Epoxy resin is an important thermosetting resin. Due to its excellent bonding, electrical insulation, chemical stability, and mechanical properties, it is widely used in adhesives, coatings, electronic packaging, transportation, aerospace, and other fields. However, after curing, conventional epoxy resin forms a stable three-dimensional cross-linked network structure, which is difficult to degrade and reprocess. This not only wastes resources but also causes serious environmental pollution. To promote environmental protection and sustainable development, the degradation, recyclability, and reprocessability of epoxy resin have become a research hotspot in the polymer industry.

[0003] Recent research has found that dynamic covalent chemistry can be used to degrade epoxy resins under specific stimuli (such as heat, light, pH, or catalysts), thereby enabling their recycling. Inspired by this, researchers at home and abroad have introduced dynamic covalent bonds into the cross-linked epoxy resin network, preparing a series of novel materials with excellent degradation properties. However, the current process of epoxy resin degradation using dynamic bonds often consumes large amounts of solvent and requires specific temperature conditions. This results in relatively high energy consumption during the degradation process, hindering the widespread application of biodegradable resins in industrial fields. Summary of the Invention

[0004] In order to solve all or part of the above technical problems, the present invention provides the following technical solutions:

[0005] The first aspect of the present invention provides a degradable epoxy resin composition, comprising acetal polyester diol, an ester bond-containing epoxy resin and a cationic initiator, wherein the mass ratio of the acetal polyester diol, the ester bond-containing epoxy resin and the cationic initiator is 20-50:50-80:5-10;

[0006] The structure of the acetal polyester diol is shown in Formula I:

[0007]

[0008] Wherein, R1 includes a group containing an acetal structure, and R2 includes an aliphatic chain group or an aliphatic ring group.

[0009] The present invention takes spiroacetal / ketone compounds as a starting point and utilizes the ring-opening chain transfer reaction between acetal polyester diol and ester-containing epoxy resin in the presence of a cationic initiator to obtain a series of degradable epoxy resin compositions. The epoxy resin containing ester bonds in the degradable epoxy resin composition is copolymerized with the acetal polyester diol to form a cross-linked network system containing different ester bonds at the same time. The acetal structure can be decomposed into aldehydes and alcohols in an acidic aqueous solution, so that the cured product formed by the resin composition can be degraded in an acidic aqueous solution and has excellent degradability. In addition, the cured product of the degradable epoxy resin composition has excellent mechanical properties and is suitable for high-end application fields that require high toughness and rapid degradation of polymer materials.

[0010] In some embodiments, the acetal polyester diol includes at least one of the substances having structures shown in the following I-1 to I-11:

[0011]

[0012]

[0013] The above-mentioned acetal polyester diol can be prepared by esterifying acetal diol (HO-R1-OH) with dibasic acid (HOOC-R2-COOH). The specific preparation method can be prepared by any known method in the prior art (such as the method in CN202111088640.9), and the present invention is not particularly limited to this.

[0014] The R1 group in the acetal polyester diol structure is derived from the acetal diol HO-R1-OH. The acetal diols used to form the acetal polyester diols shown in I-1 to I-11 are the following compounds (1) to (11):

[0015]

[0016] In some embodiments, the molecular weight of the acetal polyester diol is 4000-80000 g / mol.

[0017] In some embodiments, R2 in Formula I is C1-C 10 Fatty chain groups or C3~C 10 Alicyclic group.

[0018] In some embodiments, the ester bond-containing epoxy resin includes at least one of the compound represented by Formula II and the compound represented by Formula III:

[0019]

[0020] Among them, R a 、R bare independently aliphatic chain groups or aliphatic ring groups.

[0021] Furthermore, R a 、R b Independently C2~C 10 Fatty chain groups or C3~C 10 aliphatic ring groups.

[0022] Furthermore, the ester bond-containing epoxy resin includes at least one of the compounds represented by formula II-1, formula II-2, formula II-3, formula III-1, formula III-2, and formula III-3:

[0023]

[0024] In some embodiments, the cationic initiator includes a cationic photoinitiator and / or a cationic thermal initiator.

[0025] Furthermore, the cationic photoinitiator includes one or more of diazonium salts, diaryliodonium salts, triarylsulfonium salts, alkylsulfonium salts, iron arene salts, sulfonyloxy ketones or triarylsiloxane ethers, but is not limited thereto.

[0026] Furthermore, the cationic thermal initiator includes one or a combination of multiple of antimonates, phosphates, alkylammonium salts, aryldiazonium salts or onium salts, but is not limited thereto.

[0027] A second aspect of the present invention provides the use of the degradable epoxy resin composition described in any one of the technical solutions in the preparation of adhesives, coatings, electronic consumer products, electronic packaging or composite materials.

[0028] A third aspect of the present invention provides a degradable epoxy resin cured material, which is formed by thermally curing and / or photocuring the degradable epoxy resin composition described in any one of the technical solutions.

[0029] In some embodiments, the thermal curing includes curing the degradable epoxy resin composition at a temperature of 50 to 100° C. for 3 to 6 hours.

[0030] In some embodiments, the photocuring comprises: irradiating the degradable epoxy resin composition under ultraviolet light for 5 to 10 minutes. The ultraviolet light is, for example, 365 nm ultraviolet light, but is not limited thereto.

[0031] In some embodiments, the degradation rate of the degradable epoxy resin cured material is greater than 99%.

[0032] In some embodiments, the glass transition temperature of the degradable epoxy resin cured material is above 80°C, and in some preferred embodiments, it can reach 80-150°C.

[0033] In some embodiments, the tensile strength of the degradable epoxy resin is greater than 70 MPa, and in some preferred embodiments, it can reach 70 to 140 MPa.

[0034] In some embodiments, the unnotched impact strength of the degradable epoxy resin is 30 kJ / m 2 In some preferred embodiments, the above can reach 30-50 kJ / m 2 .

[0035] A fourth aspect of the present invention provides a degradable structure, which includes the degradable epoxy resin cured product.

[0036] The fifth aspect of the present invention provides a method for degrading the degradable epoxy resin cured material. The method comprises: immersing the degradable epoxy resin cured material in an acidic solution, and the degradation rate can reach above 99%.

[0037] In some embodiments, the hydrogen ion concentration of the acidic solution is greater than 0.1 mol / L, preferably 0.1-0.5 mol / L.

[0038] In some embodiments, the soaking time is 2-24 hours.

[0039] In some embodiments, the temperature of the acidic solution is 25°C or above, preferably above 50°C, and more preferably 50-100°C.

[0040] The degradable epoxy resin cured material can be completely degraded under relatively mild conditions (such as room temperature and low hydrogen ion concentration, such as 0.1 mol / L). Of course, the degradation rate can be accelerated by increasing the temperature and hydrogen ion concentration.

[0041] Compared with the prior art, the present invention has at least the following beneficial effects:

[0042] (1) The present invention takes the spiroacetal / ketone structure as the starting point and utilizes the ring-opening chain transfer reaction between acetal polyester diol and ester-containing epoxy resin in the presence of a cationic initiator to obtain a series of degradable epoxy resin compositions. The cured resin materials have both excellent mechanical properties and degradability, and are suitable for high-end application fields that require high mechanical strength and rapid degradation of polymer materials.

[0043] (2) Compared with other degradable epoxy resin systems containing dynamic bonds, the spiroacetal structure can effectively improve the toughness and heat resistance of the epoxy resin; based on the excellent degradation performance of the degradable epoxy resin, it can be degraded in common acidic solutions, and the required degradation temperature is relatively mild, the degradation rate is relatively fast, and the degradation is complete, thus solving the problems of high energy consumption and waste of resources required for degrading epoxy resins in the prior art;

[0044] (3) The preparation method of the resin composition provided by the present invention is simple, easy to operate, the reaction conditions are controllable, easy to implement, and suitable for large-scale industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments recorded in this application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0046] Figure 1 This is the NMR spectrum of the acetal polyester diol used in the degradable resin composition in Example 12 of the present invention. DETAILED DESCRIPTION

[0047] The technical solutions of the present invention are described in detail below in conjunction with specific embodiments so that those skilled in the art can better understand and implement the technical solutions of the present invention. The specific functional details disclosed herein should not be interpreted as limiting, but rather as a basis for the claims and as a representative basis for teaching those skilled in the art to employ the present invention in various ways in virtually any appropriate detailed embodiment.

[0048] In addition, unless otherwise specified, the various raw materials used in the following examples can be purchased from the market and other channels, the various production and testing equipment used are also equipment known in the art, and the testing methods used are also testing methods known in the art.

[0049] In a specific embodiment of the present invention, the test method for the glass transition temperature of the degradable epoxy resin cured material is based on ASTM E1545-22; the test method for the tensile strength is based on GB / T 2567-2021; and the test method for the unnotched impact strength is based on GB / T 2567-2021.

[0050] The degradation rate of a degradable epoxy resin cured product in an acidic aqueous solution is tested by grinding the cured product into a powder, then placing it in an acidic solution for degradation. After degradation is complete, the solution is filtered, the filter cake is dried, and the degradation rate of the cured powder is analyzed. Degradation rate (%) = (1 - mass of the dried filter cake / mass of the cured powder) * 100%).

[0051] The acetal polyester diol used in the following specific embodiments is prepared with reference to the prior art CN202111088640.9.

[0052] Example 1

[0053] This embodiment provides a degradable epoxy resin composition, which includes acetal polyester diol, epoxy resin and iron arene salt photoinitiator (I-261) uniformly mixed in a mass ratio of 20:80:5.

[0054] The structure of the acetal polyester diol used in this embodiment is as follows, with a molecular weight of 53200 g / mol; R2 is -CH2-:

[0055]

[0056] The structure of the epoxy resin used in this embodiment is as follows:

[0057]

[0058] The degradable epoxy resin composition was irradiated under 365 nm ultraviolet light for 10 minutes to obtain a degradable epoxy resin cured product.

[0059] The relevant properties of the prepared epoxy resin cured product were tested. The results showed that the glass transition temperature of the biodegradable epoxy resin cured product was 125°C, the tensile strength was 79 MPa, and the unnotched impact strength was 35 kJ / m 2 , in an acidic aqueous solution of 0.5MH at 35°C + The degradation rate within 12 hours is 99%.

[0060] Example 2

[0061] This embodiment provides a degradable epoxy resin composition, which includes uniformly mixed acetal polyester diol, epoxy resin and diaryl iodonium salt photoinitiator (4,4'-diacetamidophenyl iodonium hexafluorophosphate) in a mass ratio of 30:70:6.

[0062] The structure of the acetal polyester diol used in this embodiment is as follows, with a molecular weight of 48600 g / mol; R2 is -CH2-:

[0063]

[0064] The structure of the epoxy resin used in this embodiment is as follows:

[0065]

[0066] The degradable epoxy resin composition was irradiated under 365 nm ultraviolet light for 8 minutes to obtain a degradable epoxy resin cured product.

[0067] The properties of the prepared epoxy resin cured product were tested. The test results showed that the glass transition temperature of the biodegradable epoxy resin cured product was 122°C, the tensile strength was 76 MPa, and the unnotched impact strength was 35 kJ / m 2 , in an acidic solution of 0.2MH at 85℃ + The degradation rate in 10 hours is 99%.

[0068] Example 3

[0069] This embodiment provides a degradable epoxy resin composition, which includes acetal polyester diol, epoxy resin and iron arene salt photoinitiator (I-262) uniformly mixed in a mass ratio of 40:60:10.

[0070] The structure of the acetal polyester diol used in this embodiment is as follows, with a molecular weight of 62200 g / mol; R2 is -CH2CH2-:

[0071]

[0072] The epoxy resin structure used in this embodiment is as follows:

[0073]

[0074] The degradable epoxy resin composition was irradiated under 365 nm ultraviolet light for 5 minutes to obtain a degradable epoxy resin cured product.

[0075] The relevant properties of the prepared biodegradable epoxy resin cured product were tested. The test results showed that the glass transition temperature of the biodegradable epoxy resin cured product was 112°C, the tensile strength was 81MPa, and the unnotched impact strength was 45kJ / m 2 , 0.5MH acid solution at 25℃ + The degradation rate within 12 hours is 99%.

[0076] Example 4

[0077] Example 4 provides a degradable epoxy resin composition, which includes a uniform mixture of acetal polyester diol, epoxy resin and triarylsulfonium salt photoinitiator (S-phenyl-S-(2-benzoxazole)-S-[4-(S-2-benzopurazole)phenyl]sulfur trifluoromethanesulfonate) in a mass ratio of 35:75:5.

[0078] The acetal polyester diol used in this embodiment has the following structure, a molecular weight of 51500 g / mol, and R2 is -CH2CH2-:

[0079]

[0080] The epoxy resin structure used in this embodiment is as follows:

[0081]

[0082] The degradable epoxy resin composition was irradiated under 365 nm ultraviolet light for 10 minutes to obtain a degradable epoxy resin cured product.

[0083] The relevant properties of the degradable epoxy resin cured product were tested. The test results showed that the glass transition temperature of the degradable epoxy resin cured product was 140°C, the tensile strength was 85MPa, and the unnotched impact strength was 47kJ / m 2 , in an acidic aqueous solution of 0.4MH at 100℃ + The degradation rate in 10 hours is 99%.

[0084] Example 5

[0085] This embodiment provides a degradable epoxy resin composition, which includes acetal polyester diol, epoxy resin and alkyl ammonium salt thermal initiator (alkyl dimethyl ammonium chloride) uniformly mixed in a mass ratio of 30:70:5.

[0086] The structure of the acetal polyester diol used in this embodiment is as follows, with a molecular weight of 39200 g / mol; R2 is -CH2CH2-:

[0087]

[0088] The epoxy resin structure used in this embodiment is as follows:

[0089]

[0090] The degradable epoxy resin composition was cured at 80° C. for 6 hours to obtain a degradable epoxy resin cured product.

[0091] The relevant properties of the prepared biodegradable epoxy resin cured product were tested. The test results showed that the glass transition temperature of the biodegradable epoxy resin cured product was 126°C, the tensile strength was 92MPa, and the unnotched impact strength was 43kJ / m 2 , in an acidic aqueous solution of 0.4MH at 100℃ + The degradation rate within 12 hours is 99%.

[0092] Example 6

[0093] This embodiment provides a degradable epoxy resin composition, which includes acetal polyester diol, epoxy resin and antimonate thermal initiator (N-benzylpyrazine hexafluoroantimonate) uniformly mixed in a mass ratio of 40:60:8.

[0094] The structure of the acetal polyester diol used in this embodiment is as follows, with a molecular weight of 58800 g / mol; R2 is -CH2CH2-:

[0095]

[0096] The structure of the epoxy resin used in this embodiment is as follows:

[0097]

[0098] The degradable epoxy resin composition was cured at 90° C. for 4 hours to obtain a degradable epoxy resin cured product.

[0099] The relevant properties of the prepared epoxy resin cured product were tested. The test results showed that the glass transition temperature of the biodegradable epoxy resin cured product was 95°C, the tensile strength was 102MPa, and the unnotched impact strength was 45kJ / m 2 , in an acidic solution of 0.5MH at 65℃ + The degradation rate within 24 hours is 99%.

[0100] Example 7

[0101] Example 7 provides a degradable epoxy resin composition, which includes a uniform mixture of acetal polyester diol, epoxy resin and triarylsulfonium salt photoinitiator (S-phenyl-S-(2-benzoxazole)-S-[4-(S-2-benzopurazole)phenyl]sulfur trifluoromethanesulfonate) in a mass ratio of 35:75:5.

[0102] The acetal polyester diol used in this embodiment has the following structure, a molecular weight of 36500 g / mol, and R2 is -CH2CH2-:

[0103]

[0104] The epoxy resin structure used in this embodiment is as follows:

[0105]

[0106] The degradable epoxy resin composition was irradiated under 365 nm ultraviolet light for 10 minutes to obtain a degradable epoxy resin cured product.

[0107] The relevant properties of the degradable epoxy resin cured product were tested. The test results showed that the glass transition temperature of the degradable epoxy resin cured product was 96°C, the tensile strength was 72MPa, and the unnotched impact strength was 50kJ / m 2 , in an acidic solution of 0.2MH at 100℃ + The degradation rate within 24 hours is 99%.

[0108] Example 8

[0109] This embodiment provides a degradable epoxy resin composition, which includes acetal polyester diol, epoxy resin and antimonate thermal initiator (N-benzylpyrazine hexafluoroantimonate) uniformly mixed in a mass ratio of 40:60:8.

[0110] The structure of the acetal polyester diol used in this embodiment is as follows, with a molecular weight of 78200 g / mol; R2 is -CH2CH2-:

[0111]

[0112] The structure of the epoxy resin used in this embodiment is as follows:

[0113]

[0114] The degradable epoxy resin composition was cured at 80° C. for 6 hours to obtain a degradable epoxy resin cured product.

[0115] The relevant properties of the prepared epoxy resin cured product were tested. The test results showed that the glass transition temperature of the biodegradable epoxy resin cured product was 131°C, the tensile strength was 91MPa, and the unnotched impact strength was 39kJ / m 2 , in an acidic solution of 0.5MH at 85℃ + The degradation rate within 24 hours is 99%.

[0116] Example 9

[0117] This embodiment provides a degradable epoxy resin composition, which includes acetal polyester diol, epoxy resin and iron arene salt photoinitiator (I-261) uniformly mixed in a mass ratio of 30:70:5.

[0118] The structure of the acetal polyester diol used in this embodiment is as follows, with a molecular weight of 41200 g / mol; R2 is

[0119]

[0120] The structure of the epoxy resin used in this embodiment is as follows:

[0121]

[0122] The degradable epoxy resin composition was irradiated under 365 nm ultraviolet light for 10 minutes to obtain a degradable epoxy resin cured product.

[0123] The relevant properties of the prepared epoxy resin cured product were tested. The results showed that the glass transition temperature of the biodegradable epoxy resin cured product was 129°C, the tensile strength was 75MPa, and the unnotched impact strength was 40kJ / m 2 , in an acidic aqueous solution at 50°C 0.5MH + The degradation rate within 24 hours is 99%.

[0124] Example 10

[0125] Example 10 provides a degradable epoxy resin composition, which includes a uniform mixture of acetal polyester diol, epoxy resin and triarylsulfonium salt photoinitiator (S-phenyl-S-(2-benzoxazole)-S-[4-(S-2-benzopurazole)phenyl]sulfur trifluoromethanesulfonate) in a mass ratio of 30:70:5.

[0126] The acetal polyester diol used in this embodiment has the following structure, with a molecular weight of 55300 g / mol; R2 is

[0127]

[0128] The epoxy resin structure used in this embodiment is as follows:

[0129]

[0130] The degradable epoxy resin composition was irradiated under 365 nm ultraviolet light for 10 minutes to obtain a degradable epoxy resin cured product.

[0131] The relevant properties of the degradable epoxy resin cured product were tested. The test results showed that the glass transition temperature of the degradable epoxy resin cured product was 116°C, the tensile strength was 80MPa, and the unnotched impact strength was 50kJ / m 2 , in an acidic solution of 0.3MH at 80℃ + The degradation rate within 24 hours is 99%.

[0132] Example 11

[0133] Example 11 provides a degradable epoxy resin composition, which includes a uniform mixture of acetal polyester diol, epoxy resin and triarylsulfonium salt photoinitiator (S-phenyl-S-(2-benzoxazole)-S-[4-(S-2-benzopurazole)phenyl]sulfur trifluoromethanesulfonate) in a mass ratio of 35:65:5.

[0134] The acetal polyester diol used in this embodiment has the following structure, with a molecular weight of 41600 g / mol; R2 is

[0135]

[0136] The epoxy resin structure used in this embodiment is as follows:

[0137]

[0138] The degradable epoxy resin composition was irradiated under 365 nm ultraviolet light for 10 minutes to obtain a degradable epoxy resin cured product.

[0139] The relevant properties of the degradable epoxy resin cured product were tested. The test results showed that the glass transition temperature of the degradable epoxy resin cured product was 120°C, the tensile strength was 97MPa, and the unnotched impact strength was 42kJ / m 2 , in an acidic solution of 0.5MH at 80℃ + The degradation rate within 24 hours is 99%.

[0140] Example 12

[0141] This embodiment provides a degradable epoxy resin composition, which includes acetal polyester diol, epoxy resin and antimonate thermal initiator (N-benzylpyrazine hexafluoroantimonate) uniformly mixed in a mass ratio of 40:60:8.

[0142] The structure of the acetal polyester diol used in this embodiment is as follows, with a molecular weight of 72000 g / mol; R2 is

[0143]

[0144] Figure 1 This is the NMR spectrum of the acetal polyester diol used in Example 12.

[0145] The structure of the epoxy resin used in this embodiment is as follows:

[0146]

[0147] The degradable epoxy resin composition was cured at 90° C. for 3 hours to obtain a degradable epoxy resin cured product.

[0148] The relevant properties of the prepared epoxy resin cured product were tested. The test results showed that the glass transition temperature of the biodegradable epoxy resin cured product was 103°C, the tensile strength was 112MPa, and the unnotched impact strength was 45kJ / m 2 , in an acidic solution of 0.5MH at 80℃ + The degradation rate within 24 hours is 99%.

[0149] Example 13

[0150] Example 13 provides a degradable epoxy resin composition, which includes a uniform mixture of acetal polyester diol, epoxy resin and triarylsulfonium salt photoinitiator (S-phenyl-S-(2-benzoxazole)-S-[4-(S-2-benzopurazole)phenyl]sulfur trifluoromethanesulfonate) in a mass ratio of 40:60:5.

[0151] The acetal polyester diol used in this embodiment has the following structure, with a molecular weight of 69300 g / mol; R2 is

[0152]

[0153] The epoxy resin structure used in this embodiment is as follows:

[0154]

[0155] The degradable epoxy resin composition was irradiated under 365 nm ultraviolet light for 10 minutes to obtain a degradable epoxy resin cured product.

[0156] The relevant properties of the degradable epoxy resin cured product were tested. The test results showed that the glass transition temperature of the degradable epoxy resin cured product was 120°C, the tensile strength was 97MPa, and the unnotched impact strength was 42kJ / m 2 , in an acidic solution of 0.5MH at 60℃ + The degradation rate within 12 hours is 99%.

[0157] Example 14

[0158] Example 14 provides a degradable epoxy resin composition, which includes uniformly mixed acetal polyester diol, epoxy resin and diaryl iodonium salt photoinitiator (4,4′-diacetamidophenyl iodonium hexafluorophosphate) in a mass ratio of 30:70:5.

[0159] The structure of the acetal polyester diol used in this embodiment is as follows, with a molecular weight of 59100 g / mol; R2 is

[0160]

[0161] The structure of the epoxy resin used in this embodiment is as follows:

[0162]

[0163] The degradable epoxy resin composition was irradiated under 365 nm ultraviolet light for 10 minutes to obtain a degradable epoxy resin cured product.

[0164] The relevant properties of the prepared epoxy resin cured product were tested. The test results showed that the glass transition temperature of the degradable epoxy resin cured product was 119°C, the tensile strength was 96MPa, and the unnotched impact strength was 45kJ / m 2 , in an acidic solution of 0.3MH at 85℃ + The degradation rate within 12 hours is 99%.

[0165] Example 15

[0166] Example 15 provides a degradable epoxy resin composition comprising uniformly mixed acetal polyester diol, epoxy resin and antimonate thermal initiator (N-benzylpyrazine hexafluoroantimonate) in a mass ratio of 35:65:8.

[0167] The structure of the acetal polyester diol used in this embodiment is as follows, with a molecular weight of 39800 g / mol; R2 is

[0168]

[0169] The structure of the epoxy resin used in this embodiment is as follows:

[0170]

[0171] The degradable epoxy resin composition was cured at 80° C. for 6 hours to obtain a degradable epoxy resin cured product.

[0172] The relevant properties of the prepared epoxy resin cured product were tested. The test results showed that the glass transition temperature of the biodegradable epoxy resin cured product was 113°C, the tensile strength was 101MPa, and the unnotched impact strength was 45kJ / m 2 , in an acidic solution of 0.4MH at 80℃ + The degradation rate within 24 hours is 99%.

[0173] Example 16

[0174] Example 16 provides a degradable epoxy resin composition, which includes uniformly mixed acetal polyester diol, epoxy resin and antimonate thermal initiator (N-benzylpyrazine hexafluoroantimonate) in a mass ratio of 40:60:10.

[0175] The structure of the acetal polyester diol used in this embodiment is as follows, with a molecular weight of 48800 g / mol; R2 is

[0176]

[0177] The structure of the epoxy resin used in this embodiment is as follows:

[0178]

[0179] The degradable epoxy resin composition was cured at 80° C. for 6 hours to obtain a degradable epoxy resin cured product.

[0180] The relevant properties of the prepared epoxy resin cured product were tested. The test results showed that the glass transition temperature of the biodegradable epoxy resin cured product was 95°C, the tensile strength was 102MPa, and the unnotched impact strength was 45kJ / m 2 , in an acidic solution of 0.5MH at 65℃ + The degradation rate within 24 hours is 99%.

[0181] Example 17

[0182] Example 17 provides a degradable epoxy resin composition comprising uniformly mixed acetal polyester diol, epoxy resin and diaryliodonium salt photoinitiator (4,4′-diacetamidophenyliodonium hexafluorophosphate) in a mass ratio of 35:65:5.

[0183] The structure of the acetal polyester diol used in this embodiment is as follows, with a molecular weight of 69300 g / mol; R2 is -CH2CH2CH2-:

[0184]

[0185] The structure of the epoxy resin used in this embodiment is as follows:

[0186]

[0187] The degradable epoxy resin composition was irradiated under 365 nm ultraviolet light for 8 minutes to obtain a degradable epoxy resin cured product.

[0188] The relevant properties of the prepared epoxy resin cured product were tested. The test results showed that the glass transition temperature of the biodegradable epoxy resin cured product was 111°C, the tensile strength was 88MPa, and the unnotched impact strength was 44kJ / m 2 , in an acidic solution of 0.5MH at 90℃ + The degradation rate within 12 hours is 99%.

[0189] Example 18

[0190] Example 18 provides a degradable epoxy resin composition, which includes uniformly mixed acetal polyester diol, epoxy resin and diaryl iodonium salt photoinitiator (4,4′-diacetamidophenyl iodonium hexafluorophosphate) in a mass ratio of 40:60:8.

[0191] The structure of the acetal polyester diol used in this embodiment is as follows, with a molecular weight of 71100 g / mol; R2 is -CH2CH2CH2-:

[0192]

[0193] The structure of the epoxy resin used in this embodiment is as follows:

[0194]

[0195] The degradable epoxy resin composition was irradiated under 365 nm ultraviolet light for 10 minutes to obtain a degradable epoxy resin cured product.

[0196] The relevant properties of the prepared epoxy resin cured product were tested. The test results showed that the glass transition temperature of the biodegradable epoxy resin cured product was 106°C, the tensile strength was 97MPa, and the unnotched impact strength was 40kJ / m 2 , in an acidic solution of 0.2MH at 80℃ + The degradation rate within 12 hours is 99%.

[0197] Example 19

[0198] Example 19 provides a degradable epoxy resin composition comprising uniformly mixed acetal polyester diol, epoxy resin and diaryliodonium salt photoinitiator (4,4′-diacetamidophenyliodonium hexafluorophosphate) in a mass ratio of 40:60:5.

[0199] The structure of the acetal polyester diol used in this embodiment is as follows, with a molecular weight of 11400 g / mol; R2 is -CH2CH2CH2CH2-:

[0200]

[0201] The structure of the epoxy resin used in this embodiment is as follows:

[0202]

[0203] The degradable epoxy resin composition was irradiated under 365 nm ultraviolet light for 8 minutes to obtain a degradable epoxy resin cured product.

[0204] The relevant properties of the prepared epoxy resin cured product were tested. The test results showed that the glass transition temperature of the degradable epoxy resin cured product was 117°C, the tensile strength was 89 MPa, and the unnotched impact strength was 42 kJ / m 2 , in an acidic solution of 0.5MH at 85℃ + The degradation rate is 99% within 16 hours.

[0205] Example 20

[0206] Example 20 provides a degradable epoxy resin composition comprising uniformly mixed acetal polyester diol, epoxy resin and antimonate thermal initiator (N-benzylpyrazine hexafluoroantimonate) in a mass ratio of 50:50:10.

[0207] The structure of the acetal polyester diol used in this embodiment is as follows, with a molecular weight of 51400 g / mol; R2 is -CH2CH2CH2CH2-:

[0208]

[0209] The structure of the epoxy resin used in this embodiment is as follows:

[0210]

[0211] The degradable epoxy resin composition was cured at 90° C. for 4 hours to obtain a degradable epoxy resin cured product.

[0212] The relevant properties of the prepared epoxy resin cured product were tested. The test results showed that the glass transition temperature of the biodegradable epoxy resin cured product was 99°C, the tensile strength was 106MPa, and the unnotched impact strength was 45kJ / m 2 , in an acidic solution of 0.5MH at 70℃ + The degradation rate within 24 hours is 99%.

[0213] Comparative Example 1

[0214] In Comparative Example 1, commercial polyester polyol (hexanediol adipate), epoxy resin and diazonium fluoroborate initiator were uniformly mixed in a mass ratio of 20:80:5 to obtain an epoxy resin composition.

[0215] The structure of the epoxy resin used in Comparative Example 1 is as follows:

[0216]

[0217] The epoxy resin composition was irradiated under 365 nm ultraviolet light for 10 minutes to obtain an epoxy resin cured product.

[0218] The relevant properties of the epoxy resin cured product were tested in the same manner as in Example 1. The test results showed that the epoxy resin cured product had a glass transition temperature of 105°C, a tensile strength of 51 MPa, and an unnotched impact strength of 37 kJ / m 2 , 0.5MH acid solution at 35℃ + The degradation rate within 12 hours was 0%.

[0219] Comparative Example 2

[0220] The only difference between Comparative Example 2 and Example 1 is that the epoxy resin used in Comparative Example 2 is an epoxy resin without an ester bond, specifically bisphenol A epoxy resin E51. The remaining steps are the same as in Example 1. The properties of the resulting epoxy resin cured material are as follows: a glass transition temperature of 95°C, a tensile strength of 61 MPa, and an unnotched impact strength of 30 kJ / m 2 , in 0.5MH alkaline aqueous solution at 35℃ + The degradation rate within 12 hours is 40%.

[0221] Comparative Example 1 and Comparative Example 2, the epoxy resin cured product prepared using the ester-bond-containing epoxy resin contains an acetal structure, which can be quickly decomposed into aldehydes and alcohols under acidic conditions, giving the material efficient biodegradability.

[0222] Table 1 summarizes the relevant properties of the epoxy resin cured products in the above examples and comparative examples.

[0223] Table 1 Related properties of epoxy resin cured products in Examples and Comparative Examples

[0224]

[0225]

[0226] In summary, the present invention leverages the unique degradation properties of acetal structures to develop a series of novel biodegradable epoxy resin compositions that rapidly decompose in low-concentration acidic solutions. These resin compositions have broad application prospects in composite materials and encapsulation resins, heralding a new era in the practical application of biodegradable epoxy resins and potentially driving this field towards a more environmentally friendly and sustainable future.

[0227] The various aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and are not intended to limit the present invention, the scope of which is defined solely by the claims. Other embodiments, modifications and uses will be apparent to those skilled in the art without departing from the spirit and scope of the invention as claimed.

[0228] In addition, the inventors of this case also referred to the aforementioned embodiments and conducted experiments using other raw materials, process operations, and process conditions described in this specification, and obtained relatively ideal results.

[0229] Although the present invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions, and / or additions may be made and that substantial equivalents may be substituted for the elements of the embodiments without departing from the spirit and scope of the present invention. Additionally, many modifications may be made to adapt specific circumstances or materials to the teachings of the present invention without departing from the scope of the present invention. Therefore, it is not intended herein to limit the present invention to the disclosed specific embodiments for carrying out the present invention, but rather to include all embodiments within the scope of the appended claims. Furthermore, unless specifically stated, any use of the terms first, second, etc. does not indicate any order or importance, but rather uses the terms first, second, etc. to distinguish one element from another.

Claims

1. A degradable epoxy resin composition, characterized in that The invention comprises acetal polyester diol, ester bond-containing epoxy resin and cationic initiator, wherein the mass ratio of the acetal polyester diol, ester bond-containing epoxy resin and cationic initiator is 20-50:50-80:5-10; The structure of the acetal polyester diol is shown in Formula I: Wherein, R1 includes a group containing an acetal structure, and R2 includes an aliphatic chain group or an aliphatic ring group.

2. The degradable epoxy resin composition according to claim 1, characterized in that The acetal polyester diol includes one of the substances with structures shown in the following formulas I-1 to I-11:

3. The degradable epoxy resin composition according to claim 1 or 2, wherein: The molecular weight of the acetal polyester diol is 4000 to 80000 g / mol; And / or, R2 in Formula I is C1~C 10 Fatty chain groups or C3~C 10 aliphatic ring groups.

4. The degradable epoxy resin composition according to claim 1, wherein: The ester bond-containing epoxy resin includes at least one of the compound represented by formula II and the compound represented by formula III: Among them, R a 、R b are independently aliphatic chain groups or aliphatic ring groups, preferably, R a 、R b Independently C2~C 10 Fatty chain groups or C3~C 10 aliphatic ring groups.

5. The degradable epoxy resin composition according to claim 4, characterized in that The ester bond-containing epoxy resin includes at least one of the compounds represented by formula II-1, formula II-2, formula II-3, formula III-1, formula III-2, and formula III-3:

6. The degradable epoxy resin composition according to claim 1, wherein: The cationic initiator includes a cationic photoinitiator and / or a cationic thermal initiator; Preferably, the cationic photoinitiator comprises one or more of a diazonium salt, a diaryliodonium salt, a triarylsulfonium salt, an alkylsulfonium salt, an iron arene salt, a sulfonyloxy ketone or a triarylsiloxane ether; Preferably, the cationic thermal initiator comprises one or a combination of multiple of antimonates, phosphates, alkylammonium salts, aryldiazonium salts or onium salts.

7. Use of the degradable epoxy resin composition according to any one of claims 1 to 6 in the preparation of adhesives, coatings, electronic consumer products, electronic packaging or composite materials.

8. A degradable epoxy resin cured product, characterized in that: It is formed by thermally curing and / or light curing the degradable epoxy resin composition according to any one of claims 1 to 6; Preferably, the thermal curing comprises: curing the degradable epoxy resin composition at a temperature of 50 to 100° C. for 3 to 6 hours; Preferably, the photocuring comprises: irradiating the degradable epoxy resin composition under ultraviolet light for 5 to 10 minutes; Preferably, the degradation rate of the degradable epoxy resin cured material is above 99%; Preferably, the glass transition temperature of the degradable epoxy resin cured product is above 80°C, more preferably 80-150°C; Preferably, the tensile strength of the degradable epoxy resin is above 70 MPa, more preferably 70 to 140 MPa; Preferably, the unnotched impact strength of the degradable epoxy resin is 30 kJ / m 2 More preferably, 30 to 50 kJ / m 2 .

9. A degradable structure, characterized in that The invention comprises the degradable epoxy resin cured product according to claim 8.

10. The method for degrading a degradable epoxy resin cured material according to claim 9, characterized in that: include: soaking the degradable epoxy resin cured product in an acidic solution; Preferably, the hydrogen ion concentration of the acidic solution is 0.1 mol / L or more, more preferably 0.1-0.5 mol / L; Preferably, the soaking time is 2-24 hours; Preferably, the temperature of the acidic solution is 25°C or above, more preferably above 50°C, and particularly preferably 50-100°C.

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