A new method of interfacial chain growth polymerization and ultrahigh molecular weight polymers

Abstract

The application discloses a new interface chain growth polymerization method and an ultrahigh molecular weight polymer and belongs to the technical field of ultrahigh molecular weight polymer preparation. The new interface chain growth polymerization method comprises the following steps: mixing a combination catalyst of an organic base and a hydrogen bond donor, an initiator and monomers to perform an interface chain growth polymerization reaction; the monomers are selected from lactide, lactone, internal thioester, lactam, acrylate or olefin; the initiator is selected from one or more of alcohol substances and thiol substances; and the hydrogen bond donor is selected from structures shown in the following formula 1 or formula 2. The new method effectively inhibits polymerization side reactions through polymer chain and solvent phase separation, and ultrahigh molecular weight polymers are obtained. The ultrahigh molecular weight polymers have good thermal and mechanical properties, excellent barrier properties, and outstanding oxygen barrier capacity. In addition, the polyethylene thioester can be recycled through solution depolymerization.

Description

Technical Field

[0001] This invention relates to the field of ultra-high molecular weight polymer preparation technology, and in particular to a novel method for interfacial chain growth polymerization and an ultra-high molecular weight polymer. Background Technology

[0002] The large-scale use and disposal of plastics has caused serious resource waste and environmental pollution. How to economically and environmentally dispose of plastic waste has become an urgent global issue. Closed-loop recycling of plastics allows them to be directly converted from polymer materials into original monomers after use, achieving resource recycling and reuse at the same level. This is an effective way to fundamentally solve the problem of plastic waste disposal.

[0003] Although some closed-loop recycled polymers have been reported, enabling monomer-polymer-monomer closed-loop cycles, the challenge of recyclability and mechanical properties remains. Specifically, closed-loop recycled polymers typically have poor mechanical properties, making them difficult to meet practical application requirements. The molecular weight of a polymer directly affects its properties; therefore, increasing the molecular weight to improve the polymer's mechanical properties is an effective solution to resolving this contradiction between recyclability and mechanical performance in closed-loop recycled polymers.

[0004] Polysulfides are a promising class of closed-ring recycled polymers. Their relatively weak thioester bonds facilitate a balance between polymerization and depolymerization. However, side reactions such as thioester exchange and backbiting are prone to occur during polymerization, making it difficult to obtain high molecular weight polysulfide materials, which limits their applications to some extent. Invention patent 202110213868.X uses an organic base as a single catalyst for solution polymerization, resulting in vigorous thioester exchange but poor polymerization controllability and low molecular weight. The literature Angew. Chem. Int. Ed. 2021, 60, 22547 reports on solution polymerization using an organic base as a single catalyst, with vigorous thioester exchange and poor polymerization controllability, but the molecular weight is still not ideal. The literature Polymer 2021, 215, 123386 reports on homopolymerization and copolymerization experiments with other monomers using common organic bases, but only low molecular weight polymers were synthesized, with poor thermodynamic stability and mechanical properties, limiting their practical applications. The literature Macromolecules 2015, 48, 5481-5486 reported the solution ring-opening polymerization of caprolactone thioester catalyzed by DBU and thiourea, which could only yield polythioesters with medium molecular weight, less than 35,000.

[0005] Therefore, researching and developing efficient catalysts and polymerization methods to suppress side reactions during polymerization and synthesize high molecular weight recyclable polysulfide materials has become an urgent technical challenge. Summary of the Invention

[0006] In view of this, the technical problem to be solved by the present invention is to provide a novel method for interfacial chain growth polymerization and an ultra-high molecular weight polymer. The novel interfacial chain growth polymerization method achieves the synthesis of ultra-high molecular weight polymers by effectively suppressing intra-chain and inter-chain side reactions present during polymer synthesis.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0008] This invention provides a novel method for interface chain growth and aggregation, comprising the following steps:

[0009] A combination of organic base and hydrogen bond donor catalyst, initiator and monomer is mixed to carry out interfacial chain growth polymerization reaction;

[0010] The monomer is selected from lactones, lactones, lactones, lactams, acrylates, or olefins;

[0011] The initiator is selected from one or more of alcohols and thiols;

[0012] The hydrogen bond donor is selected from the structure shown in Formula 1 or Formula 2:

[0013]

[0014] Among them, R 1 Selected from O, S, or Se;

[0015] R 2 and R 3 Independently selected from hydrogen, C 1-30 Perfluoroalkyl, C 1-30 Straight-chain or branched aliphatic alkyl groups, C 1-30 Substituted or unsubstituted alicyclic hydrocarbon groups, substituted or unsubstituted C 6-30 Aromatic group, C 2-30 alkenyl, C 2-30 alkynyl group, C 3-30 Heterocyclic, substituted or unsubstituted C 5-30 One or more of the heteroaryl groups;

[0016] The replaced C 6-30 Aromatic substituents or substituted C 5-30 The substituents of the heteroaryl group are independently selected from one or more of trifluoromethyl, nitrile, nitro, and halogen.

[0017] More preferably, the R of the present invention 2 and R 3 Independently selected from one or more of the following structures:

[0018]

[0019] in, Indicates the connection location.

[0020] In a further preferred embodiment of the present invention, the hydrogen bond donor is selected from any of the following structures:

[0021]

[0022] In the novel interfacial chain growth polymerization method described in this invention, when the polymer chain grows to the critical chain length during polymerization, its solubility decreases, and it precipitates out of the solution. However, due to the activation effect of the combined catalyst of organic base and hydrogen bond donor, the polymer chain ends still dissolve and continue to polymerize with monomers in the solution at the solid / liquid interface. This causes the polymer chain to separate from the solvent into solid and liquid phases, becoming free outside the polymerization system. This effectively suppresses intra- and inter-chain side reactions during polymerization, thereby obtaining ultra-high molecular weight polymers.

[0023] In the above-mentioned novel method for interfacial chain growth polymerization, the organic base and hydrogen bond donor in the combined catalyst synergistically catalyze, suppressing side reactions in the polymerization process and increasing the solubility of polymer chain ends in the monomer solution phase, thereby promoting the continuous progress of interfacial chain growth polymerization.

[0024] In the novel interfacial chain growth polymerization method described in this invention, the polymer precipitates after reaching a certain degree of polymerization. However, the polymer chain ends retain solubility in the solution phase containing monomers and catalysts. The precipitation of the polymer does not terminate the polymerization, allowing the polymerization to continue at the interface between the monomer solution and the solid polymer. Furthermore, the phase separation between the grown polymer chain ends and the polymer bulk (solid phase) reduces the probability of attacking functional groups on the polymer chain, thereby reducing side reactions and promoting the interfacial chain growth polymerization reaction.

[0025] Preferably, the organic base is selected from one or more of 4-dimethylaminopyridine, DBU, TBD, t-BuP2, sodium thiophene, and triethylamine.

[0026] Preferably, the initiator is selected from benzyl alcohol, methanol, ethanol, benzyl thiol, 1,4-phenyldithiol, alkyl thiols with 1-20 carbon atoms, or thiophenol.

[0027] Preferably, the molar ratio of the organic base to the hydrogen bond donor is 1:(0.5-5).

[0028] Preferably, the molar ratio of the monomer to the initiator is (1000-20000):1;

[0029] Preferably, the molar ratio of the combined catalyst of the organic base and hydrogen bond donor to the initiator is (0.01-1):1; more preferably (0.01-0.1):1. In some specific embodiments of the present invention, it is 0.02:1.

[0030] Preferably, the concentration of the monomer is 4-8 mol / L. In some specific embodiments of the present invention, it is preferably 6 mol / L.

[0031] Preferably, the lactide is selected from lactide or glycolide;

[0032] Preferably, the lactone is selected from proprolactone, valproic acid, or caprolactone;

[0033] Preferably, the lactone is selected from lactide, glycolide, proprolactone, or caprolactone.

[0034] Preferably, the lactam is selected from autolactam or propiolactam;

[0035] Preferably, the acrylate is selected from methyl methacrylate;

[0036] Preferably, the olefin is selected from styrene.

[0037]

[0038] Preferably, the temperature of the interfacial chain growth polymerization reaction is -20℃ to 80℃.

[0039] The preferred time for the interfacial chain growth polymerization reaction is 0.1-48 h.

[0040] The solvent for the interfacial chain growth polymerization reaction is selected from one or more of chloroform, toluene, n-hexane, petroleum ether, dichloromethane, dioxane, tetrahydrofuran, and dimethyl sulfoxide.

[0041] After the above-mentioned interfacial chain growth polymerization reaction is completed, post-processing such as quenching and separation is also included.

[0042] The quenching is preferably performed using a trifluoroacetic acid / dichloromethane mixed solution.

[0043] The separation is preferably achieved by filtration or centrifugation.

[0044] This invention also provides an ultra-high molecular weight polymer, prepared by the above-described novel interfacial chain growth polymerization method;

[0045] The monomers of the ultra-high molecular weight polymer are selected from lactones, lactones, lactones, lactams, acrylates, or olefins.

[0046] The preferred range of the lactone, lactone, lactone, lactam, acrylate or olefin is the same as above, and will not be repeated here.

[0047] Preferably, when the internal thioester is glycolide thioester, the ultra-high molecular weight polymer is a glycolide thioester with a weight-average molecular weight greater than 500 kg / mol. In some specific embodiments of the present invention, the weight-average molecular weight of the glycolide thioester is 501.3 kg / mol, 700.5 kg / mol, 505.2 kg / mol, 500.1 kg / mol, 504.1 kg / mol, 501.8 kg / mol, 505.1 kg / mol, or 502.1 kg / mol.

[0048] The poly(lactic acid thioester) described in this invention exhibits excellent thermal and mechanical properties, comparable to isotactic polypropylene (iPP), and possesses high tensile strength and toughness. Furthermore, the poly(lactic acid thioester) demonstrates outstanding water vapor barrier properties, with a water vapor transport rate comparable to low-density polyethylene, reaching 0.95 g / mm². -2 day -1 ， Far lower than the biodegradable polymer polylactic acid (8.6 g mm m -2 day -1 In addition, it has outstanding oxygen barrier capabilities, with an oxygen permeability of 0.0027 Barrer. Its oxygen barrier performance is 30 times that of commonly used beverage packaging material PET (polyethylene terephthalate), 100 times that of biodegradable plastic polylactic acid, 400 times that of isotactic polypropylene, and 1000 times that of low-density polyethylene.

[0049] Preferably, in this invention, the poly(glycolic acid thioester) is subjected to solution depolymerization under alkaline conditions to obtain glycolide thioester monomer;

[0050] Preferably, the depolymerization temperature of the solution is 25°C-100°C; more preferably, it is 40°C-70°C. In some embodiments of the present invention, it is 60°C.

[0051] The above method achieves a closed-loop recycling of ethylene glycol thioester monomers through solution depolymerization. This recycling method is simple, low-cost, and suitable for large-scale industrial production. Preferably, the alkaline conditions are provided by one or more of 4-dimethylaminopyridine, triethylamine, pyridine, N,N-diisopropylethylamine, sodium hydroxide, and sodium thiophene; more preferably, sodium thiophene or 4-dimethylaminopyridine; and even more preferably, sodium thiophene.

[0052] Preferably, the solvent for solution depolymerization is selected from one or more of chloroform, toluene, dichloromethane, dioxane, tetrahydrofuran, and dimethyl sulfoxide; more preferably, it is chloroform, tetrahydrofuran, or dimethyl sulfoxide. In some specific embodiments of the present invention, dimethyl sulfoxide (DMSO) is used.

[0053] Compared with the prior art, the novel interfacial chain growth polymerization method provided by the present invention includes the following steps: mixing a combination catalyst of an organic base and a hydrogen bond donor, an initiator, and a monomer to carry out an interfacial chain growth polymerization reaction; wherein the monomer is selected from lactones, lactones, lactones, lactams, acrylates, or olefins; the initiator is selected from one or more alcohols and thiols; and the hydrogen bond donor is selected from the structure shown in Formula 1 or Formula 2, wherein R 1 Selected from O, S, or Se; R 2 and R 3 Independently selected from hydrogen, C 1-30 Perfluoroalkyl, C 1-30 Straight-chain or branched aliphatic alkyl groups, C 1-30 Substituted or unsubstituted alicyclic hydrocarbon groups, substituted or unsubstituted C 6-30 Aromatic group, C 2-30 alkenyl, C 2-30 alkynyl group, C 3-30 Heterocyclic, substituted or unsubstituted C 5-30 One or more of the heteroaryl groups; the substituted C 6-30 Aromatic substituents or substituted C 5-30 The substituents of the heteroaromatic group are independently selected from one or more of trifluoromethyl, nitrile, nitro, and halogen groups. The novel method effectively suppresses polymerization side reactions by separating the polymer chain from the solvent phase, yielding an ultra-high molecular weight polymer. The poly(glycolic acid thioester) in the ultra-high molecular weight polymer exhibits excellent thermal and mechanical properties, as well as superior barrier properties, especially outstanding oxygen barrier capabilities. Furthermore, the poly(glycolic acid thioester) can be recovered through solution depolymerization, overcoming the problem of poor water vapor barrier properties in traditional biodegradable materials. This will effectively promote the application of poly(glycolic acid thioester) materials in the closed-loop recycling plastics industry. Attached Figure Description

[0054] Figure 1 The 1H NMR spectrum of the poly(glycolic acid) thioester prepared in Example 1;

[0055] Figure 2 The carbon NMR spectrum of the poly(glycolic acid) thioester prepared in Example 1;

[0056] Figure 3 The poly(glycolic acid sulfide) material prepared in Example 1 was hot-pressed into a film at 175°C and cut into dumbbell-shaped strips.

[0057] Figure 4 The ultra-high molecular weight poly(glycolic acid) prepared in Example 1 was processed into bottles by single-screw melt extrusion and subsequent blow molding at 165°C.

[0058] Figure 5 The ultra-high molecular weight poly(ethylene glycol) sulfide prepared in Example 1 was melt-spun at 175°C to produce filaments;

[0059] Figure 6 The ultra-high molecular weight polyglycolic acid thioester prepared in Example 1 was used to fabricate a three-dimensional red cup using melt filament at a nozzle temperature of 200°C. Detailed Implementation

[0060] To further illustrate the present invention, the novel interfacial chain growth polymerization method and ultra-high molecular weight polymer provided by the present invention will be described in detail below with reference to embodiments.

[0061] Comparative Example 1

[0062]

[0063] Weigh or measure 10 equivalents of catalyst 4-dimethylaminopyridine and 1 equivalent of initiator benzyl mercaptan in a glove box. Weigh approximately 20,000 equivalents of ethylene glycol monophosphate monomer and place it in a reactor (the reactor was pre-treated by evacuation, heating, cooling, and nitrogen purging; this process was repeated three times). Add solvent, with a monomer concentration of 2 mol / L and a monomer / initiator / catalyst molar ratio of 20,000 / 1 / 10, and proceed with solution polymerization. After polymerization is complete, quench with trifluoroacetic acid / dichlorohydrin solution and filter to obtain the polymer. After drying for 24 hours, analyze the polymer molecular weight using a double reptation model to obtain M. w =19.5 kg / mol, M w / M n =3.5. 1 HNMR (500MHz, CDCl3): δ4.12 (1H). 13 C NMR (125MHz, CDCl3): δ193.13,39.14.

[0064] Example 1

[0065]

[0066] Weigh or measure 50 equivalents of catalyst 4-dimethylaminopyridine, 50 equivalents of TU1, and 1 equivalent of initiator benzyl mercaptan in a glove box. Weigh approximately 20,000 equivalents of ethylene glycol monophosphate monomer and place it in a reactor (the reactor was pre-treated by evacuation, heating, cooling, and nitrogen purging; this process was repeated three times). Add dioxane monomer at a concentration of 6 mol / L, with a monomer / initiator / catalyst molar ratio of 20,000 / 1 / 50, and perform interfacial polymerization at 25°C. After polymerization, quench with trifluoroacetic acid / dichlorohydrin solution and filter to obtain the polymer. After drying for 24 hours, analyze the polymer molecular weight using a double reptation model to obtain M. w =501.3 kg / mol, M w / Mn =4.6. Figure 1 of 1 H NMR (500MHz, CDCl3): δ4.12 (1H). Figure 2 of 13 C NMR (125MHz, CDCl3): δ193.13,39.14.

[0067] Example 2

[0068]

[0069] Weigh or measure 50 equivalents of catalyst DBU, 50 equivalents of TU1, and 1 equivalent of initiator in a glove box. Weigh approximately 20,000 equivalents of ethylene glycol monosulfide monomer and place it in a reactor (the reactor was pre-treated by evacuation, heating, cooling, and nitrogen purging; this process was repeated three times). Add toluene, with a monomer concentration of 2 mol / L and a monomer / initiator / catalyst molar ratio of 20,000 / 1 / 50. Perform interfacial polymerization at 25°C. After polymerization, quench with trifluoroacetic acid / dichlorohydrin solution and filter to obtain the polymer. After drying for 24 hours, analyze the polymer molecular weight using GPC to obtain M. w =700.5 kg / mol, M w / M n =1.56. 1 H NMR (500MHz, CDCl3): δ5.24(1H),1.56(3H).

[0070] Example 3

[0071]

[0072] Weigh or measure 1 equivalent of catalyst 4-dimethylaminopyridine, 1 equivalent of TU1, and 1 equivalent of initiator benzyl mercaptan in a glove box. Weigh approximately 20,000 equivalents of ethylene glycol monophosphate monomer and place it in a reactor (the reactor was pre-treated by evacuation, heating, cooling, and nitrogen purging; this process was repeated three times). Add dioxane and perform interfacial polymerization at 50°C. The monomer concentration is 6 mol / L, and the monomer / initiator / catalyst molar ratio is 20,000 / 1 / 1. After polymerization, quench with trifluoroacetic acid / dichlorohydrin solution and filter to obtain the polymer. After drying for 24 hours, analyze the polymer molecular weight using a double reptation model to obtain M. w =505.2 kg / mol, M w / M n =4.0.

[0073] Example 4

[0074]

[0075] Weigh or measure 50 equivalents of catalyst TBD, 50 equivalents of TU1 (thiourea), and 1 equivalent of initiator benzyl mercaptan in a glove box. Weigh approximately 20,000 equivalents of glycolide monomer and place it in a reactor (the reactor was pre-treated by evacuation, heating, cooling, and nitrogen purging; this process was repeated three times). Add dichloromethane, with a monomer concentration of 6 mol / L and a monomer / initiator / catalyst molar ratio of 20,000 / 1 / 50. Perform interfacial polymerization at 50°C. After polymerization, quench with trifluoroacetic acid / dichloromethane solution and filter to obtain the polymer. After drying for 24 hours, analyze the polymer molecular weight using a double reptation model to obtain M. w =500.1 kg / mol, M w / M n =4.7.

[0076] Example 5

[0077]

[0078] Weigh or measure 50 equivalents of sodium thiophene catalyst, 50 equivalents of TU1, and 1 equivalent of benzyl mercaptan initiator in a glove box. Weigh approximately 20,000 equivalents of ethylene glycol monophosphate monomer and place it in a reactor (the reactor was pre-treated by evacuation, heating, cooling, and nitrogen purging; this process was repeated three times). Add dioxane, with a monomer concentration of 6 mol / L and a monomer / initiator / catalyst molar ratio of 20,000 / 1 / 50. Perform interfacial polymerization at 25°C. After polymerization, quench with trifluoroacetic acid / dichlorohydrin solution and filter to obtain the polymer. After drying for 24 hours, analyze the polymer molecular weight using a double reptation model to obtain M. w =504.1 kg / mol, M w / M n =4.7.

[0079] Example 6

[0080]

[0081] Weigh or measure 50 equivalents of triethylamine catalyst, 50 equivalents of TU1, and 1 equivalent of benzyl mercaptan initiator in a glove box. Weigh approximately 20,000 equivalents of ethylene glycol monophosphate monomer and place it in a reactor (the reactor was pre-treated by evacuation, heating, cooling, and nitrogen purging; this process was repeated three times). Add dichloromethane, with a monomer concentration of 6 mol / L and a monomer / initiator / catalyst molar ratio of 20,000 / 1 / 50. Perform interfacial polymerization at 25°C. After polymerization, quench with trifluoroacetic acid / dichloromethane solution and filter to obtain the polymer. After drying for 24 hours, analyze the polymer molecular weight using a double reptation model to obtain M. w =501.8 kg / mol, Mw / M n =4.7.

[0082] Example 7

[0083]

[0084] Weigh or measure 50 equivalents of catalyst DBU, 50 equivalents of Q1, and 1 equivalent of initiator benzyl mercaptan in a glove box. Weigh approximately 20,000 equivalents of thioglycolate monomer and place it in a reactor (the reactor was pre-treated by evacuation, heating, cooling, and nitrogen purging; this process was repeated three times). Add solvent, with a monomer concentration of 6 mol / L and a monomer / initiator / catalyst molar ratio of 20,000 / 1 / 50, and proceed with interfacial polymerization. After polymerization, quench with trifluoroacetic acid / dichlorohydrin solution and filter to obtain the polymer. After drying for 24 hours, analyze the polymer molecular weight using a double reptation model to obtain M. w =504.1 kg / mol, M w / M n =4.7.

[0085] Example 8

[0086]

[0087] Weigh or measure 50 equivalents of catalyst DBU, 50 equivalents of U1, and 1 equivalent of initiator benzyl mercaptan in a glove box. Weigh approximately 20,000 equivalents of glycolide monomer and place it in a reactor (the reactor was pre-treated by evacuation, heating, cooling, and nitrogen purging; this process was repeated three times). Add dioxane, with a monomer concentration of 6 mol / L and a monomer / initiator / catalyst molar ratio of 20,000 / 1 / 50. Perform interfacial polymerization at 50°C. After polymerization, quench with trifluoroacetic acid / dichlorohydrin solution and filter to obtain the polymer. After drying for 24 hours, analyze the polymer molecular weight using a double reptation model to obtain M. w =502.1 kg / mol, M w / M n =4.7.

[0088] Example 9

[0089] Depolymerization and recycling

[0090]

[0091] The specific steps are as follows:

[0092] 50 mg of the poly(ethylene glycol) thiolated material from Example 1 was dissolved in 0.5 mL of DMSO, and 0.01 equivalents of sodium thiophene were added. The reaction was carried out at 60 °C for 2 min. Monitoring of the reaction solution confirmed that the poly(ethylene glycol) thiolated material was recovered as ethylene glycol.

[0093] Example 10

[0094] The specific steps for barrier performance testing are as follows:

[0095] The polysulfide material from Example 1 was hot-pressed into a film at 175°C, and then cut into circular films with diameters of 5 cm and 10 cm for water vapor and oxygen barrier tests. The water vapor barrier performance was 0.95 g mmm. -2 day -1 The oxygen barrier capacity is 0.0027 Barrer, and the carbon dioxide barrier capacity is 0.0095 Barrer (Table 1).

[0096] Table 1 Performance Test Results

[0097]

[0098] Note: In the table, PLA stands for polylactic acid, PET stands for polyethylene terephthalate, iPP stands for commercial isotactic polypropylene, and LDPE stands for low-density polyethylene.

[0099] Example 11

[0100] The specific steps are as follows:

[0101] The ultra-high molecular weight poly(ethylene glycol) thioester prepared in Example 1 has melt processing properties and can be processed into bottles (e.g., bottles) at 165°C via single-screw melt extrusion and subsequent blow molding. Figure 4 (As shown). It can also be melt-spun at 175°C to produce filaments (such as...). Figure 5 (As shown). Finally, PTGA and red polyethylene masterbatch were extruded together using a twin-screw extruder at 165°C to produce filaments suitable for additive manufacturing. A 3D-printed red cup (as shown) was achieved by manufacturing the molten filament at a nozzle temperature of 200°C. Figure 6 As shown in the figure, this demonstrates the direct melt-processability of this material.

[0102] Example 12

[0103] Mechanical performance testing

[0104] The specific steps are as follows:

[0105] Poly(glycolic acid thioester) materials with a molecular weight of 19.5 kg / mol in Comparative Example 1 and as high as 504.1 kg / mol in Example 1 were hot-pressed into films at 175°C and cut into dumbbell-shaped strips. Tensile tests showed that: Poly(glycolic acid thioester) with a molecular weight of 19.5 kg / mol had a tensile strength σb = 20.16 MPa and an elongation at break εb = 8.6%; Poly(glycolic acid thioester) with a molecular weight of 501.3 kg / mol had a tensile strength σb = 36.15 MPa and an elongation at break εb = 464.2% (performance tests are shown in Table 2). Figure 3 )

[0106] Table 2 Mechanical Performance Test Results

[0107]

[0108] The above description of the embodiments is only for the purpose of helping to understand the method and core ideas of the present invention. It should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principles of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims

1. A novel method for interface chain growth and aggregation, characterized in that, Includes the following steps: A combination of organic base and hydrogen bond donor catalyst, initiator and monomer is mixed to carry out interfacial chain growth polymerization reaction; The monomer is selected from lactones, lactones, lactones, lactams, acrylates, or olefins; The initiator is selected from one or more of alcohols and thiols; The hydrogen bond donor is selected from the structure shown in Formula 1 or Formula 2: Among them, R 1 Selected from O, S, or Se; R 2 and R 3 Independently selected from hydrogen, C 1-30 Perfluoroalkyl, C 1-30 Straight-chain or branched aliphatic alkyl groups, C 1-30 Substituted or unsubstituted alicyclic hydrocarbon groups, substituted or unsubstituted C 6-30 Aromatic group, C 2-30 alkenyl, C 2-30 alkynyl group, C 3-30 Heterocyclic, substituted or unsubstituted C 5-30 One or more of the heteroaryl groups; The replaced C 6-30 Aromatic substituents or substituted C 5-30 The substituents of the heteroaryl group are independently selected from one or more of trifluoromethyl, nitrile, nitro, and halogen.

2. The novel method for interface chain growth and aggregation according to claim 1, characterized in that, The R 2 and R 3 Independently selected from one or more of the following structures: Where ︴ represents the connection position.

3. The novel method for interface chain growth and aggregation according to claim 1 or 2, characterized in that, The hydrogen bond donor is selected from any of the following structures:

4. The novel method for interface chain growth and aggregation according to claim 1, characterized in that, The organic base is selected from one or more of 4-dimethylaminopyridine, DBU, TBD, t-BuP2, sodium thiophene, and triethylamine; The initiator is selected from benzyl alcohol, methanol, ethanol, benzyl thiol, 1,4-phenyldithiol, alkyl thiols with 1-20 carbon atoms, or benzyl thiophenol.

5. The novel method for interface chain growth and aggregation according to claim 1, characterized in that, The molar ratio of the organic base to the hydrogen bond donor is 1:(0.5-5); The molar ratio of the monomer to the initiator is (1000-20000):1; The molar ratio of the combined catalyst of organic base and hydrogen bond donor to initiator is (0.01-1):1; The concentration of the monomer is 4-8 mol / L.

6. The novel method for interface chain growth and aggregation according to claim 1, characterized in that, The lactide is selected from lactide or glycolide; The lactone is selected from proprolactone, valproic acid, or caprolactone; The lactone is selected from lactide, ethylene lactide, proprolactone or caprolactone. The lactam is selected from autolactam or propiolactam; The acrylate is selected from methyl methacrylate; The olefin is selected from styrene.

7. The novel method for interface chain growth and aggregation according to claim 1, characterized in that, The temperature range for the interfacial chain growth polymerization reaction is -20℃ to 80℃. The solvent for the interfacial chain growth polymerization reaction is selected from one or more of chloroform, toluene, n-hexane, petroleum ether, dichloromethane, dioxane, tetrahydrofuran, and dimethyl sulfoxide.

8. An ultra-high molecular weight polymer, characterized in that, Prepared by the novel interfacial chain growth polymerization method according to any one of claims 1-7; The monomers of the ultra-high molecular weight polymer are selected from lactones, lactones, lactones, lactams, acrylates, or olefins.

9. The ultra-high molecular weight polymer according to claim 8, characterized in that, When the internal thioester is glycolide thioester, the weight-average molecular weight of the ultra-high molecular weight polymer is greater than that of polyethylene glycolide thioester with a molecular weight of 500 kg / mol.

10. The ultra-high molecular weight polymer according to claim 9, characterized in that, The poly(glycolic acid thioester) is subjected to solution depolymerization under alkaline conditions to obtain glycolide thioester monomer; The temperature at which the solution depolymerizes is 25℃-100℃.

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