Additive for recycling thermosetting materials, recyclable thermosetting composition and its application

Abstract

The present invention discloses an additive for recycling thermosetting materials, a recyclable thermosetting composition, and its application. Specifically, the additive composition includes at least one copolymer, the copolymer having at least one urethane group, at least one carbonate group, and / or at least one urea group, and the number average molecular weight of the copolymer is in the range of 100-50,000 Da.

Description

[Technical Field]

[0001] The present invention discloses an additive for recycling thermosetting materials, a recyclable thermosetting composition, and its application, specifically, the composition of the additive includes a copolymer and a processing aid. [Background technology]

[0002] Thermosets are high molecular weight polymers whose structural and physical properties, cost, and processability allow them to be used as substitutes for other materials such as thermoplastics, metals, and wood.

[0003] In the prior art, thermosetting materials have a cross-linked, three-dimensional chemical structure that makes them difficult to recycle or reuse. Therefore, methods for recycling thermosetting materials have been very expensive and inefficient. Traditionally, discarded thermosetting materials have been incinerated, resulting in low energy utilization and air pollution. Meanwhile, mechanical recycling methods have the drawback of only recovering a small amount of inorganic filler. To date, environmental and cost barriers remain insurmountable when it comes to recycling discarded thermosetting materials.

[0004] As described above, in the field of thermosetting materials technology, there is still an urgent need to research and develop technical solutions that can provide recyclable thermosetting materials that are compatible with green chemistry and a circular economy in order to break through current technological bottlenecks and meet future industrial demands. Summary of the Invention [Problem to be solved by the invention]

[0005] According to the background of the invention mentioned above, in order to meet the industrial demand, a first object of the present invention is to provide an additive for recycling thermosetting materials.

[0006] Specifically, the additive composition for recycling thermoset materials of the present invention includes at least one copolymer and / or at least one processing aid.

[0007] Specifically, the copolymer has at least one urethane group, at least one carbonate group and / or at least one urea group, and the number average molecular weight of the copolymer is in the range of 100-50,000 Da.

[0008] Specifically, the processing aid includes an amine, a catalyst, a solvent, or a mixture thereof. Preferably, the processing aid is a hydroxy compound, an amine compound, an amino-hydroxy compound, or a combination thereof.

[0009] Specifically, the catalysts include amines, imidazoles, metals and their salts, Lewis acids, or Lewis bases. The amines include quaternary ammonium salts, dimethylamine, diethylamine, triethylamine, triethanolamine, dimethylaniline, or pyridine. The amidine catalysts include 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,4-diazabicyclo[2.2.2]octane (DBACO), or aromatic dimethylamine compounds. The aliphatic amines include diethylenetriamine (DETA), triethylenetetramine (TETA), or polyether polyamines. The imidazole catalysts include imidazolidinyl urea, diethyltetramethylimidazole, or mixtures thereof. The metals and their salts include aluminum, cobalt, nickel, copper, iron, zinc, chromium, vanadium, titanium, manganese, potassium, zirconium, and their oxide, halide, sulfate, nitrate, or phosphate complexes. The Lewis acid includes boron trifluoride and its complexes. The Lewis base includes C1-C10 linear or branched alkyl phosphorus compounds, aromatic phosphorus compounds, or halogen-substituted phosphorus compounds. Other types of catalysts include thiourea and its derivatives, titanates, or rare earth metal compounds.

[0010] Specifically, the catalyst loading is 1.5-15 wt.% based on the weight of the thermosetting material.

[0011] Specifically, the solvent includes an aprotic solvent or an ionic liquid. The aprotic solvent includes dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), or N-methyl-2-pyrrolidone (NMP). The ionic liquid is a pyridinium cation ionic liquid or an imidazolium cation ionic liquid, and the corresponding anion is BF4. - , B(CN)4 - , CH3BF3 - , CH2CHBF3 - , CF3BF3 - , C2F5BF3 - , n-C3F7BF3 - , n-C4F9BF3 - , PF6 - , CF3CO2 - , CF3SO3 - , N(SO2CF3)2 - , N(COCF3)(SO2CF3) - , N(SO2F)2 - , N(CN)2 - , C(CN)3 - , SCN - , SeCN - , CuCl2 - , AlCl4 - and F(HF)2.3 anion.

[0012] Specifically, the processing aid has the effect of helping the copolymer of the present invention and the thermosetting material form a homogeneous phase. The processing aid also has the technical effect of catalyzing the reaction between the copolymer of the present invention and the thermosetting material. Generally, a hydroxy compound, an amine compound, a hydroxy group-amine compound, or a combination thereof reacts with the thermosetting material to produce an intermediate product with a low molecular weight. The intermediate product and the copolymer of the present invention have better compatibility, for example, with a (urethane-carbonate) copolymer or / and a copolymer containing a carbonate group.

[0013] Specifically, the additive comprises 0.5-99.5 wt.% of the copolymer and 99.5-0.5 wt.% of the processing aid.

[0014] A second object of the present invention is to disclose a recyclable thermosetting composition, which comprises an additive (or copolymer) and a thermosetting material, wherein the sum of the weight percentage of the additive (or copolymer) and the weight percentage of the thermosetting material is 100%.

[0015] Specifically, the copolymer has at least one urethane group and at least one carbonate group and / or at least one urea group. The weight percentage of the copolymer is 0.1-85 wt.%, based on the total weight of the recyclable thermosetting composition. The thermosetting material includes polyurethane, polyurethane foam material, epoxy resin, phenolic resin, reinforced composite material, benzoxazine resin, acrylic resin, or a combination thereof.

[0016] Specifically, the additive (or copolymer) and the thermosetting material are mixed or blended to obtain a recyclable thermosetting composition, which may be a homogeneous or heterogeneous phase mixture.

[0017] Specifically, the additive (or copolymer) and the thermosetting material produce decomposition products of the thermosetting material at elevated temperatures, and the decomposition products of the recyclable thermosetting material can be recycled to produce new thermosetting materials.

[0018] A third object of the present invention is to provide a recycling process (recycling method) for waste thermosetting materials, including but not limited to the following steps:

[0019] Step 1: Providing a mixture, the mixture including at least one copolymer, at least one processing aid, and at least one waste thermosetting material, the copolymer having at least one urethane group, at least one carbonate group, and / or at least one urea group, and the weight percentage of the copolymer is 0.1-85 wt.%, based on the total weight of the mixture.

[0020] Step 2: Heat the mixture to 50-220°C to obtain a product, which contains inorganic and organic substances.

[0021] Step 3: Carrying out a process to separate the inorganic and organic materials, the organic materials including relatively high molecular weight organic compounds and relatively low molecular weight organic compounds, the process including extraction, crystallization, distillation, filtration, or a combination thereof.

[0022] Step 4: A second process is carried out to separate the relatively high molecular weight organic compounds from the relatively low molecular weight organic compounds, which may include extraction, crystallization, distillation, filtration, or a combination thereof, and the relatively high molecular weight organic compounds are used as raw materials for recycling epoxy resins, polyurethanes, benzoxazine resins, phenolic resins, acrylic resins, polyurethane foam materials, or reinforced composite materials.

[0023] Specifically, the copolymer has at least one urethane group, at least one carbonate group and / or at least one urea group, and the number average molecular weight of the copolymer is in the range of 100-50,000 Da.

[0024] Specifically, the processing aid is a decomposition agent and includes at least one catalyst and at least one solvent.

[0025] Specifically, the catalysts include amines, imidazoles, metals and their salts, Lewis acids, or Lewis bases. The amines include quaternary ammonium salts, dimethylamine, diethylamine, triethylamine, triethanolamine, dimethylaniline, or pyridine. The amidine catalysts include 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,4-diazabicyclo[2.2.2]octane (DBACO), or aromatic dimethylamine compounds. The aliphatic amines include diethylenetriamine (DETA), triethylenetetramine (TETA), or polyether polyamines. The imidazole catalysts include imidazolidinyl urea, diethyltetramethylimidazole, or mixtures thereof. The metals and their salts include aluminum, cobalt, nickel, copper, iron, zinc, chromium, vanadium, titanium, manganese, potassium, zirconium, and their oxide, halide, sulfate, nitrate, or phosphate complexes. The Lewis acid includes boron trifluoride and its complexes. The Lewis base includes C1-C10 linear or branched alkyl phosphorus compounds, aromatic phosphorus compounds, or halogen-substituted phosphorus compounds. Other types of catalysts include thiourea and its derivatives, titanates, or rare earth metal compounds.

[0026] Specifically, the catalyst loading is 1.5-15 wt.% based on the weight of the thermosetting material.

[0027] Specifically, the solvent includes an aprotic solvent or an ionic liquid. The aprotic solvent includes dimethylformamide (DMF), dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO), or N-methyl-2-pyrrolidone (NMP). The ionic liquid is a pyridinium cation ionic liquid or an imidazolium cation ionic liquid, and the corresponding anion is BF4. - , B(CN)4 - , CH3BF3 - , CH2CHBF3 - , CF3BF3 - , C2F5BF3 - , n-C3F7BF3 -, n-C4F9BF3 - , PF6 - , CF3CO2 - , CF3SO3 - , N(SO2CF3)2 - , N(COCF3)(SO2CF3) - , N(SO2F)2 - , N(CN)2 - , C(CN)3 - , SCN - , SeCN - , CuCl2 - , AlCl4 - , and F(HF)2.3 - is selected from the group consisting of:

[0028] Specifically, the inorganic material includes glass fibers, inorganic matrices or inorganic fillers in different forms.

[0029] Specifically, the organic matter includes organic compounds with relatively high molecular weights and organic compounds with relatively low molecular weights.

[0030] Specifically, the relatively high molecular weight organic compounds are raw materials for recycling epoxy resins, polyurethanes, phenolic resins, acrylic resins, benzoxazine resins, polyurethane foam materials or reinforced composite materials.

[0031] Specifically, the relatively low molecular weight organic compound includes urea, polyurea, cyclic urea, and cyclic urethane monomers or oligomers.

[0032] As described above, the present invention provides a novel additive for recycling thermosetting materials. The additive composition includes a copolymer, which has at least one urethane group and at least one carbonate group and / or at least one urea group. Technical advantages of the present invention include, but are not limited to, the following: Specifically, the additive or polymer can react with a thermosetting material to produce a decomposition product that can be recycled and reused. Furthermore, the decomposition product can be recycled to produce a new thermosetting material. Furthermore, after mixing discarded thermosetting materials with the additive, new resin materials can be regenerated, simplifying the recycling process. Based on this, the present invention can provide a technologically innovative solution for recycling and reusing thermosetting materials based on the principles of lean chemistry. [Brief explanation of the drawings]

[0033] [Figure 1] 1H-NMR spectrum of copolymer PCC-0.25. [Figure 2] 1H-NMR spectrum of copolymer PCC-0.5. [Figure 3] 1H-NMR spectrum of copolymer PCC-0.99. [Figure 4] 1 is a 1H-NMR spectrum of copolymer PCC-1.0S. [Figure 5] 1 is an FTIR spectrum of sample PCC-E1. [Figure 6] 1 is an FTIR spectrum of sample PCC-E1-M1. [Figure 7] FTIR spectrum of sample rEP-1. [Figure 8] 1 is an FTIR spectrum of sample PCC-PF1. [Figure 9] 1 is an FTIR spectrum of sample PCC-PF1-M1. [Figure 10] FTIR spectrum of sample rPF-1. [Figure 11]1 is an FTIR spectrum of sample PCC-PMMA1. [Figure 12] 1 is an FTIR spectrum of sample PCC-PMMA1-M1. [Figure 13] FTIR spectrum of sample rPMMA-1. [Figure 14] 1 is an FTIR spectrum of sample PCC-PU1. [Figure 15] 1 is an FTIR spectrum of sample PCC-PU-T1. [Figure 16] 1 is an FTIR spectrum of sample rPU-1. [Figure 17] 1 is an FTIR spectrum of sample PCC-BZ1. [Figure 18] 1 is an FTIR spectrum of sample PCC-BZ1-T1. [Figure 19] FTIR spectrum of sample rBZ-1. [Figure 20] 1 is an FTIR spectrum of sample PCC-C1. [Figure 21] 1 is an FTIR spectrum of sample PCC-C1-R1. [Figure 22] FTIR spectrum of sample rC-1. DETAILED DESCRIPTION OF THE INVENTION

[0034] A first embodiment of the present invention discloses an additive for recycling thermoset materials.

[0035] Specifically, the additive composition for recycling thermosetting materials comprises at least one copolymer, and preferably further comprises at least one processing aid.

[0036] Specifically, the copolymer contains at least one urethane group, at least one carbonate group and / or at least one urea group, and the number average molecular weight of the copolymer ranges from 100 to 50,000 Da.

[0037] Specifically, the processing aid comprises an amine, a catalyst, a solvent, or a mixture thereof. Preferably, the processing aid is a hydroxy compound, an amine compound, an amine hydroxy compound, or a combination thereof.

[0038] In a specific embodiment, the catalyst includes an amine, an imidazole, a metal and its salt, a Lewis acid, or a Lewis base. Examples of the amine include quaternary ammonium salts, dimethylamine, diethylamine, triethylamine, triethanolamine, dimethylaniline, or pyridine. Examples of the amidine catalyst include 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,4-diazabicyclo[2.2.2]octane (DBACO), or an aromatic dimethylamine compound. Examples of the aliphatic amine include diethylenetriamine (DETA), triethylenetetramine (TETA), or a polyether polyamine. Examples of the imidazole catalyst include imidazolidinyl urea, diethyltetramethylimidazole, or a mixture thereof. Examples of the metal and its salt include aluminum, cobalt, nickel, copper, iron, zinc, chromium, vanadium, titanium, manganese, potassium, zirconium, and their oxides, halides, sulfates, nitrates, and phosphates. The Lewis acid includes boron trifluoride and its complexes. The Lewis base includes C1-C10 linear or branched alkylphosphorus compounds, aromatic phosphorus compounds, or halogen-substituted phosphorus compounds. Other catalysts include thiourea and its derivatives, titanates, or rare earth metal compounds.

[0039] In a specific embodiment, the catalyst loading is 1.5-15 wt.% based on the weight of the thermosetting material.

[0040] In a specific embodiment, the solvent comprises an aprotic solvent or an ionic liquid, such as dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), or N-methyl-2-pyrrolidone (NMP). The ionic liquid is a pyridinium cation ionic liquid or an imidazolium cation ionic liquid, and the corresponding anion is BF4. - , B(CN)4 - , CH3BF3 - , CH2CHBF3 - , CF3BF3 - , C2F5BF3 - , n-C3F7BF3 - , n-C4F9BF3 - , PF6 - , CF3CO2 - , CF3SO3 - , N(SO2CF3)2 - , N(COCF3)(SO2CF3) - , N(SO2F)2 - , N(CN)2 - , C(CN)3 - , SCN - , SeCN - , CuCl2 - , AlCl4 - and F(HF)2.3 anion.

[0041] Specifically, the processing aid can help (promote) the formation of a uniform phase (homogeneous phase) between the copolymer of the present invention and the thermosetting material. At the same time, the processing aid also has the technical effect of catalyzing the reaction between the copolymer of the present invention and the thermosetting material. Generally, a hydroxy compound, an amine compound, a hydroxy group-amine compound, or a combination thereof reacts with the thermosetting material to obtain an intermediate product with a low molecular weight. The intermediate product has better compatibility with the copolymer of the present invention, such as a (urethane-carbonate) copolymer or / and a copolymer having a carbonate group.

[0042] In a preferred embodiment, the additive composition comprises 0.5-99.5 wt.% of the copolymer and 99.5-0.5 wt.% of the processing aid. Preferably, the additive composition comprises 5-50 wt.% of the copolymer and 95-50 wt.% of the processing aid.

[0043] In a preferred embodiment, the copolymer comprises at least one urethane group and at least one carbonate group and / or at least one urea group, and the number average molecular weight of the copolymer ranges from 100 to 50,000 Da.

[0044] In a preferred embodiment, the copolymer is a (urethane-carbonate) copolymer, a (urethane-urea) copolymer, a (carbonate-urea) copolymer, a (urethane-carbonate-urea) copolymer, or a combination thereof.

[0045] In a specific embodiment, the urethane group has a structure shown in formula (1) or formula (2).

[0046] Formula (1): JPEG2025532583000001.jpg2655

[0047] Formula (2): JPEG2025532583000002.jpg2848

[0048] In a specific embodiment, R1 is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a polyether group having a molecular weight of 50 to 10,000, or a polysilyl ether group having a molecular weight of 50 to 10,000; R2 is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, an alkylphenyl group having 7 to 20 carbon atoms, or an alkylphenol group having 6 to 20 carbon atoms; R3 is a hydroxy group, an amine group, a carbonyl group, a carboxylic acid group, an ester group, or an amide group; X is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a polyether group having a molecular weight of 50 to 10,000, or a polysilyl ether group having a molecular weight of 50 to 10,000; and n is an integer from 1 to 10.

[0049] In a specific embodiment, the carbonate group has the structure shown in formula (3):

[0050] Formula (3): JPEG2025532583000003.jpg1436

[0051] In specific embodiments, R2 is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, an alkylphenyl group having 7 to 20 carbon atoms, or an alkylphenol group having 6 to 20 carbon atoms.

[0052] In a specific embodiment, the urea group has the structure shown in formula (4):

[0053] Formula (4): JPEG2025532583000004.jpg2465

[0054] In a specific embodiment, R1 is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a polyether group having a molecular weight of 50 to 10,000, or a polysilyl ether group having a molecular weight of 50 to 10,000; R3 is a hydroxy group, an amine group, a carbonyl group, a carboxylic acid group, an ester group, or an amide group; X is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a polyether group having a molecular weight of 50 to 10,000, or a polysilyl ether group having a molecular weight of 50 to 10,000; and n is an integer from 1 to 10.

[0055] In an exemplary embodiment, the copolymer is a (urethane-carbonate) copolymer and has the structure shown in formula (5).

[0056] Formula (5): JPEG2025532583000005.jpg27160

[0057] In a specific embodiment, m shown in formula (5) is an integer selected from 1-100, and x and y are each an integer selected from 1-1000.

[0058] In a specific embodiment, the weight average molecular weight of the (urethane-carbonate) copolymer represented by formula (5) is in the range of 1,000-100,000 Da.

[0059] In a specific embodiment, the glass transition temperature (T g ) is greater than 50°C. In a preferred embodiment, its glass transition temperature (T g ) exceeds 80°C.

[0060] In a preferred embodiment, the processing aid comprises diphenyl carbonate, ethanolamine, bisphenol A, anisole, polytetramethylene ether glycol, or a combination thereof.

[0061] In specific embodiments, the amine compound comprises a primary amine, a diamine, a polyamine, or a polyetherdiamine.

[0062] In specific embodiments, the catalyst comprises a metal catalyst or an organic salt.

[0063] A second embodiment of the present invention discloses a recyclable thermosetting composition.

[0064] Specifically, the recyclable thermosetting composition includes a copolymer and at least one thermosetting material, wherein the weight percent of the copolymer plus the weight percent of the thermosetting material equals 100%.

[0065] Specifically, the copolymer comprises at least one urethane group and at least one carbonate group and / or at least one urea group, and the weight percentage of the copolymer is 0.1-85 wt.%, based on the total weight of the recyclable thermosetting composition.

[0066] Specifically, the copolymer and the thermosetting material are mixed or blended to form the recyclable thermosetting composition described above.

[0067] Specifically, the copolymer and the thermosetting material can produce decomposition products of the thermosetting material at high temperatures, and the decomposition products of the recyclable thermosetting material can be recycled and regenerated to produce new thermosetting materials.

[0068] The decomposition products of the recyclable thermoset material include inorganic matter, relatively high molecular weight organic compounds, and relatively low molecular weight organic compounds.

[0069] The organic compounds with relatively high molecular weights are raw materials for recycling epoxy resins, polyurethanes, benzoxazine resins, phenolic resins, acrylic resins, polyurethane foam materials or reinforced composite materials.

[0070] The relatively low molecular weight organic compounds include urea, polyurea, cyclic urea, cyclic amine ester monomers or oligomers.

[0071] In a preferred embodiment, the recyclable thermosetting composition comprises a recyclable polyurethane, a recyclable polyurethane foam material, a recyclable epoxy resin, a recyclable phenolic resin, a recyclable composite material, a recyclable benzoxazine resin, a recyclable acrylic resin, or a combination thereof.

[0072] In a specific embodiment, the recyclable polyurethane comprises 20-40 wt.% of the additive of the present invention or the copolymer described above.

[0073] In a specific embodiment, the recyclable epoxy resin comprises 30-60 wt.% of the additive of the present invention or the copolymer described above.

[0074] In a specific embodiment, the recyclable phenolic resin comprises 50-70 wt.% of the additive of the present invention or the copolymer described above.

[0075] In a specific embodiment, the recyclable benzoxazine resin comprises 10-25 wt.% of the additive of the present invention or the copolymer described above.

[0076] In a specific embodiment, the recyclable composite material comprises 35-85 wt.% of the additive of the present invention or the copolymer described above.

[0077] In a specific embodiment, the recyclable acrylic resin comprises 30-60 wt.% of the additive of the present invention or the copolymer described above.

[0078] In a preferred embodiment, the copolymer is a (urethane-carbonate) copolymer, a (urethane-urea) copolymer, a (carbonate-urea) copolymer, a (urethane-carbonate-urea) copolymer, or a combination thereof.

[0079] In a preferred embodiment, the copolymer has a number average molecular weight range of 100-50,000 Da.

[0080] In a preferred embodiment, the thermosetting material comprises polyurethane, polyurethane foam material, epoxy resin, phenolic resin, reinforced composite material, benzoxazine resin, acrylic resin, or a combination thereof.

[0081] In a specific embodiment, the urethane group has a structure shown in formula (1) or formula (2).

[0082] Formula (1): JPEG2025532583000006.jpg2555

[0083] Formula (2): JPEG2025532583000007.jpg2348

[0084] In a specific embodiment, R1 is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a polyether group having a molecular weight of 50 to 10,000, or a polysilyl ether group having a molecular weight of 50 to 10,000; R2 is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, an alkylphenyl group having 7 to 20 carbon atoms, or an alkylphenol group having 6 to 20 carbon atoms; R3 is a hydroxy group, an amine group, a carbonyl group, a carboxylic acid group, an ester group, or an amide group; X is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a polyether group having a molecular weight of 50 to 10,000, or a polysilyl ether group having a molecular weight of 50 to 10,000; and n is an integer from 1 to 10.

[0085] In a specific embodiment, the carbonate group has the structure shown in formula (3):

[0086] Formula (3): JPEG2025532583000008.jpg1436

[0087] In specific embodiments, R2 is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, an alkylphenyl group having 7 to 20 carbon atoms, or an alkylphenol group having 6 to 20 carbon atoms.

[0088] In a specific embodiment, the urea group has the structure shown in formula (4):

[0089] Formula (4): JPEG2025532583000009.jpg2365

[0090] In a specific embodiment, R1 is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a polyether group having a molecular weight of 50 to 10,000, or a polysilyl ether group having a molecular weight of 50 to 10,000; R3 is a hydroxy group, an amine group, a carbonyl group, a carboxylic acid group, an ester group, or an amide group; X is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a polyether group having a molecular weight of 50 to 10,000, or a polysilyl ether group having a molecular weight of 50 to 10,000; and n is an integer from 1 to 10.

[0091] In another embodiment, the recyclable thermoset composition further comprises 1.5-15 wt % of a processing aid, based on the total weight of the recyclable thermoset composition.

[0092] In a specific embodiment, the processing aid comprises an amine, a catalyst, a solvent, or a mixture thereof. Preferably, the processing aid is a hydroxy compound, an amine compound, an amine hydroxy compound, or a combination thereof.

[0093] In specific embodiments, the catalyst includes an amine, an imidazole, a metal and its salt, a Lewis acid, or a Lewis base. The amine includes a quaternary ammonium salt, dimethylamine, diethylamine, triethylamine, triethanolamine, dimethylaniline, or pyridine. The amidine catalyst includes 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,4-diazabicyclo[2.2.2]octane (DBACO), or an aromatic dimethylamine compound. The aliphatic amine includes diethylenetriamine (DETA), triethylenetetramine (TETA), or a polyether polyamine. The imidazole catalyst includes imidazolidinyl urea, diethyltetramethylimidazole, or a mixture thereof. The metal and its salt include aluminum, cobalt, nickel, copper, iron, zinc, chromium, vanadium, titanium, manganese, potassium, zirconium, and their oxide, halide, sulfate, nitrate, or phosphate complexes. The Lewis acid includes boron trifluoride and its complexes. The Lewis base includes C1-C10 linear or branched alkyl phosphorus compounds, aromatic phosphorus compounds, or halogen-substituted phosphorus compounds. Other types of catalysts include thiourea and its derivatives, titanates, or rare earth metal compounds.

[0094] In a specific embodiment, the catalyst loading is 1.5-15 wt.% based on the weight of the thermosetting material.

[0095] In a specific embodiment, the solvent comprises an aprotic solvent or an ionic liquid. The aprotic solvent comprises dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), or N-methyl-2-pyrrolidone (NMP). The ionic liquid is a pyridinium cation ionic liquid or an imidazolium cation ionic liquid, and the corresponding anion is BF4. - , B(CN)4 - , CH3BF3 - , CH2CHBF3 - , CF3BF3 - , C2F5BF3 - , n-C3F7BF3- , n-C4F9BF3 - , PF6 - , CF3CO2 - , CF3SO3 - , N(SO2CF3)2 - , N(COCF3)(SO2CF3) - , N(SO2F)2 - , N(CN)2 - , C(CN)3 - , SCN - , SeCN - , CuCl2 - , AlCl4 - and F(HF)2.3 anion.

[0096] A third embodiment of the present invention provides a recycling manufacturing process for waste thermosetting materials, which includes the following steps:

[0097] Step 1: Providing a mixture comprising at least one copolymer, at least one processing aid, and at least one waste thermosetting material, the copolymer comprising at least one urethane group, at least one carbonate group, and / or at least one urea group, the weight percentage of the copolymer being 0.1-85 wt.%, based on the total weight of the mixture.

[0098] Step 2: Heat the mixture to 50-220°C to obtain a product, which contains inorganic and organic substances.

[0099] Step 3: Carrying out a process to separate the inorganic and organic materials, the process including extraction, crystallization, distillation, filtration, or a combination thereof, wherein the organic materials include relatively high molecular weight organic compounds and relatively low molecular weight organic compounds.

[0100] Step 4: A second process is carried out to separate the relatively high molecular weight organic compounds from the relatively low molecular weight organic compounds. The second process may include extraction, crystallization, distillation, filtration, or a combination thereof. The relatively high molecular weight organic compounds are raw materials for recycling epoxy resins, polyurethanes, benzoxazine resins, phenolic resins, acrylic resins, polyurethane foam materials, or reinforced composite materials.

[0101] In a preferred embodiment, the copolymer is a (urethane-carbonate) copolymer, a (urethane-urea) copolymer, a (carbonate-urea) copolymer, a (urethane-carbonate-urea) copolymer, or a combination thereof.

[0102] In a preferred embodiment, the number average molecular weight range of the copolymer is 100-50,000 Da.

[0103] In a preferred embodiment, the thermosetting material comprises polyurethane, polyurethane foam material, epoxy resin, phenolic resin, reinforced composite material, benzoxazine resin, acrylic resin, or a combination thereof.

[0104] In a specific embodiment, the urethane group has a structure shown in formula (1) or formula (2).

[0105] Formula (1): JPEG2025532583000010.jpg2455

[0106] Formula (2): JPEG2025532583000011.jpg2648

[0107] In a specific embodiment, R1 is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a polyether group having a molecular weight of 50 to 10,000, or a polysilyl ether group having a molecular weight of 50 to 10,000; R2 is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, an alkylphenyl group having 7 to 20 carbon atoms, or an alkylphenol group having 6 to 20 carbon atoms; R3 is a hydroxy group, an amine group, a carbonyl group, a carboxylic acid group, an ester group, or an amide group; X is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a polyether group having a molecular weight of 50 to 10,000, or a polysilyl ether group having a molecular weight of 50 to 10,000; and n is an integer from 1 to 10.

[0108] In a specific embodiment, the carbonate group has the structure shown in formula (3):

[0109] Formula (3): JPEG2025532583000012.jpg1437

[0110] In specific embodiments, R2 is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, an alkylphenyl group having 7 to 20 carbon atoms, or an alkylphenol group having 6 to 20 carbon atoms.

[0111] In a specific embodiment, the urea group has the structure shown in formula (4):

[0112] Formula (4): JPEG2025532583000013.jpg2565

[0113] In a specific embodiment, R1 is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a polyether group having a molecular weight of 50 to 10,000, or a polysilyl ether group having a molecular weight of 50 to 10,000; R3 is a hydroxy group, an amine group, a carbonyl group, a carboxylic acid group, an ester group, or an amide group; X is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a polyether group having a molecular weight of 50 to 10,000, or a polysilyl ether group having a molecular weight of 50 to 10,000; and n is an integer from 1 to 10.

[0114] In a specific embodiment, the processing aid comprises an amine, a catalyst, a solvent, or a mixture thereof. Preferably, the processing aid is a hydroxy compound, an amine compound, an amine hydroxy compound, or a combination thereof.

[0115] In specific embodiments, the catalyst includes an amine, an imidazole, a metal and its salt, a Lewis acid, or a Lewis base. Amines include quaternary ammonium salts, dimethylamine, diethylamine, triethylamine, triethanolamine, dimethylaniline, or pyridine. Amidine catalysts include 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), 1,4-diazabicyclo[2.2.2]octane (DBACO), or an aromatic dimethylamine compound. Aliphatic amines include diethylenetriamine (DETA), triethylenetetramine (TETA), or a polyether polyamine. Imidazole catalysts include imidazolidinyl urea, diethyltetramethylimidazole, or a mixture thereof. Metals and their salts include aluminum, cobalt, nickel, copper, iron, zinc, chromium, vanadium, titanium, manganese, potassium, zirconium, and their oxide, halide, sulfate, nitrate, or phosphate complexes. Lewis acids include boron trifluoride and its complexes. Lewis bases include C1-C10 linear or branched alkylphosphorus compounds, aromatic phosphorus compounds, or halogen-substituted phosphorus compounds. Other types of catalysts include thiourea and its derivatives, titanates, or rare earth metal compounds.

[0116] In a specific embodiment, the catalyst loading is 1.5-15 wt.% based on the weight of the thermosetting material.

[0117] In a specific embodiment, the solvent comprises an aprotic solvent or an ionic liquid. The aprotic solvent comprises dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), or N-methyl-2-pyrrolidone (NMP). The ionic liquid is a pyridinium cation ionic liquid or an imidazolium cation ionic liquid, and the corresponding anion is BF4. - , B(CN)4 - , CH3BF3 - , CH2CHBF3 - , CF3BF3 - , C2F5BF3 - , n-C3F7BF3 - , n-C4F9BF3 - , PF6 - , CF3CO2 - , CF3SO3 - , N(SO2CF3)2 - , N(COCF3)(SO2CF3) - , N(SO2F)2 - , N(CN)2 - , C(CN)3 - , SCN - , SeCN - , CuCl2 - , AlCl4 - and F(HF)2.3 anion.

[0118] In an exemplary embodiment, waste polycarbonate is reacted with a diamine to obtain the urethane-carbonate copolymer of the present invention. The urethane-carbonate copolymer is mixed with waste epoxy resin to obtain a recyclable epoxy resin thermosetting composition, which is then heated to obtain decomposition products, which contain inorganic and organic matter, and are separated from each other by extraction, crystallization, distillation, filtration, or a combination thereof.

[0119] In a preferred embodiment, the inorganic materials are used to recycle and manufacture other materials.

[0120] In a preferred embodiment, the organic matter comprises a relatively high molecular weight organic compound and a relatively low molecular weight organic compound.

[0121] In a specific embodiment, the relatively high molecular weight organic compound is a raw material for recycling epoxy resins, polyurethanes, phenolic resins, acrylic resins, polyurethane foam materials or reinforced composite materials.

[0122] In a specific embodiment, the relatively low molecular weight organic compound comprises a urea, polyurea, cyclic urea, or cyclic urethane monomer or oligomer. The relatively low molecular weight organic compound is used in the manufacture of specialty chemicals.

[0123] The following are experimental examples to illustrate the technical features and technical effects of the present invention.

[0124] In the following examples and tables, Td5 represents the temperature at which the weight loss is 5 wt.% in thermogravimetric analysis (TGA), and T g represents the glass transition temperature.

[0125] Example 1: Copolymer [PCC ((urethane-carbonate) copolymer) formula (5)] General production method

[0126] First, polycarbonate (PC, 50-100 g) was dissolved in anisole (500 ml) at 75°C, and an amine compound or polyetherdiamine (10-20 g) was added. The mixture was stirred for 3 hours to react, and the anisole was removed under vacuum to obtain a copolymer (PCC; (urethane-carbonate) copolymer). FTIR analysis results (cm -1 , KBr): 3300 (-OH), 1775 (-C=O(carbonate)), and 1715 (-C=O(urethane)). 1H-NMR (600 MHz, deuterated dimethyl sulfoxide [d-DMSO]) analysis results: δ (ppm) = δ 1.20-1.40, δ 1.40-1.50, δ 1.50-1.80, δ 3.00-3.20, δ 3.70-3.90, δ 6.60-6.80, δ 6.85-7.10, δ 7.10-7.40, δ 7.60-7.80, δ 9.10-9.30. The PCC-number indicates the total molar ratio of the m-segment structure in formula (5) (the total molar ratio of the m-segment structure in the structure shown in formula (5)). For example, PCC-0.5 indicates that the total molar ratio of the m-segment structure in formula (5) is 0.5. The number is equal to m divided by the sum of m, x, and y. According to the manufacturing method of this example, copolymers PCC-0.25, PCC-0.5 and PCC-0.99 were each manufactured. 1 The H-NMR spectra are shown in Figures 1, 2 and 3.

[0127] General steps in the complete recycling process for recyclable thermosetting compositions

[0128] Recyclable thermosetting compositions containing the copolymer (PCC) of the present invention can be digested and decomposed using hydroxyl compounds or amine compounds (e.g., monoamine, diamine, or triamine compounds). Specifically, the recyclable thermosetting compositions (PCC-BZ, PCC-PF, PMMA / PCC, PCC-Bis-GMA, PCC-Bis-MA, PCC-PU, PCC-PUF, or PCC-E, which may contain organic or inorganic fillers) are digested and decomposed by heating to 100-250°C in the presence of ethanolamine. After 3 hours, the recyclable thermosetting compositions are completely dissolved, yielding decomposition products. First, the fillers are separated, and then phenolic compounds and compounds with urethane or urea functional groups are separated by distillation or extraction processes, resulting in complete recycling. The decomposition products (cm) are analyzed by Fourier spectrum analysis. -1, KBr) were analyzed: 3300-3400 (-OH of phenol and -COONH), 1716 (-C=O(carbamate), and 1670 (-C=O(urea)).

[0129] Example 2: Preparation of recyclable epoxy resin (PCC-E)

[0130] In this example, a recyclable epoxy resin (PCC-E) was prepared using the composition shown in Table 1. The thermal properties (thermal decomposition temperature Td and glass transition temperature Tg) of the recyclable epoxy resin are shown in Table 2. Specifically, the recyclable epoxy resin was prepared by mixing an epoxy resin (trade name DER332) with the additive / copolymer (PCC) of the present invention. First, the copolymer [PCC (3.00 g)] was mixed with anisole (20 ml) and heated to 75 °C under nitrogen with stirring to completely dissolve the copolymer. Then, the epoxy resin [DER332 (6.20 g)] dissolved in anisole (4 ml) was added, followed by 2 mL of a 0.1 wt% triphenylphosphine (TPP)-anisole solution. The mixture was heated to 120 °C and the majority of the solvent was removed by distillation under reduced pressure. The reaction was continued for 24 hours, and the reaction was monitored by hydrogen nuclear magnetic resonance spectroscopy until the ring-opening reaction of the epoxy groups ceased, at which point the reaction was deemed complete. The Fourier transform infrared spectrum results (cm) of the obtained recyclable epoxy resin -1 , KBr): 3300 (-OH), 1775 (-C=O(carbonate)), 1715 (-C=O(urethane)) and 913 (oxirane); Hydrogen nuclear magnetic resonance spectroscopy results: 1H-NMR (ppm, DMSO-d6): δ1.20-1.40, δ1.40-1.50, δ1.50-1.70, δ2.65-2.75, δ2.80-2.90, δ2.95-3.15, δ3.25-3.40, δ3.70-3 .90, δ3.90-4.20, δ4.20-4.30, δ6.60-6.70, δ6.80-6.90, δ6.90-7.05, δ7.08-7.20, δ7.20-7.40, δ7.60-7.80, δ9.10-9.30. Typically, the epoxy resin undergoes a curing reaction using a curing agent such as polyether polyamine, aliphatic amine, cyclic amine, aromatic amine, polyimide, polyamide, dicyandiamide, acid anhydride, or melamine as a crosslinker to form a 3D network structure. The catalyst includes Lewis acids, Lewis bases, metal alkyl oxides, boron trifluoride complexes, or fuller radical initiators. The curing process is monitored by Fourier transform infrared spectroscopy, which detects the characteristic peaks of the epoxy group (oxirane functional group at peaks of around 913 cm). -1 ) disappears.

[0131] Table 1 JPEG2025532583000014.jpg129151* NPEL-128 is the trade name for a bisphenol A type epoxy resin, and DETA is diethylenetriamine.

[0132] Table 2 JPEG2025532583000015.jpg10763

[0133] Example 2-1: Recyclable epoxy resin recycling process

[0134] Referring to Table 3, a recyclable epoxy resin (PCC-E), a decomposing agent, and a solvent (DMF, DMSO, or NMP) are mixed. The decomposing agent includes 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), zinc oxide (ZnO), boron trifluoride (BF3), or triethylenetetramine (TETA). The mixture is then heated to 70-220°C to obtain the recyclable epoxy resin decomposition product. Referring to Table 8, the recyclable epoxy resin decomposition product is mixed with the compounds shown in the table and heated to cure, obtaining a new recycled epoxy resin. The Fourier infrared spectrum of the new recycled epoxy resin matches the characteristic peaks of the infrared spectrum of the original recyclable epoxy resin. Based on this, it has been confirmed that the recyclable epoxy resin (PCC-E) of the present invention has the technical effect of being fully recyclable and cyclically renewable.

[0135] Table 3 JPEG2025532583000016.jpg176152

[0136] Table 4 JPEG2025532583000017.jpg113161* NPEL-128 is the trade name for a bisphenol A type epoxy resin.

[0137] Example 3: Production of recyclable polyurethane (PCC-PU) and recyclable polyurethane foam (PCC-PUF)

[0138] In this example, a recyclable polyurethane (PCC-PU) and a recyclable polyurethane foam (PCC-PUF) were prepared using the composition shown in Table 5. The thermal and mechanical properties of the recyclable polyurethane (PCC-PU) are shown in Table 6. Generally speaking, a solvent (e.g., DMF), a diisocyanate (e.g., MDI), and a polyol (e.g., PTMEG) were mixed and heated to 60°C under nitrogen to prepare a prepolymer. After 2 hours, the copolymer (PCC) of the present invention was added, followed by a crosslinking agent (TMP) and a catalyst (DBTDL (2 mol% of MDI)) over approximately 1 hour. The reaction was allowed to proceed, resulting in a recyclable polyurethane (PCC-PU) with a crosslinked structure. The recyclable polyurethane foam (PCC-PUF) was also prepared by the following steps: First, the polyol and copolymer (PCC) were stirred and mixed at 55°C, followed by the addition of silicone oil, water, and an amine compound, and stirring was continued. Next, an isocyanate (e.g., HDI) and a catalyst (e.g., dibutyltin dilaurate) are added, and the reaction is continued for more than 1 hour in an oven at 55°C. After that, the reaction is returned to room temperature and continued for 24 hours. Finally, a recyclable polyurethane foam (PCC-PUF) is obtained. Fourier transform infrared spectroscopy analysis results (FTIR (cm -1 ,KBr)): 3300-3400 (-COONH), and 1715 (-C=O(urethane)).

[0139] Table 5 JPEG2025532583000018.jpg165169*PLACELL 410 is the trade name of a polyester polyol. **T9 is the trade name of a tin compound catalyst.

[0140] Table 6 JPEG2025532583000019.jpg78128

[0141] Example 3-1: Recyclable polyurethane recycling process

[0142] Referring to Table 7, recyclable polyurethane (PCC-PU), a decomposition agent, and a solvent (DMF, DMSO, or NMP) are mixed. The decomposition agent includes 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), zinc oxide (ZnO), boron trifluoride (BF3), or triethylenetetramine (TETA). The mixture is then heated to 70-220°C to obtain the recyclable polyurethane decomposition product. Referring to Table 8, the recyclable polyurethane decomposition product and the compounds shown in the table are mixed and heated to cure, resulting in a new recycled polyurethane. The Fourier infrared spectrum of the new recycled polyurethane matches the characteristic peaks of the infrared spectrum of the original recyclable polyurethane, confirming the technical effect of the recyclable polyurethane of the present invention being fully recyclable and cyclically recyclable.

[0143] Table 7 JPEG2025532583000020.jpg72161

[0144] Table 8 JPEG2025532583000021.jpg91161* PLACELL 410 is the trade name for a polyester polyol.

[0145] Example 4: Preparation of recyclable acrylic resin (PCC-PMMA)

[0146] The method in Example 4 can be applied to the production of recyclable acrylic resin (PCC-PMMA), recyclable bisphenol A glycidyl methacrylate (PCC-Bis-GMA), recyclable bisphenol acrylic resin (PCC-Bis-MA), and other acrylic resins with modified functional groups. Referring to the compositions shown in Table 9, in one experiment, MMA monomer and copolymer (PCC) were first dissolved in THF (50 / 50 by weight), dried at 60°C for 1 day to form a film, and then treated under vacuum at 125°C for 1 day. The resulting film was cut and hot-pressed at 200°C for 1 day to obtain recyclable acrylic resin (PCC-PMMA). In another experiment, copolymer [PCC (5 mmol)], glycidyl methacrylate (GMA) (10 mmol), and tertiary amine (N,N-dimethylbenzylamine (0.05 mmol)) were mixed. The mixture was heated to 70°C under argon gas and the reaction was maintained for 6 hours to yield a viscous, recyclable bisphenol A glycidyl methacrylate. In another experiment, the copolymer [PCC (1.18 mmol)], methacrylic anhydride (1.88 mmol), catalyst [4-(dimethylamino)pyridine (DMAP) (0.01 mmol)], and solvent (N,N-dimethylacetamide (DMAc) 10 ml) were mixed and stirred under nitrogen at room temperature for 24 hours. The mixture was then precipitated into methanol, filtered, and dried at 80°C to yield a recyclable bisphenol A acrylate resin.All of the above examples use fuller radical initiators, which include organometallic compounds and organometallic halides, such as triethylaluminum and titanium tetrachloride, azo compounds (2,2'-azobis(isobutyronitrile) (AIBN)), organic or inorganic peroxide compounds (benzoyl peroxide, di-t-butyl peroxide), and acids, alcohols, amines, or thiols. The above reactions were monitored for acrylic acid functional groups using Fourier transform infrared spectroscopy. Specific Fourier transform infrared spectral results (FTIR) are shown below. -1 , KBr): 3300-3400(-COONH), 1715(-C=O(urethane), and 1600-1680(-C=C(acrylic)).

[0147] Table 9 JPEG2025532583000022.jpg80155

[0148] Example 4-1: Recyclable acrylic resin recycling process

[0149] Referring to Table 10, a recyclable acrylic resin (PCC-PMMA), a decomposing agent, and a solvent (DMF, DMSO, or NMP) are mixed. The decomposing agent includes 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), zinc oxide (ZnO), boron trifluoride (BF3), or triethylenetetramine (TETA). The mixture is then heated to 70-220°C to obtain the recyclable acrylic resin decomposition product. Referring to Table 11, the recyclable acrylic resin decomposition product is mixed with a copolymer shown in the table and heated to harden, thereby obtaining a new recycled acrylic resin. The Fourier infrared spectrum of the new recycled acrylic resin matches the characteristic peaks of the infrared spectrum of the original recyclable acrylic resin, confirming that the recyclable acrylic resin of the present invention is fully recyclable and has the technical effect of being recyclable.

[0150] Table 10 JPEG2025532583000023.jpg62155

[0151] Table 11 JPEG2025532583000024.jpg69161

[0152] Example 5: Preparation of recyclable phenolic resin (PCC-PF)

[0153] This example uses the composition in Table 12 to prepare a recyclable phenolic resin (PCC-PF). The recyclable phenolic resin can be prepared by reacting a mixture of different copolymers (PCC) and phenol with formaldehyde in the presence of an alkaline catalyst. Specifically, the weight percentage of phenol and copolymer (PCC-0.5) reaches 40 wt.%. Phenol (88 wt.% aqueous solution), copolymer (PCC), and formaldehyde are mixed and reacted uniformly. The molar ratio of phenol to formaldehyde is initially 1:1.25, then increased to 1:1.50, and finally increased to 1:2.0. Aqueous sodium hydroxide solution [46% (w / w, on a basis of total phenol)] is added, and the mixture is reacted at 60°C for 1 hour, then heated to 80°C for 1 hour, and then cooled to 60°C for 1 hour. The resin in Table 12 is cured under an acidic catalyst. The selected acid catalysts include xylene sulfonic acid or phosphoric acid aqueous solution. The catalyst loading is usually 3-4 wt.%. Finally, the curing process is carried out at room temperature for 8 hours, followed by aging at 80°C for 4 hours to obtain recyclable phenolic resin (PCC-PF). Fourier transform infrared spectroscopy (FTIR) (cm -1 , KBr) analytical results: 3300-3400 (-COONH), 1715 (-C=O(urethane) and 1470 (methylene of PF resins).

[0154] Table 12 JPEG2025532583000025.jpg138150*KB-3640N is the product name of a phenolic resin. **KB-3570H is the trade name of a phenolic resin.

[0155] Example 5-1: Recyclable phenolic resin recycling process

[0156] Referring to Table 13, a recyclable phenolic resin (PCC-PF), a decomposing agent, and a solvent (DMF, DMSO, or NMP) are mixed. The decomposing agent includes 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), zinc oxide (ZnO), boron trifluoride (BF3), or triethylenetetramine (TETA). The mixture is then heated to 70-220°C to obtain the recyclable phenolic resin decomposition product. Referring to Table 14, the recyclable phenolic resin decomposition product is mixed with a resin listed in the table and heated to cure, thereby obtaining a new recycled phenolic resin. The Fourier infrared spectrum of the new recycled phenolic resin matches the characteristic peaks of the infrared spectrum of the original recyclable phenolic resin. This confirms that the recyclable phenolic resin of the present invention is fully recyclable and has the technical effect of being recyclable.

[0157] Table 13 JPEG2025532583000026.jpg100154

[0158] Table 14 JPEG2025532583000027.jpg69153

[0159] Example 6: Preparation of recyclable composite material (PCC-C)

[0160] This example uses the composition in Table 15 to prepare a recyclable composite material (PCC-C). Specifically, the copolymer of the present invention (PCC) is dissolved in anisole (50 ml) under nitrogen at 75°C, added to APTES (20 mmol), and stirred for 3 hours. The anisole is removed by vacuum distillation to obtain a siliconized copolymer (PCC-1.0S). A diisocyanate (e.g., MDI or IPDI) and / or polyol can be used to prepare a silane-containing polyurethane (PU). Therefore, a mixture of diisocyanate, polyol, and copolymer (PCC-1.0S) is dissolved in DMF and polymerized with an NCO / OH equivalent ratio of 1:1. The polymerization reaction is carried out at 80°C under nitrogen for 3 hours. Next, a solution of a silane-containing compound and TEOS (or nanosilicon spheres) is added, diluted with DMF to a solids content of 10 wt.%, and a drop of concentrated hydrochloric acid (12 M HCl) and a small amount of deionized water are added to obtain a homogeneous mixture. The homogeneous mixture was poured into a Teflon container and placed in an oven at 60°C, heated to 100°C at a heating rate of 10°C / h, and maintained for 6 hours, finally obtaining a recyclable PU / SiO2 composite. The original PC polymer was analyzed by Fourier transform infrared spectroscopy, and the peak at 1773 cm -1 After digestion, the characteristic peak of the carbonate group disappears, and the peak at 1716 cm 3 representative of the polyurethane group appears. -1 A characteristic peak at 956 cm -1 The characteristic peak at 1721 cm represents the formation of siloxane (-Si-OR) groups. The above results indicate that the PC polymer was converted cleanly and other functional groups (i.e., phenol carbamate, silane, and hydroxyl functional groups) were introduced. The structure was analyzed by Fourier transform infrared spectroscopy, and the peak at 1721 cm -1 is the formation of urethane, 953 cm -1 is the formation of siloxane (-Si-OR) groups, 1015-1050 and 800 cm -1 indicates the formation of -Si-O-Si- bonds. As described above, the recyclable composite material of the present invention is produced by the sol-gel process. FTIR analysis results (cm-1 , KBr): 3300-3400(-COONH), 1716(-C=O(urethane), 1015-1050, 956(Si-OR) and 800cm -1 [-Si-O-Si-, silica group]).

[0161] Table 15 JPEG2025532583000028.jpg110163

[0162] Example 6-1: Recycling and regeneration process of recyclable composite materials

[0163] Referring to Table 16, a recyclable composite (PCC-C), a decomposition agent, and a solvent (DMF, DMSO, or NMP) are mixed. The decomposition agent includes 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), zinc oxide (ZnO), boron trifluoride (BF3), or triethylenetetramine (TETA). The mixture is then heated to 70-220°C to obtain the recyclable composite decomposition product. Referring to Table 17, the recyclable composite decomposition product is mixed with isocyanate and cured by heating to obtain a new recycled composite. The Fourier infrared spectrum of the new recycled composite matches the characteristic peaks of the infrared spectrum of the original recyclable composite. This confirms that the recyclable composite of the present invention has the technical effect of being fully recyclable and circularly recyclable.

[0164] Table 16 JPEG2025532583000029.jpg58163

[0165] Table 17 JPEG2025532583000030.jpg57163

[0166] Example 7: Preparation of recyclable benzoxazine resin (PCC-BZ)

[0167] In this example, various recyclable benzoxazine resins (PCC-BZ) were produced with reference to the compositions in Table 18. Specifically, the compositions shown in Table 18 were added to isopropanol, and the temperature was raised to reflux for three days until the reaction was complete. The isopropanol was then removed. The resulting rubbery product was dissolved in chloroform and washed three times with a 1N aqueous solution of sodium hydroxide. Finally, it was dried over anhydrous magnesium sulfate. Fourier transform infrared spectroscopy of the product revealed a peak at 1215 cm -1 , 1030cm -1 and 960 cm -1 The absorption peak was observed at 3300-3400 m, indicating that the product has a typical benzoxazine structure. After the product is cured, a recyclable benzoxazine resin is obtained. Fourier transform infrared spectroscopy analysis results (FTIR (KBr)): 3300-3400 m -1 (-COONH), 1715cm -1 (-C=O(urethane), 1215 cm -1 (asymmetric stretching COC), 1030cm -1 (symmetric stretching of COC), 930-960cm -1 (benzoxazine).

[0168] Table 18 JPEG2025532583000031.jpg120165MDI: Diphenylmethane diisocyanate PTMEG2000: Polytetramethylene ether glycol PCDL2000: Polycarbonate diol

[0169] Example 7-1: Recyclable benzoxazine resin recycling process

[0170] Referring to Table 19, recyclable benzoxazine (BZ) resin (PCC-BZ), a decomposing agent, and a solvent (DMF, DMSO, or NMP) are mixed. The decomposing agent includes 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), zinc oxide (ZnO), boron trifluoride (BF3), or triethylenetetramine (TETA). The mixture is then heated to 70-220°C to obtain the recyclable benzoxazine (BZ) resin decomposition product. Referring to Table 20, the benzoxazine (BZ) resin decomposition product is mixed with the reagents listed in Table 20 and cured by heating to obtain a new recycled benzoxazine (BZ) resin. The Fourier infrared spectrum of the new recycled benzoxazine (BZ) resin matches the characteristic peaks of the infrared spectrum of the original recyclable benzoxazine (BZ) resin. This confirms the technical effect that the recyclable benzoxazine (BZ) resin of the present invention is fully recyclable and can be cyclically regenerated.

[0171] Table 19 JPEG2025532583000032.jpg48161

[0172] Table 20 JPEG2025532583000033.jpg79163

[0173] Example 8: Method for producing aqueous dispersions of recyclable thermoset resins (PCC-BZ, PCC-PF, PCC-PMMA, PCC-Bis-GMA, PCC-Bis-MA, PCC-PU, PCC-PUF, or PCC-E)

[0174] First, a recyclable thermosetting resin (e.g., PCC-BZ, PCC-PF, PCC-PMMA, PCC-Bis-GMA, PCC-Bis-MA, PCC-PU, PCC-PUF, or PCC-E) of the copolymer (PCC) of the present invention is dissolved in a polar solvent (MEK or THF), and an emulsifier (e.g., Jeffamine M2070, M1000, or ED2003) is added. The mixture is stirred (2000 rpm) for 1 hour. The weight ratio of the copolymer (PCC), emulsifier, and solvent (MEK) is 20:3:17. Next, deionized water is added at a constant rate (1 g / min). The addition is stopped when the weight ratio of water to oil (non-aqueous medium) exceeds 0.5, resulting in an aqueous dispersion containing the recyclable thermosetting resin. The aqueous dispersion of the recyclable thermosetting resin is then distilled under reduced pressure until the solids content is 5-70 wt%. The corresponding recyclable thermosetting resin structure is obtained by curing or coating and drying. The characteristic peaks of the obtained corresponding structure are analyzed by Fourier transform infrared spectroscopy. FTIR (cm -1 , KBr): 3300-3400 cm -1 (-COONH);1715cm -1 (-C=O(urethane); 1215cm -1 (asymmetric stretching of COC);1030cm -1 (symmetric stretching of COC), 930-960cm -1 (benzoxazine); 1015-1050cm -1 ;956(Si-OR);800cm -1 [-Si-O-Si-, silica group]);1470cm -1 (methylene of PF resins);1600-1680cm -1 (-C=C(acrylic)); 1600-1680cm -1 (-C=C(acrylic));913cm -1 (oxirane).

Claims

1. 1. An additive for recycling thermosetting materials, comprising a copolymer, the copolymer comprising at least one urethane group and at least one carbonate group and / or at least one urea group, and the copolymer has a number average molecular weight in the range of 100-50,000 Da.

2. 2. The additive for recycling thermosetting materials according to claim 1, wherein the copolymer is a (urethane-carbonate) copolymer, a (urethane-urea) copolymer, a (carbonate-urea) copolymer, a (urethane-carbonate-urea) copolymer, or a combination thereof.

3. The additive for recycling thermosetting materials according to claim 1, characterized in that the urethane group has a structure shown in formula (1) or formula (2). R １ is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a polyether group having a molecular weight of 50 to 10,000, or a polysilyl ether group having a molecular weight of 50 to 10,000, R ２ is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, an alkylphenyl group having 7 to 20 carbon atoms, or an alkylphenol group having 6 to 20 carbon atoms, R ３ is a hydroxy group, an amine group, a carbonyl group, a carboxylic acid group, an ester group, or an amide group, X is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a polyether group having a molecular weight of 50 to 10,000, or a polysilyl ether group having a molecular weight of 50 to 10,000; and n is an integer from 1 to 10.

4. 2. The additive for recycling thermosetting materials according to claim 1, wherein the carbonate group has a structure shown in formula (3): R ２ is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, an alkylphenyl group having 7 to 20 carbon atoms, or an alkylphenol group having 6 to 20 carbon atoms.

5. 2. The additive for recycling thermosetting materials according to claim 1, wherein the urea group has a structure shown in formula (4): R １ is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a polyether group having a molecular weight of 50 to 10,000, or a polysilyl ether group having a molecular weight of 50 to 10,000; R ３ is a hydroxy group, an amine group, a carbonyl group, a carboxylic acid group, an ester group, or an amide group, X is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a polyether group having a molecular weight of 50 to 10,000, or a polysilyl ether group having a molecular weight of 50 to 10,000; and n is an integer from 1 to 10.

6. 1. A recyclable thermosetting composition comprising a copolymer and a thermosetting material, the copolymer comprising at least one urethane group and at least one carbonate group and / or at least one urea group, and the weight percentage of the copolymer is 0.1-85 wt. %, based on the total weight of the recyclable thermosetting composition.

7. 7. The recyclable thermosetting composition of claim 6, wherein the copolymer is a urethane-carbonate copolymer, a urethane-urea copolymer, a carbonate-urea copolymer, a urethane-carbonate-urea copolymer, or a combination thereof.

8. 7. The recyclable thermosetting composition of claim 6, wherein the copolymer has a number average molecular weight range of 100-50,000 Da.

9. 7. The recyclable thermosetting composition of claim 6, wherein the thermosetting material comprises polyurethane, polyurethane foam material, epoxy resin, phenolic resin, reinforced composite material, benzoxazine resin, acrylic resin, or combinations thereof.

10. 7. The recyclable thermosetting composition of claim 6, wherein the urethane group has a structure shown in formula (1) or formula (2). R １ is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a polyether group having a molecular weight of 50 to 10,000, or a polysilyl ether group having a molecular weight of 50 to 10,000, R ２ is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, an alkylphenyl group having 7 to 20 carbon atoms, or an alkylphenol group having 6 to 20 carbon atoms, R ３ is a hydroxy group, an amine group, a carbonyl group, a carboxylic acid group, an ester group, or an amide group, X is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a polyether group having a molecular weight of 50 to 10,000, or a polysilyl ether group having a molecular weight of 50 to 10,000; and n is an integer from 1 to 10.

11. 7. The recyclable thermosetting composition of claim 6, wherein the carbonate group has the structure shown in formula (3): R ２ is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, an alkylphenyl group having 7 to 20 carbon atoms, or an alkylphenol group having 6 to 20 carbon atoms.

12. 7. The recyclable thermosetting composition of claim 6, wherein the urea group has the structure shown in formula (4): R １ is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a polyether group having a molecular weight of 50 to 10,000, or a polysilyl ether group having a molecular weight of 50 to 10,000, R ３ is a hydroxy group, an amine group, a carbonyl group, a carboxylic acid group, an ester group, or an amide group, X is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a polyether group having a molecular weight of 50 to 10,000, or a polysilyl ether group having a molecular weight of 50 to 10,000; and n is an integer from 1 to 10.

13. 1. A process for recycling waste thermosetting materials, comprising: providing a mixture, the mixture comprising at least one copolymer, at least one processing aid, and at least one waste thermosetting material, the copolymer having at least one urethane group, at least one carbonate group, and / or at least one urea group, the weight percentage of the copolymer being 0.1-85 wt. %, based on the total weight of the mixture; heating the mixture to 50-220°C to obtain a product, the product comprising inorganic and organic materials; conducting a process to separate the inorganic matter and the organic matter, the process comprising extraction, crystallization, distillation, filtration, or a combination thereof, and the organic matter comprising relatively high molecular weight organic compounds and relatively low molecular weight organic compounds; and performing a second process to separate the relatively high molecular weight organic compounds from the relatively low molecular weight organic compounds, the second process comprising extraction, crystallization, distillation, filtration, or a combination thereof.

14. 14. The process for recycling waste thermosetting materials according to claim 13, wherein the copolymer is a (urethane carbonate) copolymer, a (urethane-urea) copolymer, a (carbonate-urea) copolymer, a (urethane-carbonate-urea) copolymer, or a combination thereof.

15. The process for recycling waste thermosetting materials according to claim 13, wherein the number average molecular weight range of the copolymer is 100-50,000 Da.

16. 14. The recycling manufacturing process of waste thermosetting materials of claim 13, wherein the thermosetting materials include polyurethane, polyurethane foam material, epoxy resin, phenolic resin, reinforced composite material, benzoxazine resin, acrylic resin, or combinations thereof.

17. The process for recycling waste thermosetting materials according to claim 13, characterized in that the urethane group has a structure shown in formula (1) or formula (2). R １ is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a polyether group having a molecular weight of 50 to 10,000, or a polysilyl ether group having a molecular weight of 50 to 10,000, R ２ is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, an alkylphenyl group having 7 to 20 carbon atoms, or an alkylphenol group having 6 to 20 carbon atoms, R ３ is a hydroxy group, an amine group, a carbonyl group, a carboxylic acid group, an ester group, or an amide group, X is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a polyether group having a molecular weight of 50 to 10,000, or a polysilyl ether group having a molecular weight of 50 to 10,000; and n is an integer from 1 to 10.

18. The process for recycling waste thermosetting materials according to claim 13, characterized in that the carbonate group has the structure shown in formula (3). R ２ is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a phenyl group, an alkylphenyl group having 7 to 20 carbon atoms, or an alkylphenol group having 6 to 20 carbon atoms.

19. The process for recycling waste thermosetting materials according to claim 13, characterized in that the urea group has the structure shown in formula (4). R １ is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a polyether group having a molecular weight of 50 to 10,000, or a polysilyl ether group having a molecular weight of 50 to 10,000, R ３ is a hydroxy group, an amine group, a carbonyl group, a carboxylic acid group, an ester group, or an amide group, X is a linear or branched alkyl group having 2 to 20 carbon atoms, a cyclic alkyl group having 3 to 8 carbon atoms, a polyether group having a molecular weight of 50 to 10,000, or a polysilyl ether group having a molecular weight of 50 to 10,000; and n is an integer from 1 to 10.

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