Glassy polymer materials, methods of making and using the same

Abstract

The application provides a glass-like polymer material and a preparation method and application thereof. The glass-like polymer material comprises a plurality of first repeating units and a plurality of second repeating units, the structure of the first repeating unit is R0 is at least one selected from an alkylene group, an alkenylene group, an alkynylene group, an arylene group, an aralkylene group, a heteroarylene group, a heteroaralkylene group and an alicyclic group; and the second repeating unit comprises at least one of and. The glass-like polymer material has excellent mechanical properties, good biodegradability, can reduce pollution to the ecological environment, and is beneficial to wide application of the glass-like polymer material.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of high polymer materials, in particular to a glass-like high polymer material and a preparation method and application thereof. BACKGROUND

[0002] At present, the glass-like high polymer material has the characteristics of thermosetting material and thermoplastic material, has a stable crosslinking structure and excellent mechanical properties, and can realize multiple processing injection molding and shape memory self-repair. The glass-like high polymer material is mostly made of fossil resources, and after multiple uses, the low-temperature thermosetting and high-temperature thermoplastic properties make the glass-like high polymer material difficult to degrade, causing environmental pollution. In the related technology, bio-based materials can be used to replace fossil resources to prepare the glass-like high polymer material, and the glass-like high polymer material can be degraded by using specific acid or alkali solvents, but the mechanical strength of the glass-like high polymer material decreases, the preparation cost is too high, and it is difficult to apply in industry. Therefore, a glass-like high polymer material with high mechanical strength and more green and environmentally friendly degradation is needed to reduce pollution to the ecological environment and realize industrialized use. SUMMARY

[0003] In view of this, the present application provides a glass-like high polymer material and a preparation method and application thereof. The glass-like high polymer material has high mechanical strength, does not require specific acid or alkali solvents, realizes biodegradation, reduces pollution to the ecological environment, and is conducive to the application of the glass-like high polymer material.

[0004] In a first aspect, the present application provides a glass-like high polymer material, which comprises a plurality of first repeating units and a plurality of second repeating units, the structure of the first repeating unit is R0 is selected from at least one of alkylene, alkenylene, alkynylene, arylene, arylenealkylene, heteroarylene, heteroarylenealkylene and alicyclylene; and the second repeating unit comprises at least one of the following.

[0005] Optionally, the second repeating unit is

[0006] Optionally, the number of repetitions of the first repeating unit is 50-200.

[0007] Optionally, the number of repetitions of the second repeating unit is 100-400.

[0008] Optionally, the number ratio of the first repeating unit to the second repeating unit is 1:(0.5-8).

[0009] Optionally, the number average molecular weight of the glass-like high polymer material is 20000-80000.

[0010] The glass-like polymer material provided by the application has excellent mechanical strength, biodegradability, and reduced damage to the ecological environment, and is beneficial to the use of the glass-like polymer material.

[0011] In a second aspect, the application provides a preparation method of a glass-like polymer material, comprising:

[0012] The polymer and the polyisocyanate cross-linking agent are mixed to perform a cross-linking reaction, to obtain the glass-like polymer material of the first aspect, and the repeating unit of the polymer comprises at least one of

[0013] Optionally, the molar ratio of the polymer to the polyisocyanate cross-linking agent is 1:(1-1.2).

[0014] Optionally, the polymer comprises at least one of polytrimethylene carbonate, poly2,2-dimethyltrimethylene carbonate, and a copolymer of trimethylene carbonate and 2,2-dimethyltrimethylene carbonate.

[0015] Optionally, the polyisocyanate cross-linking agent comprises at least one of hexamethylene polyisocyanate, diphenylmethane polyisocyanate, and dicyclohexylmethane polyisocyanate.

[0016] Optionally, the preparation of the copolymer of trimethylene carbonate and 2,2-dimethyltrimethylene carbonate comprises:

[0017] The trimethylene carbonate, the 2,2-dimethyltrimethylene carbonate, a copolymerization catalyst, and an initiator are mixed to form a reaction solution, and the copolymer of trimethylene carbonate and 2,2-dimethyltrimethylene carbonate is prepared through a copolymerization reaction.

[0018] Optionally, the copolymerization catalyst comprises at least one of 2-ethyltin acetate and aluminum isopropoxide.

[0019] Optionally, the structure of the initiator is The R1, the R2, the R3, and the R4

[0020] are alkylene groups, the R 5 , the R 6 , the R 7 , and the R 8 are at least three hydroxyl groups.

[0021] Optionally, in the reaction solution, the molar ratio of the trimethylene carbonate to the 2,2-dimethyltrimethylene carbonate is 1:(0.33-3); the molar percentage of the copolymerization catalyst is 0.03%-0.1% based on the solute of the reaction solution, and the molar percentage of the initiator is 0.05%-0.2%.​

[0022] Optionally, the reaction time of the copolymerization reaction is 24-36 hours.

[0023] Optionally, the cross-linking reaction is followed by drying, the temperature of the drying is 65-75℃, and the time of the drying is 48-60 hours.

[0024] The preparation method of the glass-like polymer material provided in the application is novel, the preparation process is simple, and the prepared product has excellent performance.

[0025] In a third aspect, the application provides a structural member, the material of the structural member comprising the glass-like polymer material of the first aspect or the glass-like polymer material prepared by the preparation method of the second aspect.

[0026] The structural member provided in the application has excellent mechanical properties, is environmentally friendly, and is conducive to the wide application of the structural member. DETAILED DESCRIPTION

[0027] The technical solutions in the embodiments of the application will be described clearly and completely below. Obviously, the described embodiments are only some of the embodiments of the application, but not all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative work fall within the scope of protection of the application.

[0028] The application provides a glass-like polymer material, which comprises a plurality of first repeating units and a plurality of second repeating units, the structure of the first repeating unit is The R0 is selected from at least one of alkylene, alkenylene, alkynylene, arylene, arylenealkylene, heteroarylene, heteroarylenealkylene and alicyclylene; the second repeating unit comprises at least one of the following.

[0029] The glass-like polymer material of the application belongs to polycarbonate materials, and comprises the first repeating unit and the second repeating unit. The first repeating unit plays a cross-linking role and enhances the mechanical properties of the glass-like polymer material. The glass-like polymer material behaves as a thermosetting material with excellent mechanical strength at 200℃ and below, and the first repeating unit is decomposed at more than 200℃, so that the glass-like polymer material behaves as a thermoplastic material. The carbon-nitrogen bond is broken, the repeating units are decrosslinked, the glass-like polymer material is converted from thermosetting material to thermoplastic material, and after the temperature drops (at 200 DEG C or below), the carbon-nitrogen bond is restored, the repeating units are recrosslinked, and the glass-like polymer material is converted from thermosetting material. The second repeating unit has good mechanical properties and biodegradability, so that the glass-like polymer material is biodegradable without the need for external acid or base solvent, reducing environmental pollution, and the glass-like polymer material has high mechanical strength, which is conducive to the use of the glass-like polymer material.

[0030] In the present application, R0 in the first repeating unit includes at least one of alkylene, alkenylene, alkynylene, arylene, arylenealkyl, heteroarylene, heteroarylenealkyl and alicyclylene. In an embodiment of the present application, R0 has an isocyanate group, and the isocyanate group can be connected to any one of alkylene, alkenylene, alkynylene, arylene, arylenealkyl, heteroarylene, heteroarylenealkyl and alicyclylene.

[0031] In an embodiment of the present application, when R0 is alkylene, the alkylene is a divalent saturated group formed by removing one hydrogen atom from an alkyl group, and the number of carbon atoms in the alkylene is 1-8. Specifically, the number of carbon atoms in the alkylene can be but is not limited to 1, 2, 3, 4, 5, 6, 7 or 8. Exemplarily, the alkylene can be but is not limited to -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2- or -CH2CH2CH2CH2CH2CH2-, etc. In an embodiment of the present application, R0 can be -CH2CH2CH2CH2CH2CH2-. In another embodiment of the present application, R0 can also be

[0032] In an embodiment of the present application, when R0 is arylene, the arylene is a divalent aromatic group, and the number of carbon atoms in the arylene is 6-30. Specifically, the number of carbon atoms in the arylene can be but is not limited to 6, 10, 12, 14, 18, 22, 24, 26 or 30, etc. Exemplarily, the arylene can be but is not limited to phenylene, naphthylene, anthrylene, tetracenylene, pentacenylene or tetrahydronaphthylene, etc. In an embodiment of the present application, R0 can be phenylene.

[0033] In an embodiment of the present application, when R0 is arylenealkyl, the arylenealkyl is a composite group formed by connecting arylene and alkylene, and the number of carbon atoms in the arylenealkyl is 7-40. Specifically, the number of carbon atoms in the arylenealkyl can be but is not limited to 7, 8, 9, 10, 15, 18, 20, 25, 26, 30, 32, 37 or 40, etc. Exemplarily, the arylenealkyl can be but is not limited to Etc. In one embodiment of this application, R0 can be...

[0034] In one embodiment of this application, when R0 is an alicyclic group, the alicyclic group is a divalent alicyclic group, and the number of carbon atoms in the alicyclic group is 3-30. Specifically, the number of carbon atoms in the alicyclic group can be, but is not limited to, 3, 5, 9, 10, 13, 15, 18, 23, 26, or 30. For example, the alicyclic group can include, but is not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, or cyclopentenyl. In one embodiment of this application, R0 can be...

[0035] In this application, the second repeating unit includes At least one of the following is used to impart biodegradability to the glass-like polymer material and to improve its mechanical properties. In this application, the second repeating unit includes... hour, The two groups can be directly connected or connected with intervals; when directly connected, the order of connection of the two groups is not limited. In one embodiment of this application, the second repeating unit can be... This can further improve the mechanical strength and biodegradability of glass-like polymer materials. In another embodiment of this application, the second repeating unit can be...

[0036] In one embodiment of this application, the glass-like polymer material further includes Among them, R1, R2, R3 and R4 are alkylene groups, and R5, R6, R7 and R8 are independently selected from hydroxyl, alkyl, alkylene and single bond.

[0037] In an embodiment of the present application, the alkylene group includes straight chain alkylene group and branched chain alkylene group. Specifically, the number of carbon atoms of the alkylene group can be, but is not limited to, 1, 2, 3 or 4. Exemplarily, the alkylene group can be, but is not limited to, methylene, ethylene, 1,3-propylene, isopropylene, butylene, 1-methylpropylene or 2-methylpropylene. In an embodiment of the present application, R1and R2may be methylene, R3and R4may be ethylene. In another embodiment of the present application, R1, R2, R3and R4may be methylene. In an embodiment of the present application, the alkyl group includes branched chain alkyl group and straight chain alkyl group. Specifically, the number of carbon atoms of the alkyl group can be, but is not limited to, 1, 2, 3 or 4. Exemplarily, the alkyl group can be, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl. In an embodiment of the present application, R5may be methyl, R6may be hydroxyl, R7may be ethylene, and R8may be single bond. In another embodiment of the present application, R5may be n-propyl, R6may be single bond, R7may be methylene, and R8may be hydroxyl. In an embodiment of the present application, R1and R5, R2and R6, R3and R7, and R4and R8are two groups connected together, and the number of carbon atoms of the two groups connected together is less than 5. For example, when the number of carbon atoms of R1is 1, the number of carbon atoms of R5may be 0, 1, 2 or 3; for example, when the number of carbon atoms of R2is 2, the number of carbon atoms of R6may be 0, 1 or 2; for example, when the number of carbon atoms of R3is 3, the number of carbon atoms of R7may be 0 or 1; for example, when the number of carbon atoms of R4is 3, the number of carbon atoms of R8may be 0 or 1.

[0038] In the present application The first repeating unit and / or the second repeating unit can be connected to the adjacent second repeating unit.

[0039] The present application does not limit the connection order, connection position and connection number of the first repeating unit, the second repeating unit and ; that is, the first repeating unit and the second repeating unit can be connected to any position on ; for example, the first repeating unit and the second repeating unit can be connected to any position of R5, R6, R7and / or R8, or can be connected to any position of R1, R2, R3and / or R4. In some embodiments, the structure of the glass-like polymer material can be as shown in formula I-1 to formula I-5:

[0040]

[0041] Wherein, a1, a2, a3, a4, a5, a6 and a7 are independently selected from integers greater than or equal to 50. Specifically, a1, a2, a3, a4, a5, a6, a7 can be, but are not limited to, integers greater than or equal to 50, 100, 150, 200, 250, 300 or 400, etc. 500, 1000, 2000 or 5000, etc. In an embodiment of the present application, a1, a2, a3, a4, a5, a6, a7 can be integers greater than or equal to 100.

[0042] In an embodiment of the present application, the number of repetitions of the first repeating unit in the glass-like polymer material is 50-200, which is beneficial to further improve the cross-linking degree of the glass-like polymer material and improve the mechanical properties of the glass-like polymer material. Specifically, the number of repetitions of the first repeating unit can be, but is not limited to, 50, 80, 100, 120, 140, 160, 180 or 200, etc. In an embodiment of the present application, the number of repetitions of the first repeating unit can be 50-80. In another embodiment of the present application, the number of repetitions of the first repeating unit can be 70-100.

[0043] In an embodiment of the present application, the number of repetitions of the second repeating unit in the glass-like polymer material is 100-400, which is beneficial to further enhance the biodegradable properties of the glass-like polymer material. Specifically, the number of repetitions of the second repeating unit can be, but is not limited to, 100, 150, 200, 250, 300, 350 or 400, etc. In an embodiment of the present application, the number of repetitions of the second repeating unit can be 150-350. In another embodiment of the present application, the number of repetitions of the second repeating unit can be 200-400.

[0044] In an embodiment of the present application, the number ratio of the first repeating unit to the second repeating unit in the glass-like polymer material is 1:(0.5-8). Specifically, the number ratio of the first repeating unit to the second repeating unit can be, but is not limited to, 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:4, 1:5, 1:7 or 1:8, etc. In an embodiment of the present application, the number ratio of the first repeating unit to the second repeating unit can be 1:2, which is beneficial to improve the comprehensive performance of the glass-like polymer material. In another embodiment of the present application, the number ratio of the first repeating unit to the second repeating unit can be 1:5.

[0045] In an embodiment of the present application, the number average molecular weight of the glass-like polymer material is 20000-80000. At this time, the number average molecular weight of the glass-like polymer material is in a suitable range, so that the glass-like polymer material has more excellent biodegradability and mechanical properties. Specifically, the number average molecular weight of the glass-like polymer material can be, but is not limited to, 20000, 25000, 30000, 40000, 50000, 60000 or 70000, etc. In an embodiment of the present application, the number average molecular weight of the glass-like polymer material can be 25000-55000. In another embodiment of the present application, the number average molecular weight of the glass-like polymer material can be 50000-80000.

[0046] The present application also provides a preparation method of a glass-like polymer material, comprising:

[0047] The polymer and the polyisocyanate crosslinking agent are mixed to perform a crosslinking reaction, so as to obtain the glass-like polymer material of any one of the above embodiments. The repeating unit of the polymer comprises at least one of In the preparation method of the glass-like polymer material provided by the present application, the polyisocyanate crosslinking agent and the polymer perform a crosslinking reaction, so as to form a glass-like polymer material with excellent mechanical strength; and the glass-like polymer material has The polymer with the repeating unit can form a glass-like polymer material with excellent biodegradability after the crosslinking reaction with the polyisocyanate crosslinking agent, which is beneficial to the use of the glass-like polymer material. At the same time, since the carbon-nitrogen bond in the polyisocyanate crosslinking agent will be broken at a temperature above 200℃, the crosslinking property is lost, and the carbon-nitrogen bond is restored at a temperature below 200℃, so that the glass-like polymer material can become a thermoplastic material at a temperature above 200℃, and the carbon-nitrogen bond is restored at a temperature below 200℃, so that the glass-like polymer material becomes a thermosetting material with excellent mechanical strength.

[0048] In the present application, the repeating unit of the polymer comprises at least one of For example, the repeating unit of the polymer can be The repeating number of the repeating units of the polymer is 100-400. Specifically, the repeating number of the repeating units of the polymer can be, but is not limited to, 100, 150, 200, 250, 300 or 400, etc. In an embodiment of the present application, the repeating number of the repeating units of the polymer can be an integer greater than 100. For example, the polymer can be, but is not limited to, at least one of polytrimethylene carbonate, poly 2,2-dimethyltrimethylene carbonate and a copolymer of trimethylene carbonate and 2,2-dimethyltrimethylene carbonate (P(TMC-co-DTC)). The above-mentioned polymers have biodegradability, which improves the biodegradability of the glass-like polymer material. In an embodiment of the present application, the polymer can be a copolymer of trimethylene carbonate and 2,2-dimethyltrimethylene carbonate, which can further improve the mechanical properties and biodegradability of the glass-like polymer material. In another embodiment of the present application, the polymer can be polytrimethylene carbonate and a copolymer of trimethylene carbonate and 2,2-dimethyltrimethylene carbonate.

[0049] In an embodiment of the present application, the preparation of the copolymer of trimethylene carbonate and 2,2-dimethyltrimethylene carbonate includes: mixing trimethylene carbonate, 2,2-dimethyltrimethylene carbonate, a copolymerization catalyst and an initiator to form a reaction solution, and preparing the copolymer of trimethylene carbonate and 2,2-dimethyltrimethylene carbonate through copolymerization. In an embodiment of the present application, the molar ratio of trimethylene carbonate to 2,2-dimethyltrimethylene carbonate in the reaction solution is 1:(0.33-3). Trimethylene carbonate and 2,2-dimethyltrimethylene carbonate have high activity, which can improve the biodegradability of the glass-like polymer material. 2,2-dimethyltrimethylene carbonate has a methyl side chain, which can improve the mechanical properties of the glass-like molecule. The glass-like polymer material prepared by the appropriate mixing ratio of trimethylene carbonate and 2,2-dimethyltrimethylene carbonate can have more excellent biodegradability and mechanical properties. Specifically, the molar ratio of trimethylene carbonate to 2,2-dimethyltrimethylene carbonate can be, but is not limited to, 1:0.33, 1:0.5, 1:0.8, 1:1, 1:1.2, 1:1.5, 1:2, 1:2.5 or 1:3, etc. In an embodiment of the present application, the molar ratio of trimethylene carbonate to 2,2-dimethyltrimethylene carbonate can be 1:(0.33-1). In another embodiment of the present application, the molar ratio of trimethylene carbonate to 2,2-dimethyltrimethylene carbonate can be 1:(1-3).

[0050] In an embodiment of the present application, the preparation of 2,2-dimethyltrimethylene carbonate comprises: dissolving neopentyl glycol, triphosgene (bis(trichloromethyl) carbonate) and monomer catalyst in anhydrous organic solvent to obtain a monomer reaction solution, and obtaining 2,2-dimethyltrimethylene carbonate by reaction. The entire process is kept anhydrous and free of active hydride, and high-purity 2,2-dimethyltrimethylene carbonate can be prepared by the above preparation process, which is beneficial to improve the degradability and mechanical strength of the glass-like polymer material. In an embodiment of the present application, the monomer catalyst comprises a mixture of 4-N,N-dimethylpyridine and triethylamine, and the anhydrous organic solvent can be an anhydrous chloroalkane solvent. For example, the organic solvent can be anhydrous dichloromethylbenzene.

[0051] In an embodiment of the present application, in the monomer reaction solution, the molar percentage of neopentyl glycol is 45%-55%, the molar percentage of triphosgene is 45%-55%, and the molar percentage of the monomer catalyst is 0.1%-0.5%. Specifically, the molar percentage of neopentyl glycol can be, but is not limited to, 45%, 46%, 48%, 49%, 50%, 51%, 53% or 55%, etc.; the molar percentage of triphosgene can be, but is not limited to, 45%, 46%, 48%, 49%, 50%, 51%, 53% or 55%, etc.; and the molar percentage of the monomer catalyst can be, but is not limited to, 0.1%, 0.2%, 0.25%, 0.3%, 0.4% or 0.5%, etc. In an embodiment of the present application, in the monomer reaction solution, the molar percentage of neopentyl glycol can be 50%, the molar percentage of triphosgene can be 50%, and the molar percentage of the monomer catalyst can be 0.5%. The monomer catalyst comprises a mixture of 4-N,N-dimethylpyridine and triethylamine in a molar ratio of 1:1.

[0052] In an embodiment of the present application, anhydrous dichloromethane is obtained by mixing dichloromethane with sodium metal, condensing and refluxing, and collecting the distillate. The sodium metal can remove water and active hydrogen-containing components in the dichloromethane to obtain anhydrous dichloromethane. Specifically, 350 mL of dichloromethane can be measured by a graduated cylinder and poured into a 500 mL distillation flask. An appropriate amount of sodium metal block is cut into thin wires and placed in the flask. After standing for 1 h of air condensation and reflux, distillation is started. When the temperature of the thermometer at the branch port is 40°C, the distillate is collected and placed in a desiccator.

[0053] In an embodiment of the present application, triethylamine is mixed with phthalic anhydride, and after condensation reflux and distillation, the fraction is collected to obtain anhydrous triethylamine. The use of phthalic acid glycoside to remove water, ethylamine and diethylamine and other components with active hydrogen in triethylamine is conducive to the use of monomer catalyst. Specifically, 150 mL of triethylamine can be measured by a measuring cylinder, poured into a 250 mL distillation flask, and an appropriate amount of phthalic anhydride is added. After air condensation reflux for 3 hours, distillation is started, and when the temperature of the thermometer at the branch port is 90°C, the fraction is collected and placed in a dryer.

[0054] In the present application, the preparation process of 2,2-dimethyltrimethylene carbonate is as follows:

[0055]

[0056] In an embodiment of the present application, the molar percentage of the copolymerization catalyst is 0.03%-0.1% based on the solute of the reaction solution. The copolymerization catalyst can be but is not limited to at least one of 2-ethyltin acetate and aluminum isopropyl alcohol. Specifically, the molar percentage of the copolymerization catalyst can be but is not limited to 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09% or 0.1%, etc. In an embodiment of the present application, the copolymerization catalyst can be 2-ethyltin acetate, and the molar percentage of the copolymerization catalyst can be 0.05%.

[0057] In an embodiment of the present application, the molar percentage of the initiator is 0.05%-0.2% based on the solute of the reaction solution. Specifically, the molar percentage of the initiator can be but is not limited to 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.12%, 0.15% or 0.2%, etc. In an embodiment of the present application, the molar percentage of the initiator can be 0.1%.

[0058] In an embodiment of the present application, the structure of the initiator is R1, R2, R3 and R4 are alkylene groups, and R 5 , R 6 , R 7 and R 8 at least three of which are hydroxyl groups. R1, R2, R3 and R4 can be independently selected from alkylene groups with 1-4 carbon atoms. Specifically, the number of carbon atoms of the alkylene group can be but is not limited to 1, 2, 3 or 4, etc. 5 , R 6 , R 7 and R 8 at least three of which are hydroxyl groups. R1, R2, R3 and R4 can be independently selected from alkylene groups with 1-4 carbon atoms. Specifically, the number of carbon atoms of the alkylene group can be but is not limited to 1, 2, 3 or 4, etc. 5 , R 6 , R 7 and R 8independently selected from alkyl and hydroxyl; that is, R 5 , R 6 , R 7 , and R 8 may all be hydroxyl, or three of them can be hydroxyl and one can be alkyl. In some embodiments, R 5 , R 6 , and R 7 may be hydroxyl and R 8 may be methyl; in some embodiments, R 5 , R 6 , and R 8 may be hydroxyl and R 7 may be propyl; in some embodiments, R 5 , R 6 , R 7 , and R 8 may all be hydroxyl, further increasing the activity of the initiator. Exemplary structures of the initiator can be shown in Formula II-1 to Formula II-6:

[0059]

[0060] In an embodiment of the present application, the initiator can be In this case, the preparation process of the copolymer of trimethylene carbonate and 2,2-dimethyltrimethylene carbonate is as follows:

[0061]

[0062] wherein at least one of M1, M2, and M3 is n is an integer greater than or equal to 100. Specifically, M1, M2, and M3 are selected from at least one of hydroxyl and Exemplarily, M1 and M2 are M3 is hydroxyl.

[0063] R1and R 5 , R2and R 6 , R3and R 7 , and R4and R 8 are two groups connected together. In an embodiment of the present application, the sum of the number of carbon atoms of the two groups connected together in the initiator is less than 5, which is beneficial to increase the activity of the initiator and promote the copolymerization reaction. For example, when the number of carbon atoms of R1is 1, the number of carbon atoms of R 5 may be 0, 1, 2, or 3; for example, when the number of carbon atoms of R2is 2, the number of carbon atoms of R 6 may be 0, 1, or 2; for example, when the number of carbon atoms of R3is 3, the number of carbon atoms of R 7 may be 0 or 1; for example, when the number of carbon atoms of R4is 3, the number of carbon atoms of R 8 may be 0 or 1.

[0064] In an embodiment of the present application, the solvent of the copolymerization reaction solution needs to meet the following conditions: the boiling point is higher than 150°C (e.g., 150°C-190°C), the solvent can dissolve the polymerization monomer and does not react with the polymer and the polymerization monomer. Specifically, the solvent of the copolymerization reaction solution can be, but is not limited to, anhydrous toluene and xylene. In an embodiment of the present application, the solvent of the copolymerization reaction solution can be anhydrous toluene.

[0065] In an embodiment of the present application, the reaction time of the copolymerization reaction is 24h-36h. Specifically, the reaction time of the copolymerization reaction can be, but is not limited to, 24h, 26h, 28h, 29h, 30h, 32h, 34h or 36h, etc. In an embodiment of the present application, the reaction time of the copolymerization reaction can be 24h-30h. In another embodiment of the present application, the reaction time of the copolymerization reaction can be 26h-36h.

[0066] In an embodiment of the present application, the reaction temperature of the copolymerization reaction is 150°C-190°C. Specifically, the reaction temperature of the copolymerization reaction can be, but is not limited to, 150°C, 160°C, 165°C, 170°C, 175°C, 180°C or 190°C, etc. In an embodiment of the present application, the reaction temperature of the copolymerization reaction is 178°C-182°C. In another embodiment of the present application, the reaction temperature of the copolymerization reaction is 165°C-190°C.

[0067] In an embodiment of the present application, after the copolymerization reaction, washing is further included. The washing solution of the washing can be, but is not limited to, one or more of dichloromethane solution, a mixed solution of ethanol and n-hexane with a volume ratio of 1:1, and a mixed solution of ethanol and diethyl ether with a volume ratio of 1:1. In an embodiment of the present application, the washing solution can be the dichloromethane solution and the mixed solution of ethanol and n-hexane with a volume ratio of 1:1. In another embodiment of the present application, the washing solution can be the mixed solution of ethanol and diethyl ether.

[0068] In an embodiment of the present application, after the copolymerization reaction, recrystallization is performed, which is beneficial to obtain a copolymer crystal of trimethylene carbonate and 2,2-dimethyltrimethylene carbonate with high purity. The recrystallization reagent of the copolymer can be, but is not limited to, at least one of toluene, dichloromethane and ethyl acetate. In an embodiment of the present application, the recrystallization reagent of the copolymer can be toluene. In another embodiment of the present application, the recrystallization reagent of the copolymer can be ethyl acetate.

[0069] In the present application, the polyisocyanate-based crosslinking agent includes at least two isocyanate groups; the structure of the polyisocyanate-based crosslinking agent is R0is selected from at least one of alkylene, alkenylene, alkynylene, arylene, aralkylene, heteroarylene, heteroaralkylene, and cycloaliphatic. When the polyisocyanate-based crosslinking agent includes three or more isocyanate groups, one or more isocyanate groups can also be included in the first repeating unit R0, i.e., alkylene, alkenylene, alkynylene, arylene, aralkylene, heteroarylene, heteroaralkylene, and cycloaliphatic having an isocyanate group.

[0070] The carbon-nitrogen bond in the polyisocyanate-based crosslinking agent improves the thermoplasticity and thermoset of the glass-like polymer material. Specifically, the polyisocyanate-based crosslinking agent can be, but is not limited to, hexamethylene diisocyanate, diphenyl methane diisocyanate, or dicyclohexyl methane diisocyanate. In an embodiment of the present application, when R0is -CH2CH2CH2CH2CH2CH2-, the diisocyanate-based crosslinking agent can be hexamethylene diisocyanate. In another embodiment of the present application, when R0is , the diisocyanate-based crosslinking agent can be dicyclohexyl methane diisocyanate.

[0071] In an embodiment of the present application, the molar ratio of the polymer and the polyisocyanate-based crosslinking agent is 1:1-1.2. Specifically, the molar ratio of the polymer and the polyisocyanate-based crosslinking agent can be, but is not limited to, 1:1, 1:1.05, 1:1.08, 1:1.1, 1:1.12, 1:1.15, 1:1.17, or 1:1.2, etc. In an embodiment of the present application, the molar ratio of the polymer and the polyisocyanate-based crosslinking agent can be 1:1.1, the polyisocyanate-based crosslinking agent is slightly more than the polymer, and a glass-like polymer material with excellent performance can be obtained, and the preparation cost is saved. In another embodiment of the present application, the molar ratio of the polymer and the polyisocyanate-based crosslinking agent can be 1:1.15.

[0072] In an embodiment of the present application, after the crosslinking reaction is completed, the mixture of the polymer and the polyisocyanate-based crosslinking agent is poured into a mold, and dried after standing for 24-48 h. The material of the mold should not react with the hydroxyl and cyanate groups, for example, non-metal, non-oxidizing, high-temperature-resistant materials, and the specific material of the mold can be polytetrafluoroethylene. The standing time can be, but is not limited to, 24 h, 25 h, 28 h, 30 h, 35 h, 40 h, 45 h, or 48 h, etc. In an embodiment of the present application, the standing time can be 24 h.

[0073] In an embodiment of the present application, the drying temperature is 65-75°C, and the drying time is 48-60h. A suitable drying temperature and time can result in a glass-like polymer material with good film-forming property. Specifically, the drying temperature can be, but is not limited to, 65°C, 67°C, 68°C, 69°C, 70°C, 72°C or 75°C, and the drying time can be 48h, 49h, 50h, 51h, 53h, 55h, 56h, 59h or 60h. In an embodiment of the present application, the drying temperature is 70-75°C, and the drying time is 48-55h. In another embodiment of the present application, the drying temperature is 65-70°C, and the drying time is 50-60h.

[0074] The present application also provides a structural member, the material of which comprises the glass-like polymer material of any of the above embodiments. The structural member comprising the glass-like polymer material can replace the existing polymer material structural member, improve the mechanical properties of the product, reduce the pollution to the ecological environment, and facilitate the wide application of the glass-like material.

[0075] The effects of the technical solutions of the present application are further described below through specific examples.

[0076] Example 1

[0077] Trimethylene carbonate (0.51g, 5.0mmol), 2,2-dimethyltrimethylene carbonate (0.65g, 5.0mmol), a copolymerization catalyst (0.05% Sn(Oct)2 by mole) and an initiator (0.1% trimethylolpropane by mole) were mixed to form a reaction solution in dry toluene (0.1mol / L), and a copolymerization reaction was performed in a constant-temperature oil bath at 180°C for 24h. After the reaction, dichloromethane (5ml), ethanol (50ml) and n-hexane (50ml) were added in sequence, and the obtained solid was washed with a 1:1 mixture of ethanol and diethyl ether to obtain a copolymer of trimethylene carbonate and 2,2-dimethyltrimethylene carbonate.

[0078] The copolymer of trimethylene carbonate and 2,2-dimethyltrimethylene carbonate and hexamethylene diisocyanate were dissolved in anhydrous dichloromethane to form a saturated solution for crosslinking reaction. After complete mixing, the obtained solution was poured into a polytetrafluoroethylene mold with a length of 60mm, a width of 40mm and a height of 0.5mm, and the mold was left to stand for 24h to evaporate the solvent. Next, the colorless reaction mixture was placed in an oven at 70°C for 48h to obtain a glass-like polymer material, which was in the form of a film.

[0079] Example 2

[0080] The difference from Example 1 is that the molar ratio of triethylene carbonate to 2,2-dimethyl triethylene carbonate is 3:1.

[0081] Example 3

[0082] The difference from Example 1 is that the molar ratio of triethylene carbonate to 2,2-dimethyl triethylene carbonate is 1:3.

[0083] Example 4

[0084] The difference from Example 1 is that the molar ratio of triethylene carbonate to 2,2-dimethyl triethylene carbonate is 1:5.

[0085] Example 5

[0086] The difference from Example 1 is that the molar ratio of triethylene carbonate to 2,2-dimethyl triethylene carbonate is 1:0.1.

[0087] Example 6

[0088] The difference from Example 1 is that the molar ratio of the copolymerization catalyst is 0.1%, and the molar percentage of the initiator is 0.05%.

[0089] Example 7

[0090] The difference from Example 1 is that the molar ratio of the copolymerization catalyst is 0.03%, and the molar percentage of the initiator is 0.2%.

[0091] Example 8

[0092] The difference from Example 1 is that the polymer is poly triethylene carbonate.

[0093] Example 9

[0094] The difference from Example 1 is that the polymer is poly 2,2-dimethyl triethylene carbonate.

[0095] Comparative Example 1

[0096] In a vacuum distillation cooling reflux reaction device, the polyol modified cardanol and tert-butyl acetoacetate were mixed in a molar ratio of 1:3, stirred at 130°C for 12h, distilled to remove n-butanol solution, and then vacuum distilled at 140°C to remove excess tert-butyl acetoacetate, to obtain a light brown liquid, which is acetoacetate cardanol. The acetoacetate cardanol (1.00g, 1.10mmol) and curing agent 4,4-diaminocyclohexyl methane (0315g, 1.49mmol) were mixed in a weighing bottle, stirred at room temperature for 1min. Then the mixture was poured into a flat rectangular glass container, and the container was transferred to an oven and placed at 30°C for 10h and at 80°C for 5h. After the sample was completely cured, a cardanol-based glassy high polymer material with an ethylene amine acetate bond was obtained.

[0097] Comparative Example 2

[0098] The difference from Example 1 is that the copolymer of trimethylene carbonate and 2,2-dimethyl trimethylene carbonate prepared in Example 1 is directly used.

[0099] Comparative Example 3

[0100] The difference from Example 1 is that the copolymer of trimethylene carbonate and 2,2-dimethyl trimethylene carbonate prepared in Example 2 is directly used.

[0101] Comparative Example 4

[0102] The difference from Example 1 is that the copolymer of trimethylene carbonate and 2,2-dimethyl trimethylene carbonate prepared in Example 3 is directly used.

[0103] Performance test

[0104] The tensile properties of the samples prepared in Examples 1-9 and Comparative Examples 1-4 above were tested according to ASTM D638; the sample gauge length was 50mm, the load loading speed was 5mm / min, and continuous loading was performed until the sample was destroyed, and the tensile strength of the sample was obtained. The sample was heated to 200°C and then injection molded, and the tensile properties were tested again to characterize the dynamic crosslinking structure, and the test results are shown in Table 1.

[0105] The biodegradability of the samples prepared in Examples 1-9 and Comparative Example 1 above was tested according to GB / T19277, and the degradation time was 6 months, and the test results are shown in Table 2.

[0106] The number average molecular weight of the samples prepared in the above Examples 1-9 and Comparative Examples 1-4 was determined by gel permeation chromatography (GPC) using an Agilent G7820B, 1260 Infinity II High Temperature GPC SYSTEM, and the test results are shown in Table 3.

[0107] Table 1: Tensile property test

[0108]

[0109] Table 2: Biodegradability test

[0110] Biodegradability (%) Degree of disintegration (%) Example 1 64 91 Example 2 71 93 Example 3 52 88 Example 4 46 79 Example 5 76 95 Example 6 42 62 Example 7 79 98 Example 8 80 97 Example 9 45 77 Comparative Example 1 Comparative Example 2 43 72

[0111] Table 3: Number average molecular weight test

[0112]

[0113]

[0114] In the tensile property results shown in Table 1, the glass-like polymer materials of Examples 1-9 and Comparative Example 1 are both thermosetting and thermoplastic, and the tensile strength and elongation at break are basically unchanged after melt secondary injection molding. Comparative Examples 2-4 show that the mechanical properties, especially the tensile strength, of the degradable material (polycarbonate) without crosslinking are lower than those of the glass-like polymer material prepared after crosslinking. The tensile strength of the glass-like polymer material obtained in this application is much higher than that of Comparative Example 1, indicating that the mechanical properties of the glass-like polymer material prepared from bio-based material are lower than those of the glass-like polymer material prepared from degradable material (polycarbonate). As can be seen from Experimental Examples 1-5 and Examples 8-9, 2,2-dimethyltrimethylene carbonate can improve the mechanical properties of the glass-like polymer material, and as the proportion of 2,2-dimethyltrimethylene carbonate increases and the proportion of trimethylene carbonate decreases, the tensile strength and elongation at break of the glass-like polymer material gradually increase.

[0115] In the biodegradability results shown in Table 2, the glass-like polymer materials of Examples 1-9 and Comparative Example 1 are all biodegradable. In Examples 1-9, the biodegradability of the glass-like polymer material prepared from degradable material (polycarbonate) is higher than that of the glass-like polymer material prepared from bio-based material of Comparative Example 1, and as the proportion of 2,2-dimethyltrimethylene carbonate in the glass-like polymer material decreases and the proportion of trimethylene carbonate increases, the biodegradation rate and disintegration degree of the glass-like polymer material gradually increase, which is contrary to the mechanical property law of the glass-like polymer material.

[0116] The number average molecular weight of the crosslinked glass-like polymer material in the examples and comparative example 1 is higher than that of the polycarbonate material in the uncrosslinked comparative examples 2-4. However, the number average molecular weight of the glass-like polymer material in example 7 is relatively low due to the low content of the copolymerization catalyst and the low degree of copolymerization, resulting in generally low mechanical properties and biodegradability. The smaller the number average molecular weight of the glass-like polymer material, the higher the degree of disintegration and the degree of decomposition of the polymer into small molecules, but the biodegradation rate is less affected; the larger the number average molecular weight of the glass-like polymer material, the better the mechanical properties.

[0117] Therefore, the application can prepare a biodegradable glass-like polymer material with excellent mechanical properties, which is conducive to the wide application of the glass-like polymer material.

[0118] The above describes the preferred embodiments of the application, but should not be construed as limiting the scope of the application. It should be noted that for those skilled in the art, without departing from the principles of the application, a number of improvements and refinements can be made, which are also considered within the scope of protection of the application.

Claims

1. A vitreous-like polymeric material, characterized in that, The glass-like polymeric material includes a plurality of first repeat units and a plurality of second repeat units, the first repeat units having a structure of R0 is selected from at least one of alkylene, alkenylene, alkynylene, arylene, arylenealkylene, heteroarylene, heteroarylenealkylene, and aliphatic ring; the second repeat units include 2. The glass-like polymeric material of claim 1, wherein The second repeating unit is 3. The glass-like polymeric material of claim 1, wherein The repeating number of the first repeating unit is 50-200; The repeating number of the second repeating unit is 100-400; The number ratio of the first repeating unit to the second repeating unit is 1:(0.5-8).

4. The glass-like polymeric material of claim 1, wherein The number average molecular weight of the glass-like polymer material is 20000-80000.

5. A method of producing a vitreous-like polymeric material, characterized by, Comprising: The polymer and the polyisocyanate-based crosslinking agent are mixed to perform a crosslinking reaction, thereby obtaining the glass-like polymer material according to any one of claims 1-2; the repeating unit of the polymer comprises 6. The production method according to claim 5, wherein The molar ratio of the polymer to the polyisocyanate crosslinking agent is 1:(1-1.2).

7. The production method according to claim 5, wherein The polymer comprises at least one of polytrimethylene carbonate, poly2, 2-dimethyltrimethylene carbonate and copolymer of trimethylene carbonate and 2, 2-dimethyltrimethylene carbonate; the polyisocyanate crosslinking agent comprises at least one of hexamethylene diisocyanate, diphenylmethane diisocyanate and dicyclohexylmethane diisocyanate.

8. The production method according to claim 7, wherein The preparation of the copolymer of trimethylene carbonate and 2, 2-dimethyltrimethylene carbonate comprises: Mixing trimethylene carbonate, 2, 2-dimethyltrimethylene carbonate, copolymerization catalyst and initiator to form a reaction solution, and preparing the copolymer of trimethylene carbonate and 2, 2-dimethyltrimethylene carbonate through copolymerization reaction.

9. The production method according to claim 8, wherein The copolymerization catalyst includes at least one of tin 2-ethylacetate and aluminum isopropoxide; the structure of the initiator is The R1, the R2, the R3, and the R4 are alkylene groups, the R 5 , the R 6 , the R 7 , and the R 8 At least three of the R1, the R2, the R3, and the R4 are hydroxyl groups.

10. The production method according to claim 8, wherein In the reaction solution, the molar ratio of the trimethylene carbonate to the 2, 2-dimethyltrimethylene carbonate is 1:(0.33-3); The molar percentage of the copolymerization catalyst is 0.03%-0.1% and the molar percentage of the initiator is 0.05%-0.2% based on the solute of the reaction solution; The reaction time of the copolymerization reaction is 24h-36h.

11. The production method according to claim 5, wherein The crosslinking reaction is followed by drying, the temperature of the drying is 65℃-75℃, and the time of the drying is 48h-60h.

12. A structural member, characterized by The material of the structural member comprises the glass-like polymer material of any one of claims 1-4 or the glass-like polymer material prepared by the preparation method of any one of claims 5-11.

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