TWI768347B - Thermosetable composition, epoxy curable product prepared thereby and a method for degrading epoxy curable product - Google Patents

Abstract

The present disclosure provides a thermosetable composition. The thermosetable composition includes an epoxy, a polycarbonate or a polycarbonate alloy and a catalyst, wherein the equivalent ratio of the carbonate group of the polycarbonate to the epoxy group of the epoxy resin is 0.8 to 1.2. The polycarbonate has a structure represented by formula (I), and the polycarbonate alloy is a blend of polycarbonate represented by formula (I) and acrylonitrile-butadiene-styrene copolymer or styrene-acrylonitrile copolymer, in which each symbol is as defined in the specification. Thus, the epoxy curable product obtained by using the carbonate group reacted with the epoxy group, so that the polycarbonate-derived product can be converted into useful epoxy thermosetting material without pre-treatment.

Description

Curable composition, epoxy cured product prepared therefrom and method for degrading epoxy cured product

The present invention relates to a curable composition, its prepared epoxy cured product and a method for degrading the epoxy cured product, in particular to a curable composition comprising epoxy resin, catalyst and polycarbonate or polycarbonate alloy A product, an epoxy cured product prepared therefrom, and a method for degrading the epoxy cured product.

Polycarbonate is obtained by the interfacial condensation reaction of bisphenol and phosgene, or by transesterification with diphenyl carbonate, among which bisphenol A is the most commonly used bisphenol. Bisphenol A polycarbonate (or PC for short) is a polymer with good optical and mechanical properties, and is often used in data access, such as CD, DVD and other audio-visual discs, safety glass and automotive parts. In addition to pure resins, polycarbonate alloys such as PC/ABS alloys (Acrylonitrile-Butadiene-Styrene copolymer) or PC/SAN alloys (styrene-acrylonitrile copolymers) , Styrene-Acrylonitrile copolymer) is also widely used.

At present, there are two methods for recycling PC. The first is a physical recycling method through mechanical processing or physical mixing of other materials; the second is a method of degrading polymer chains to obtain useful monomers, such as bisphenol. A. Bis(hydroxyethyl) ether of PBA, dimethyl carbonate, diethyl carbonate, hydroxy-N,N'-diphenylene-isopropyl biscarbamate, N,N'-dibenzyl The chemical degradation method of base urea; the third system recovers polycarbonate by thermal cracking. Among them, the chemical degradation method requires suitable solvents and separation procedures to avoid causing environmental problems, while the thermal cracking method has very low monomer selectivity.

In view of this, if polycarbonate can be directly used as a reactant to react with epoxy resin, the recycling industry of polycarbonate can be attractive, and it has become the goal of the relevant industry.

One object of the present invention is to provide a curable composition, which comprises epoxy resin, catalyst and polycarbonate or polycarbonate alloy, and undergoes a curing reaction to prepare an epoxy cured product, and the epoxy cured product can be cured Degradation, so that the product can be recycled and reused, reducing the burden on the environment.

式(I)； 其中X為單鍵、-O-、-SO₂ -、-C(=O)-、-(CH₂ )_q -、式(i)、式(ii)、式(iii)、式(iv)、式(v)、式(vi)、式(vii)或式(viii)所示之一結構：

式(i)、 式(ii)、 式(iii)、 式(iv)、

式(v)、 式(vi)、 式(vii)、 式(viii)， R為氫、碳數1至6的烷基、苯基或鹵素基，q為1至6之整數。另外，聚碳酸酯合金係式(I)所示之聚碳酸酯與丙烯腈-丁二烯-苯乙烯共聚合物或苯乙烯-丙烯腈共聚合物形成的混摻物。One embodiment of the present invention provides a curable composition comprising epoxy resin, polycarbonate or polycarbonate alloy and a catalyst, wherein the carbonate group of the polycarbonate is equivalent to the epoxy group of the epoxy resin. The ratio is 0.8 to 1.2, and the polycarbonate has one of the structures shown in formula (I):

Formula (I); Wherein X is a single bond, -O-, -SO ₂ -, -C(=O)-, -(CH ₂ ) _q -, formula (i), formula (ii), formula (iii), formula (iv) , formula (v), formula (vi), formula (vii) or one of the structures shown in formula (viii):

Formula (i), Formula (ii), Formula (iii), Formula (iv),

Formula (v), Formula (vi), Formula (vii), Formula (viii), R is hydrogen, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen group, and q is an integer of 1 to 6. In addition, the polycarbonate alloy is a blend of the polycarbonate represented by the formula (I) and acrylonitrile-butadiene-styrene copolymer or styrene-acrylonitrile copolymer.

According to the curable composition described in the preceding paragraph, the catalyst may be selected from the group consisting of 4-dimethylaminopyridine, imidazole, 2-methylimidazole, and 2-ethyl-4-methylimidazole.

According to the curable composition described in the preceding paragraph, the additive amount of the catalyst may be 0.1 to 5 weight percent of the epoxy resin content.

According to the curable composition described in the preceding paragraph, wherein the epoxy resin can be bisphenol A epoxy resin, novolac epoxy resin, methyl novolac epoxy resin, dicyclopentadiene phenol epoxy resin, naphthalene-containing epoxy resin Resin, phosphorus-based epoxy resin, or a mixture thereof.

The curable composition described in the preceding paragraph may further include a solvent for dissolving the polycarbonate and the epoxy resin to form a solution with a solid content of 10 to 30 wt %.

Another embodiment of the present invention provides an epoxy cured product obtained by performing a curing reaction with the aforementioned curable composition.

According to the epoxy cured product described in the preceding paragraph, the curing reaction is completed by heating the curable composition, and a curing temperature of the curing reaction is 180 ^° C to 240 ^° C.

式(1)、 式(2)、

式(3)、 式(4)。 According to the epoxy cured product described in the preceding paragraph, it can have a partial structure as shown in formula (1), formula (2), formula (3) or formula (4):

Formula 1), Formula (2),

Formula (3), Formula (4).

Yet another embodiment of the present invention provides a method for aminolytic degradation of an epoxy cured product, comprising providing the aforementioned epoxy cured product and performing a degradation step, wherein the degradation step is to react an amine group-containing compound with the epoxy cured product, The epoxy cured product is degraded by aminolysis.

A further embodiment of the present invention provides a method for degrading an epoxy cured product by alcoholysis, comprising providing the aforementioned epoxy cured product and performing a degradation step, wherein the degradation step is to catalyze an alcohol group-containing compound under the catalysis of an ionic liquid Reacts with epoxy cured products to degrade epoxy cured products by alcoholysis.

Thereby, the curable composition of the present invention uses polycarbonate as the hardener of epoxy resin, and forms epoxy cured product with excellent properties under catalyst catalysis, and can be degraded so that it can be recycled and reused , in line with environmental benefits.

Various embodiments of the present invention are discussed in greater detail below. However, this embodiment can be an application of various inventive concepts and can be embodied in various specific scopes. The specific embodiments are for illustrative purposes only, and are not intended to limit the scope of the disclosure.

>Curable composition>

The present invention provides a curable composition comprising epoxy resin, polycarbonate or polycarbonate alloy and catalyst, wherein the equivalent ratio of carbonate group of polycarbonate to epoxy group of epoxy resin is 0.8 to 1.2.

式(I)； 其中X為單鍵、-O-、-SO₂ -、-C(=O)-、-(CH₂ )_q -、式(i)、式(ii)、式(iii)、式(iv)、式(v)、式(vi)、式(vii)或式(viii)所示之一結構：

式(i)、 式(ii)、 式(iii)、 式(iv)、

式(v)、 式(vi)、 式(vii)、 式(viii)， R為氫、碳數1至6的烷基、苯基或鹵素基(F、Cl、Br、I)，q為1至6之整數，且式(I)為聚碳酸酯的重複單元。另外，前述聚碳酸酯合金係式(I)所示之聚碳酸酯與丙烯腈-丁二烯-苯乙烯共聚合物(Acrylonitrile-Butadiene-Styrene copolymer, ABS)或苯乙烯-丙烯腈共聚合物(Styrene-Acrylonitrile copolymer, SAN)形成的混摻物。The aforementioned polycarbonate has a structure as shown in formula (I):

Formula (I); Wherein X is a single bond, -O-, -SO ₂ -, -C(=O)-, -(CH ₂ ) _q -, formula (i), formula (ii), formula (iii), formula (iv) , formula (v), formula (vi), formula (vii) or one of the structures shown in formula (viii):

Formula (i), Formula (ii), Formula (iii), Formula (iv),

Formula (v), Formula (vi), Formula (vii), Formula (viii), R is hydrogen, an alkyl group having 1 to 6 carbons, a phenyl group or a halogen group (F, Cl, Br, I), q is an integer of 1 to 6, and the formula (I) is a repeating unit of polycarbonate. In addition, the aforementioned polycarbonate alloy is a polycarbonate represented by formula (I) and acrylonitrile-butadiene-styrene copolymer (Acrylonitrile-Butadiene-Styrene copolymer, ABS) or styrene-acrylonitrile copolymer (Styrene-Acrylonitrile copolymer, SAN).

The aforementioned epoxy resin can be bisphenol A epoxy resin (Diglycidyl ether of Bisphenol A, DGEBA), novolac epoxy resin (Phenol novolac epoxy, PNE), cresol novolac epoxy resin (CNE), bicyclic epoxy resin Dicyclopentadiene-phenol epoxy (DNE), naphthalene-containing epoxy (Naphthalene-containing epoxy), phosphorus-based epoxy or a mixture thereof. In other words, the aforementioned epoxy resins may be used alone, or two or more of them may be used simultaneously, and when two or more of them are used, they may be mixed in any ratio. In this way, desired properties can be imparted to the subsequent cured product by selecting an appropriate epoxy resin.

The aforementioned catalyst may comprise an unshared electron pair selected from the group consisting of 4-Dimethylaminopyridine (DMAP), imidazole (Imidazole), 2-Methylimidazole (2-Methylimidazole) and 2-ethyl-4 - A group consisting of 2-Ethyl-4-methylimidazole. Thereby, the unshared electron pair of the catalyst can interact with the epoxy group of the epoxy resin to facilitate the subsequent curing reaction. Specifically, the addition amount of the aforementioned catalyst may be 0.1% by weight to 5% by weight of the epoxy resin content.

In addition, the aforementioned curable composition may further comprise a solvent for dissolving the polycarbonate and the epoxy resin to form a solution with a solid content of 10 to 30 wt%.

In detail, the curable composition of the present invention utilizes the carbonate group in polycarbonate to react with the epoxy group in epoxy resin. In order to prove the above concept, the present invention first conducts a model reaction (model reaction), diphenyl carbonate (diphenyl carbonate) and glycidyl phenyl ether (glycidyl phenyl ether) are reacted under the catalyst 4-dimethylaminopyridine. Specifically, take 2.00 g (9.3 mmol) of diphenyl carbonate, 2.79 g (18.6 mol) of phenyl glycidyl ether and 0.014 g of 4-dimethylaminopyridine into a 250 mL three-necked flask , heat up to 80 ^o C to confirm the dissolution, continue to heat up to 120 ^o C and react for 2 hours. After that, the product obtained in Synthesis Example 1 was subjected to spectral analysis, and the data of hydrogen spectrum: ¹ H-NMR (DMSO-d ₆ ), δ=4.32 (8H, H ⁵ ), 5.38 (2H, H ⁶ ), 6.97 (8H , H ¹ and H ³ ), 7.28 (4H, H ² ); carbon spectrum data: ¹³ C-NMR (DMSO-d ₆ ), δ=65.9 (C ⁵ ), 74.6 (C ⁶ ), 114.4 (C ³ ) ), 120.9 (C ¹ ), 129.4 (C ² ), 153.7 (C ⁴ ); data from infrared spectroscopy: FTIR(KBr): ν(cm ^-1 )=1750 (C=O stretch of carbonyl group); and high Resolution mass spectrometry data: High resolution LC-MS (ESI-MS) m/z: [M ⁺ ] calcd. for C ₃₁ H ₃₁ O ₇ 515.20 g/mol; anal., 515.2050 g/mol. The reaction equation of Synthesis Example 1 is shown in Table 1 below. As a result, it was found that the carbonate group can react with the epoxy group. Table I

>Epoxy Cured Product>

The present invention further provides an epoxy cured product, which is obtained by carrying out a curing reaction of the curable composition, and the curing reaction is briefly described below with reference to FIG. The flow chart of the steps of the preparation method 100 of the epoxy cured product of the method. In FIG. 1 , the preparation method 100 of the epoxy cured product includes step 110 and step 120 .

Step 110 is to perform a mixing step of mixing epoxy resin, polycarbonate or polycarbonate alloy with a catalyst to obtain a curable composition. Specifically, through step 110, the polycarbonate, epoxy resin and catalyst can form a precursor solution containing a curable composition. In addition, the solvent used in the precursor solution is used to help the polycarbonate and the epoxy resin to be blended. Therefore, as long as it can dissolve the polycarbonate and the epoxy resin and does not react with the aforementioned two, it can be used as the solvent in step 110. solvent used. As for the details of polycarbonate, epoxy resin and catalyst, please refer to the above, and will not be repeated here.

Step 120 is to perform a curing step, so that the polycarbonate and the epoxy resin are cross-linked under the catalyst to form the epoxy cured product. Specifically, the polycarbonate and epoxy resin can be cross-linked under catalyst catalysis by heating the precursor solution, and the curing temperature of the final heating can be 180 ^o C to 240 ^o C, and the heating time can be 1 hour to 6 hours. More specifically, the aforementioned heating method may adopt a multi-stage heating and curing method to heat the precursor solution, for example, heating at 180 ^o C, 200 ^o C, and 220 ^o C for 2 hours each. The curing temperature and heating time of the heating can be flexibly adjusted according to the types of polycarbonate and epoxy resin used, and the present invention is not limited thereto.

>Method for aminolysis to degrade epoxy cured product>

Please refer to FIG. 2 , which is a flow chart showing the steps of a method 200 for aminolytic degradation of epoxy resin according to another embodiment of the present invention. In FIG. 2 , the method 200 for aminolytic degradation of epoxy resin includes step 210 and step 220 .

Step 210 is to provide the aforementioned epoxy cured product. Step 220 is to perform a degradation step, which is to react an amine group-containing compound with the epoxy cured product to degrade the epoxy cured product by aminolysis.

>Method for degrading epoxy cured product by alcoholysis>

Please refer to FIG. 3 , which is a flow chart of the steps of a method 300 for alcoholysis degradation of epoxy resin according to another embodiment of the present invention. In FIG. 3 , the method 300 for degrading the epoxy cured product by alcoholysis includes step 310 and step 320 .

Step 310 is to provide the aforementioned epoxy cured product. Step 320 is a degradation step, which is to react an alcohol group-containing compound with the epoxy cured product under the catalysis of an ionic liquid to degrade the epoxy cured product by alcoholysis.

The following specific examples are hereby used to further demonstrate the present invention, so as to help those skilled in the art to which the present invention pertains to fully utilize and practice the present invention without excessive interpretation, and these examples should not be regarded as It is intended to limit the scope of the invention, but to illustrate how the materials and methods of the invention may be practiced.

>Example>

Embodiment 1: take 0.50 grams of polycarbonate and 0.74 grams of bisphenol A type epoxy resin (Changchun artificial resin commodity code BE188), so that the aforementioned two are in an equivalent ratio of 1:1, with N-methyl Pyrrolidone was used as a solvent to prepare a precursor solution with a solid content of 20 wt%, which was heated to complete dissolution at 80 ^° C, and then 0.0037 g of 4-dimethylaminopyridine was added. Then use a glass coater to coat the precursor solution on the glass, raise the temperature stepwise to 80 ^o C for 12 hours to remove most of the solvent, and then cure at 180 ^o C, 200 ^o C, and 220 ^o C for 2 hours each, After soaking in water and demoulding, a yellow epoxy cured product was obtained.

Embodiment 2: get 0.50 grams of polycarbonate and 1.898 grams of bisphenol A type epoxy resin (Changchun artificial resin commodity code BE501), so that the aforementioned two are in an equivalent ratio of 1:1, with N-methyl Pyrrolidone was used as a solvent to prepare a precursor solution with a solid content of 20 wt%, and the remaining steps were the same as in Example 1. After soaking in water and demoulding, a yellow epoxy cured product was obtained.

Embodiment 3: take 0.25 grams of polycarbonate and 1.774 grams of bisphenol A type epoxy resin (Changchun artificial resin commodity code BE504), so that the aforementioned two are in an equivalent ratio of 1:1, with N-methyl Pyrrolidone was used as a solvent to prepare a precursor solution with a solid content of 20 wt%, and the remaining steps were the same as in Example 1. After soaking in water and demoulding, a yellow epoxy cured product was obtained.

Embodiment 4: get 0.50 grams of polycarbonate and 1.024 grams of dicyclopentadiene phenol epoxy resin (Changchun artificial resin commodity code DNE), so that the above two are in the ratio of equivalence ratio 1:1, with N-methyl Pyrrolidone was used as a solvent to prepare a precursor solution with a solid content of 20 wt%, and the remaining steps were the same as in Example 1. After soaking in water and demoulding, a yellow epoxy cured product was obtained.

Embodiment 5: take 0.50 g of polycarbonate and 0.807 g of methyl novolac epoxy resin (Changchun artificial resin commodity code CNE), so that the above two are in the ratio of the equivalent ratio of 1:1, with N-methylpyrrolidone. The solvent was configured as a precursor solution with a solid content of 20 wt%, and the remaining steps were the same as those in Example 1. After soaking in water and demoulding, a yellow epoxy cured product was obtained.

Embodiment 6: take 0.50 grams of polycarbonate and 1.064 grams of phosphorus-based epoxy resin (Changchun artificial resin commodity code PE), so that the above two are in the ratio of equivalent ratio 1:1, with N-methylpyrrolidone as The solvent was configured as a precursor solution with a solid content of 20 wt%, and the remaining steps were the same as in Example 1. After soaking in water and demoulding, a yellow epoxy cured product was obtained.

實施例2

實施例3

實施例4

實施例5

實施例6

Regarding the polycarbonates of Examples 1 to 6, in formula (I), X is the structure of formula (i), R is hydrogen, and the epoxy resin structure is shown in Table 2 below. Table II Example 1

Example 2

Example 3

Example 4

Example 5

Example 6

Please refer to FIG. 4, which is a schematic diagram of the appearance of the epoxy cured products of Examples 1 to 6 of the present invention, wherein (a), (b), (c), (d), (e), ( f) are the epoxy cured products of Example 1 to Example 6, respectively. It can be seen from the results in Fig. 4 that the epoxy cured products of Examples 1 to 6 are yellow transparent films and have flexibility.

式(1)。 In addition, please refer to FIG. 5 , which is a Fourier transform infrared spectrum diagram of each heating stage in Example 4 of the present invention. It can be seen from the results in Figure 5 that at room temperature (RT), the C=O absorption peak of the carbonate group is 1780 cm ^-1 , and after curing by heating, the epoxy cured product of Example 4 has a C=O absorption peak of 1780 cm -1 . The O absorption peak is 1750 cm ^-1 , and it can be seen that the carbonate group has changed from aromatic-aromatic carbonate (Ar-O(C=O)O-Ar) to aliphatic-aliphatic (RO(C=O)OR) , so the epoxy cured product of Example 4 has a partial structure as shown in formula (1):

Formula 1).

式(2)、

式(3)、

式(4)。 Similarly in Example 4, Example 1, Example 5 and Example 6 respectively have a partial structure as shown in formula (2), formula (3) and formula (4):

Formula (2),

Formula (3),

Formula (4).

The mechanical properties and thermal properties of Examples 1 to 6 were evaluated. The thermal property evaluation included glass transition temperature (T _g ), 5% thermogravimetric loss temperature (T _d5% ) and coke residual rate. The evaluation methods were as follows.

(1) Glass transition temperature: use a dynamic mechanical analyzer (Dynamic Mechanical Analyzer, DMA) to measure the storage modulus (Storage Modulus) and the Tan delta curve and temperature of the epoxy cured products obtained in Examples 1 to 6 relationship and glass transition temperature. In addition, the glass transition temperature was measured using Thermo-Mechanical Analysis (TMA), which was measured at a heating rate of 5 ^o C/min.

(2) 5% thermogravimetric loss temperature and coke residual rate: use thermogravimetric analysis (Thermo-Gravimetric Analysis, TGA) to measure the 5% thermogravimetric loss temperature of the sample and the coke residual rate (Char yield) at 800 ^o C . The condition of thermogravimetric analysis is to measure the weight change of the sample using a thermogravimetric analyzer under a nitrogen atmosphere at a heating rate of 20 ^o C/min. The 5% thermogravimetric loss temperature refers to the temperature at which the weight loss of the cured product sample reaches 5%, wherein the higher the 5% thermogravimetric loss temperature, the better the thermal stability of the sample. The coke residual ratio of 800 ^o C refers to the residual weight ratio of the sample when the heating temperature reaches 800 ^o C, and the higher the residual weight ratio of 800 ^o C, the better the thermal stability of the sample.

Please refer to FIG. 6 , which shows the stress-strain diagram of the epoxy cured products of Examples 1 to 6 of the present invention. Tensile strength and elongation at break are measured by tensile test. The tensile test is measured by EZ-SX at room temperature. The size of the test piece is 5 cm long and 1 cm wide. , 0.042 to 0.107 mm thick, and the tensile strength corresponds to the stress in Figure 6, and the elongation at break corresponds to the strain in Figure 6. The measurement results of the tensile strength and elongation at break of Examples 1 to 6 are shown in Table 3 below. Table 3 Tensile strength (MPa) Elongation at break (%) Example 1 79 7.4 Example 2 51 10.8 Example 3 48 25.3 Example 4 57 5.9 Example 5 32 2.3 Example 6 37 3.0

Please refer to FIG. 7 , which shows the dynamic thermomechanical analysis diagrams of the epoxy cured products of Examples 1 to 6 of the present invention. The measurement results of glass transition temperature, storage modulus, thermogravimetric loss temperature and coke residual rate of Examples 1 to 6 are shown in Table 4 below. In addition, the polycarbonates of Examples 1 to 4 were changed to phenolic resin as the hardener of the epoxy resin to obtain the cured epoxy resins of Comparative Examples 1 to 4. The glass transition temperature and thermogravimetric loss of The measurement results of temperature and coke residual rate are shown in Table 4 below. Table 4 T _g ( ^o C) T _d5% ( ^o C) Coke Residual Rate (%) Storage modulus (GPa) Example 1 169 382 7 2.0 Example 2 146 391 4 1.6 Example 3 125 407 2 1.2 Example 4 184 385 6 1.1 Example 5 229 394 twenty two 1.7 Example 6 200 373 20 1.1 Comparative Example 1 172 415 12 - Comparative Example 2 137 419 10 - Comparative Example 3 126 415 1 - Comparative Example 4 187 422 9 -

It can be seen from the results in Table 3 that when the tensile test is performed, it is shown that a flexible thermosetting film can be obtained by using polycarbonate as the epoxy resin hardener. From the results in Table 4, it can be seen that the thermal properties between the epoxy resin cured with polycarbonate and the epoxy resin cured with phenolic resin are close when measured by dynamic mechanical analysis, while in the test of thermogravimetric analysis, it is shown that Polycarbonate as epoxy resin hardener has good thermal stability.

>Aminolytic degradation of epoxy cured products>

Examples 7 to 10 are the results obtained by performing the aminolysis degradation reaction on the epoxy cured products of Examples 1 to 4, respectively. First, take the epoxy cured product films of Examples 1 to 4 and 1-hexylamine and place them in the reactor. After the reaction is completed, directly use a vacuum concentrator to extract the 1-hexylamine to obtain an example in which the degradation is completed. 7 to Example 10. The addition amount of epoxy cured product, the addition amount of 1-hexylamine, the reaction temperature, the reaction time and the residual weight required in Examples 7 to 10 are listed in Table 5 below. Table 5 Example 7 Example 8 epoxy cured product Example 1 Example 2 Amount of epoxy cured product (g) 0.1715 0.1870 1-Hexylamine addition amount (mL) 5 10 Reaction temperature ( ^o C) 125 125 Response time (hrs) 1.75 3.5 Residual weight (%) 0 0 Example 9 Example 10 epoxy cured product Example 3 Example 4 Amount of epoxy cured product (g) 0.1598 0.1607 1-Hexylamine addition amount (mL) 10 5 Reaction temperature ( ^o C) 125 125 Response time (hrs) 4.0 1.5 Residual weight (%) 0 0

Please refer to FIG. 8 , which shows the ¹ H-NMR analysis chart of Example 7. In detail, (a) of Figure 8 is the ¹ H-NMR chart of the product obtained by distilling off 1-hexylamine after the aminolysis reaction between Example 1 and 1-hexylamine, and (b) of Figure 8 is Example 1 After the aminolysis reaction with 1-hexylamine, 1-hexylamine was distilled off and poured into methanol to remove the ¹ H-NMR chart of small molecules.

It can be seen from the results in Fig. 8 that the products of Example 1 and 1-hexylamine after the aminolysis reaction are 1,3-dihexylurea (1,3-dihexylurea) and phenoxy resin, and through the first 8 and the results in Table 5, it can be shown that the epoxy cured product of the present invention is decomposable after reacting with the amine group-containing compound, and the residual weight of the epoxy cured product is 0%. The reaction equation of Example 7 is shown in Table 6 below. Table 6

>Degradation of epoxy resin by alcoholysis>

Example 11 and Example 12 are the results obtained by the alcoholysis degradation reaction of the epoxy cured product of Example 1. First, 3 g (19.7 mmol) of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) were combined with 1.34 g (19.7 mmol) of imidazole at room temperature Under the reaction for 8 hours, a light yellow [HDBU][IM] ionic liquid can be obtained, wherein the reaction equation of the [HDBU][IM] ionic liquid is shown in Table 7 below. Table 7

Next, take the epoxy cured product film of Example 1 and react with 2-ethylhexanol under the catalysis of ionic liquid [HDBU][IM], and react in a high-pressure reactor at 200 ^o C for 18 hours, then cool down. A paste-like liquid can be obtained at room temperature, which means that the degradation is complete, and it can be proved that the epoxy cured product of the present invention is very stable in alcoholysis. The addition amount of epoxy cured product, 2-ethylhexanol addition amount, catalyst addition amount, reaction temperature, reaction time and residual weight required in Example 11 and Example 12 are listed in Table 8 below. Table 8 Example 11 Example 12 epoxy cured product Example 1 Example 1 Amount of epoxy cured product (g) 0.9860 0.1240 Amount of 2-ethylhexanol added (g) 35 10 catalyst [HDBU][IM] [HDBU][IM] Amount of catalyst added (g) 0.947 0.270 Reaction temperature ( ^o C) 200 170 Response time (hrs) 18 12 Residual weight (%) 0 46

In addition, similarly in the aminolysis degradation test, the reaction equation of Example 1 and 2-ethylhexanol for alcoholysis degradation under the catalysis of ionic liquid is shown in Table 9 below, and through the results of Table 8, it can be explained that this The epoxy cured product of the invention and the alcohol group-containing compound have decomposability under the catalysis of the ionic liquid, and the residual weight of the epoxy cured product of Example 11 is 0%. Table 9

>Comparative Example>

Comparative Examples 5 to 7 are the results obtained by the degradation reaction of the epoxy cured product of the present invention and 2-ethylhexanol under the catalysis of different catalysts. The addition amount of epoxy cured product, 2-ethylhexanol addition amount, catalyst type, catalyst addition amount, reaction temperature, reaction time and residual weight required in Comparative Examples 5 to 7 are listed in the following table ten. Table 10 Comparative Example 5 Comparative Example 6 Comparative Example 7 epoxy cured product Example 1 Example 1 Example 4 Addition of epoxy cured product 0.3000 g 0.3276g 0.3378g 2-Ethylhexanol addition amount 15mL 15mL 15mL catalyst Ti(OBu) ₄ Zn(Ac) ₂ Zn(Ac) ₂ Amount of catalyst added (g) 0.01 0.83 0.83 Reaction temperature ( ^o C) 170 170 170 Response time (hrs) twenty four 8 48 Residual weight (%) 87 35 99

In addition, Comparative Examples 8 to 9 are the results obtained by alkali hydrolysis and degradation of the epoxy cured product of Example 1. The addition amount of epoxy cured product, water addition amount, catalyst, reaction temperature, reaction time and residual weight required in Comparative Examples 8 to 9 are listed in Table 11 below. Table 11 Comparative Example 8 Comparative Example 9 epoxy cured product Example 1 Example 1 Amount of epoxy cured product (g) 0.055 0.051 water addition 15mL 15mL catalyst 5M NaOH 5M NaOH Reaction temperature ( ^o C) 80 80 Response time (hrs) 8 8 Residual weight (%) 96 95

From the results in Table 10, it can be seen that the degradation effect of using Ti(OBu) ₄ catalyst is not good, while the degradation effect of using Zn(Ac) ₂ catalyst on the epoxy cured product of Example 1 is moderate, but for Example 4 The degradation effect of the epoxy cured product is not good, and it can be seen from the results in Table 11 that the epoxy cured product of the present invention cannot be degraded under alkaline water.

To sum up, the curable composition of the present invention uses polycarbonate as a hardener of epoxy resin and is matched with a catalyst to obtain an epoxy cured product with excellent properties, which can make polycarbonate-derived products (such as waste products) CDs) into useful epoxy thermosetting materials, and this process does not use any pretreatment procedures of degradation or cracking, and has the characteristics of low cost compared with traditional chemical modification methods. In addition, the epoxy cured product prepared by the present invention can be degraded, so that the product can be recycled and reused, thereby reducing the burden on the environment.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention. Anyone skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection of the present invention The scope shall be determined by the scope of the appended patent application.

100: Preparation method of epoxy cured product 200: Method for the degradation of epoxy cured products by aminolysis 300: Method for degrading epoxy cured products by alcoholysis 110, 120, 210, 220, 310, 320: Steps

In order to make the above and other objects, features, advantages and embodiments of the present invention more clearly understood, the accompanying drawings are described as follows: Figure 1 illustrates the preparation of epoxy cured products according to one embodiment of the present invention The flow chart of the steps of the method; Fig. 2 shows the flow chart of the steps of the method for aminolysis degradation of epoxy resin according to another embodiment of the present invention; Fig. 3 is a flow chart of the method according to another embodiment of the present invention Step flow chart of the method for degrading the epoxy cured product by alcoholysis; Fig. 4 is a schematic view of the appearance of the epoxy cured product of Example 1 to Example 6 of the present invention; Fig. 5 is a schematic diagram of Example 4 of the present invention Fourier transform infrared spectrograms of each heating stage; Fig. 6 is a stress-strain diagram of the epoxy cured products of Example 1 to Example 6 of the present invention; Fig. 7 is a diagram of Example 1 to Example 6 of the present invention Dynamic thermomechanical analysis diagram of the epoxy cured product; and FIG. 8 is a ¹ H-NMR analysis diagram of Example 7.

100: Preparation method of epoxy cured product

110, 120: Steps

Claims (10)

A curable composition comprising epoxy resin, polycarbonate or polycarbonate alloy and catalyst, wherein the equivalent ratio of carbonate group of polycarbonate to epoxy group of epoxy resin is 0.8 to 1.2 , and the polycarbonate has a structure as shown in formula (I):

Wherein X is a single bond, -O-, -SO ₂ -, -C(=O)-, -(CH ₂ ) _q -, formula (i), formula (ii), formula (iii), formula (iv) , formula (v), formula (vi), formula (vii) or one of the structures shown in formula (viii):

R is hydrogen, an alkyl group having 1 to 6 carbon atoms, a phenyl group or a halogen group, and q is an integer of 1 to 6; the polycarbonate alloy is the polycarbonate represented by the formula (I) and styrene-acrylonitrile A blend of copolymers. The curable composition of claim 1, wherein the catalyst is selected from the group consisting of 4-dimethylaminopyridine, imidazole, 2-methylimidazole, and 2-ethyl-4-methylimidazole Group. The curable composition according to claim 2, wherein the catalyst is added in an amount of 0.1 to 5 weight percent of the epoxy resin content. The curable composition according to claim 1, wherein the epoxy resin is bisphenol A epoxy resin, novolac epoxy resin, methyl novolac epoxy resin, dicyclopentadiene phenol epoxy resin, naphthalene-containing epoxy resin Epoxy resin, phosphorus-based epoxy resin, or a mixture thereof. The curable composition of claim 1, further comprising: a solvent for dissolving the polycarbonate and the epoxy resin to form a solution with a solid content of 10 to 30 weight percent. An epoxy cured product obtained by carrying out a curing reaction of the curable composition according to any one of claim 1 to claim 5. The epoxy cured product as claimed in claim 6, wherein the cured The reaction is completed by heating the curable composition, and a curing temperature of the curing reaction is 180°C to 240°C. The epoxy cured product according to claim 6, which has a partial structure as shown in formula (1), formula (2), formula (3) or formula (4):

A method for aminolysis-degrading an epoxy cured product, comprising: providing the epoxy cured product as claimed in claim 6; and performing a degradation step by reacting an amine group-containing compound with the epoxy cured product to Aminolysis degrades the epoxy cured product. A method for alcoholysis degrading epoxy cured product, comprising: providing epoxy cured product as described in claim 6; The epoxy cured product reacts to degrade the epoxy cured product by alcoholysis.

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