CN109161012A - A kind of endlap nitrogen hexadecyl ethylene oxide-tetrahydrofuran block co-polyether and its synthetic method containing carbamate structures unit - Google Patents

A kind of endlap nitrogen hexadecyl ethylene oxide-tetrahydrofuran block co-polyether and its synthetic method containing carbamate structures unit Download PDF

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CN109161012A
CN109161012A CN201811067949.8A CN201811067949A CN109161012A CN 109161012 A CN109161012 A CN 109161012A CN 201811067949 A CN201811067949 A CN 201811067949A CN 109161012 A CN109161012 A CN 109161012A
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ethylene oxide
polyether
tetrahydrofuran
block
tetrahydrofuran block
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CN109161012B (en
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张倩
莫洪昌
卢先明
刘宁
徐明辉
汪伟
朱勇
舒远杰
王晓川
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Xian Modern Chemistry Research Institute
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32Polymers modified by chemical after-treatment
    • C08G65/321Polymers modified by chemical after-treatment with inorganic compounds
    • C08G65/325Polymers modified by chemical after-treatment with inorganic compounds containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32Polymers modified by chemical after-treatment
    • C08G65/329Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33348Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
    • C08G65/33351Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group acyclic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J171/00Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02Polyalkylene oxides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
    • C08G2650/04End-capping

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Polyethers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a kind of endlap nitrogen hexadecyl ethylene oxide-tetrahydrofuran block co-polyether adhesive containing carbamate structures unit, its structural formula is as shown in figure (I), its synthetic method includes the following steps: with terminal hydroxy group ethylene oxide-tetrahydrofuran block co-polyether (HTPE) for parent, by nucleophilic addition occurs with 2- chloroethyl isocyanate, nucleophilic displacement of fluorine then carried out with sodium azide again finally obtain a kind of Huisgen that can be used for react the cured endlap nitrogen based adhesive containing carbamate structures unit of progress.This synthetic method is simple, and side reaction is few, high income, and the curing mode of the adhesive of synthesis has wide environmental suitability.Present invention is mainly used for composite solidpropellants.

Description

A kind of endlap nitrogen hexadecyl ethylene oxide-tetrahydro furan containing carbamate structures unit It mutters block co-polyether and its synthetic method
Technical field
The present invention relates to a kind of, and endlap nitrogen hexadecyl ethylene oxide-tetrahydrofuran block containing carbamate structures unit is total Polyethers adhesive and its synthetic method, the compound can be used as the adhesive of composite solidpropellant, belong to solid propellant neck Domain.
Background technique
Terminal hydroxy group ethylene oxide-tetrahydrofuran block co-polyether (HTPE) is one kind with tetrahydrofuran and ethylene oxide polymerization Obtained multiblock ether.HTPE propellant based on the adhesive is the novel Insensitive Propellant of one kind of external report, with Improve the tactics that the HTPB composite propellant based on end hydroxy butadiene (HTPB) adhesive is felt immediately for the purpose of ammunition characteristic to lead Bullet solid propellant is current good mechanical performance and the insensitiveness that can fully meet MIL-STD-2105C insensitiveness technical requirements Propellant kind.HTPE adhesive forms urethane crosslinks network structure with Isocyanates curing agent generally in propellant In be applied.But there are shortcomings during using and saving for the propellant based on conventional urethane system: 1. different Cyanic acid ester group is a more active group, during carrying out cured with hydroxyl, moreover it is possible to the CO in air2, it is micro Moisture occurs side reaction and generates bubble, to influence the combustibility of propellant, mechanical property, processing cost and security performance Deng;2. the curing system is poor for the compatibility of energetic oxidizer molecule (such as: AND, HNF etc.), to limit propulsion The integral energy of agent is horizontal.
In order to solve the problems, such as isocyanate cure systems defect and, domestic and international researcher has developed based on clickization The curing mode of Huisgen reaction is learned, which generates the cross-linked network of polytriazoles structure using end alkynyl radical and azido reaction Structure, it is few, insensitive to water with side reaction, good etc. many with the compatibility of energetic oxidizer molecule (such as: ADN, HNF etc.) Advantage.Currently, the end position study on the modification for HTPE is less, and such as: the Li Hui of Xi'an Inst. of Modern Chemistry is " a kind of in patent The end alkynyl radical Ethylene Oxide-Tetrahydrofuran Copolyether and its synthetic method of amido-containing acid ester unit " (number of accepting: 201610808357.1) in, the block co-polyether adhesive PUPE that HTPE is modified as end alkynyl radical by chain, structural formula are prolonged using PDI As shown in (II).
Firstly, two steps for needing to distinguish operate in the synthesis process of the method: the first step, using TDI method excessive greatly (3~5 times) synthesize propargyl (3- isocyanate group -4- methyl) carbanilate, second step, then life is reacted with HTPE At the end alkynyl radical polybutadiene of amido-containing acid ester unit.The method synthesis process is complicated for operation, and the post-processing of intermediate is to environment Humidity requires harshness, there are wastage of material phenomenon and is not easy to realize technique amplification.Secondly, the PUPE adhesive glass of method synthesis Glass transition temperature is -58.6 DEG C, is increased by a relatively large margin relative to having for parent adhesive.Finally, elastomer obtained by PUPE, Tensile strength is 1.13MPa, and fracture elongation 320.2%, mechanical strength is bad.
Summary of the invention
It is a kind of with wide environmental suitability the technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide And the higher end azido polyethers adhesive containing carbamate structures unit of mechanical property.
Insight of the invention is that moisture sensitivity in the solidification process of traditional HTPE adhesive, to influence propellant Mechanical property and security performance etc., but the interaction of hydrogen bond that gained polyurethane elastomer is generated due to urethane unit So that the excellent mechanical property that its polyurethane elastomer has, and traditional polytriazole elastomer have solidification process to water not Sensitive wide environmental suitability, but due to lacking the interaction between segment in polytriazole elastomer and mechanical property is undesirable.
In order to solve the above-mentioned technical problem, a kind of endlap nitrogen basic ring oxygen containing carbamate structures unit of the invention Ethane-tetrahydrofuran block co-polyether, structural formula are as follows:
Wherein, X=10~60 are integer;Y=10~60 are integer;M is the positive integer more than or equal to 1.
A kind of endlap nitrogen hexadecyl ethylene oxide-tetrahydrofuran block copolymerization containing carbamate structures unit of the invention Ether synthetic route is as follows:
Wherein, X=10~60 are integer;Y=10~60 are integer;M is the positive integer more than or equal to 1.
A kind of endlap nitrogen hexadecyl ethylene oxide-tetrahydrofuran block copolymerization containing carbamate structures unit of the invention Ether synthetic method the following steps are included:
Step 1: end chloro ethylene oxide-tetrahydrofuran block co-polyether synthesis
Terminal hydroxy group ethylene oxide-tetrahydrofuran block co-polyether and dibutyl tin dilaurate are added in reaction flask, stirs It mixes uniformly, 2- chloroethyl isocyanate is then added, starts to be to slowly warm up to 50~90 DEG C after mixing evenly, the reaction was continued 3~ For 24 hours, colorless viscous shape liquid is obtained as end chloro ethylene oxide-tetrahydrofuran block co-polyether.Wherein, terminal hydroxy group epoxy second Alkane-tetrahydrofuran block co-polyether and 2- chloroethyl isocyanate molar ratio are 1:2~4, terminal hydroxy group ethylene oxide-tetrahydrofuran Block co-polyether and tin dilaurate tetrabutyl alkene molar ratio are 1:1 × 10-3~4 × 10-3
Step 2: the synthesis of endlap nitrogen hexadecyl ethylene oxide-tetrahydrofuran block co-polyether
In reaction flask be added end chloro ethylene oxide-tetrahydrofuran block co-polyether, N,N-dimethylformamide and Sodium azide is to slowly warm up to 50~90 DEG C after mixing evenly, reacts 12~72h, reaction system is down to room temperature, is removed under reduced pressure Solvent, obtaining orange-yellow viscous liquid is endlap nitrogen hexadecyl ethylene oxide-tetrahydrofuran block co-polyether, wherein end chloro Ethylene oxide-tetrahydrofuran block co-polyether and sodium azide molar ratio are 1:2~6, sodium azide and N, N- dimethyl formyl The mass volume ratio of amine is the grams per milliliter of 1:10~100.
Advantages of the present invention:
ATUTPE adhesive according to the present invention, firstly, of the invention a kind of containing carbamate structures unit In endlap nitrogen hexadecyl ethylene oxide-tetrahydrofuran block co-polyether molecular structure, other than containing there are two azido is held, strand two Side is introduced with the carbamate groups compared with strong hydrogen bonding effect, is played the role of physical crosslinking point in the elastomer, is used for The content and microphase separation degree of hard segment can be improved in synthesis polytriazole elastomer, to improve mechanical property, tensile strength can Up to 2.229MPa, fracture elongation 433.95%, and the tensile strength 1.13MPa in documents 1, fracture elongation 320.2%, secondly, the adhesive synthetic method uses " one pot of two-step method ": the first step almost quantitatively generates intermediate ClUTPE, post-processing approach is easily operated, and gained intermediate can direct plunge into next step;Second step, nitrine are combined to also belong to In routine operation, post processing mode is simple, stable yield.Again, the glass transition temperature of gained AUTPE adhesive be- 67.6 DEG C, changes less relative to parent adhesive, largely ensure that the cryogenic mechanics performance of elastomer.In addition, It is the liquid polymer with good fluidity under the adhesive room temperature state, and, it can be achieved that room in the presence of proper catalyst Temperature solidification.
Specific embodiment:
Test equipment:
Examination of infrared spectrum is tested using the 870 type Fourier Transform Infrared Spectrometer of Nexus of U.S. Nicolet company;
Nuclear magnetic resonance spectroscopy test is tested using the AVANCE AV500 type Nuclear Magnetic Resonance of Bruker company of Germany;
Number-average molecular weight test uses Britain PL company GPC-50 type gel permeation chromatograph;GPC test condition: chromatographic column For PLgel MIXED-E series connection;Mobile phase is THF;Column temperature is 40 DEG C;Detector is differential refraction detector.
Elasticity performance test uses Japan SHIMADZU AG-X Plus type electronic universal material experiment-machine.
Embodiment 1
Step 1: end chloro ethylene oxide-tetrahydrofuran block co-polyether (ClTUTPE) synthesis
It is furnished with mechanical stirring, reflux condensing tube at one, in the 250mL three neck round bottom flask of thermometer, sequentially adds end Hydroxyl ethylene oxide-tetrahydrofuran block co-polyether (22.200g, 7.818mmol) and dibutyl tin dilaurate (0.0138g, 0.022mmol), it stirs evenly.Then 2- chloroethyl isocyanate (1.741g, 16.5mmol) is added, starts after mixing evenly 80 DEG C are to slowly warm up to, the reaction was continued 19h.After reaction, the complete 2- chloroethyl isocyanate of unreacted is removed, is obtained colourless Viscous liquid is end chloro ethylene oxide-tetrahydrofuran block co-polyether 23.8189g, yield 99.87%.
Structural Identification:
IR, νmax(cm-1): 3510,3330 (- NH-), 2940,2860 (- CH2), 1724 (C=O), 1114 (- C-O- C-), 778 (C-Cl).
1H NMR(CDCl3, 500MHz): 5.47,4.23,3.63,3.58,3.47,3.41,2.46,1.62.
13C NMR(CDCl3, 500MHz): 156.26,70.56,69.44,68.85,64.11,43.76,42.76, 25.35。
Step 2: the synthesis of endlap nitrogen hexadecyl ethylene oxide-tetrahydrofuran block co-polyether (ATUTPE)
It is furnished with mechanical stirring, reflux condensing tube at one, in the 250mL three neck round bottom flask of thermometer, sequentially adds end Chloro ethylene oxide-tetrahydrofuran block co-polyether (15.892g, 5.537mmol), 30mLN, dinethylformamide and folded Sodium nitride (1.443g, 22.200mmol) is to slowly warm up to 70 DEG C after mixing evenly, reacts 72h.After reaction, decompression is steamed Except solvent, obtaining orange-yellow viscous liquid is endlap nitrogen hexadecyl ethylene oxide-tetrahydrofuran block co-polyether 15.986g, is received Rate: 94.23%.
Structural Identification:
IR, νmax(cm-1): 3505,3330 (- NH-), 2940,2860 (- CH2), 2100 (- N3), 1724 (C=O), 1114(-C-O-C-)。
1H NMR(CDCl3, 500MHz): 5.29,4.23,3.64,3.58,3.47,3.41,2.93,2.25,1.62.
13C NMR(CDCl3, 500MHz): 156.34,70.57,69.49,68.89,64.15,51.05,40.36, 25.35。
Physicochemical property: appearance is orange-yellow viscous liquid, and number-average molecular weight 5199, glass transition temperature is -67.6 ℃。
Embodiment 2
Step 1: end chloro ethylene oxide-tetrahydrofuran block co-polyether (ClTUTPE) synthesis
It is furnished with mechanical stirring, reflux condensing tube at one, in the 250mL three neck round bottom flask of thermometer, sequentially adds end Hydroxyl ethylene oxide-tetrahydrofuran block co-polyether (22.200g, 7.818mmol) and dibutyl tin dilaurate (0.0095g, 0.015mmol), it stirs evenly.Then 2- chloroethyl isocyanate (2.146g, 20.338mmol) is added, opens after mixing evenly Beginning is to slowly warm up to 70 DEG C, the reaction was continued 22h.After reaction, vacuum distillation removes the complete 2- chloroethyl isocyanic acid of unreacted Ester obtains colorless viscous shape liquid as end chloro ethylene oxide-tetrahydrofuran block co-polyether 23.843g, yield 99.97%.
Step 2: the synthesis of endlap nitrogen hexadecyl ethylene oxide-tetrahydrofuran block co-polyether (ATUTPE) is at one with organic Tool stirring, reflux condensing tube in the 250mL three neck round bottom flask of thermometer, sequentially add end chloro ethylene oxide-tetrahydrofuran Block co-polyether (15.892g, 5.537mmol), 100mL n,N-Dimethylformamide and sodium azide (1.080g, 16.611mmol), it is to slowly warm up to 80 DEG C after mixing evenly, reacts 36h.After reaction, evaporating solvent under reduced pressure obtains orange Color viscous liquid is endlap nitrogen hexadecyl ethylene oxide-tetrahydrofuran block co-polyether 15.508g, yield: 97.16%.
Embodiment 3
Step 1: end chloro ethylene oxide-tetrahydrofuran block co-polyether (ClTUTPE) synthesis
It is furnished with mechanical stirring, reflux condensing tube at one, in the 250mL three neck round bottom flask of thermometer, sequentially adds end Hydroxyl ethylene oxide-tetrahydrofuran block co-polyether (22.200g, 7.818mmol) and dibutyl tin dilaurate (0.016g, 0.025mmol), it stirs evenly.Then 2- chloroethyl isocyanate (3.282g, 31.099mmol) is added, opens after mixing evenly Beginning is to slowly warm up to 90 DEG C, the reaction was continued 7h.After reaction, vacuum distillation removes the complete 2- chloroethyl isocyanic acid of unreacted Ester obtains colorless viscous shape liquid as end chloro ethylene oxide-tetrahydrofuran block co-polyether 23.810g, yield 99.83%.
Step 2: the synthesis of endlap nitrogen hexadecyl ethylene oxide-tetrahydrofuran block co-polyether (ATUTPE)
It is furnished with mechanical stirring, reflux condensing tube at one, in the 250mL three neck round bottom flask of thermometer, sequentially adds end Chloro ethylene oxide-tetrahydrofuran block co-polyether (15.892g, 5.537mmol), 80mLN, dinethylformamide and folded Sodium nitride (2.024g, 31.134mmol) is to slowly warm up to 90 DEG C after mixing evenly, and reaction is for 24 hours.After reaction, decompression is steamed Except solvent, obtaining orange-yellow viscous liquid is endlap nitrogen hexadecyl ethylene oxide-tetrahydrofuran block co-polyether 15.000g, is received Rate 93.98%.
End azido block co-polyether adhesive application performance of the invention
(1) with the Miscibility evaluations of curing agent
Selecting three propargyl amine is curing agent, has investigated end azido block co-polyether adhesive A UTPE and curing agent Compatibility and reactivity.AUTPE adhesive and three propargyl amine hardeners of the invention has good compatibility, mixture As clear as crystal, curing reaction can smoothly be carried out at room temperature~80 DEG C by being formed by mixed liquor.
(2) mechanical property of elastomer
End azido block co-polyether adhesive A UTPE of the invention and three propargyl amine hardeners are solidified, Wu Xujia Enter plasticiser, mechanical property the results are shown in Table 1:
The mechanical property of 1 elastomer film of table
As it can be seen that the elastomer film mechanical property of end azido block co-polyether adhesive A TUTPE of the invention is obviously excellent In the mechanical property of polytriazoles class elastomer reported in the literature.

Claims (2)

1. a kind of endlap nitrogen hexadecyl ethylene oxide-tetrahydrofuran block co-polyether adhesive containing carbamate structures unit, Its structural formula is such as shown in (I):
Wherein, X=10~60 are integer;Y=10~60 are integer;M is the positive integer more than or equal to 1.
2. a kind of endlap nitrogen hexadecyl ethylene oxide-tetrahydrofuran described in claim 1 containing carbamate structures unit is embedding The synthetic method of section copolyether adhesive, it is characterised in that the following steps are included:
Step 1: end chloro ethylene oxide-tetrahydrofuran block co-polyether synthesis
Terminal hydroxy group ethylene oxide-tetrahydrofuran block co-polyether and dibutyl tin dilaurate are added in reaction flask, stirring is equal It is even, 2- chloroethyl isocyanate is then added, starts to be to slowly warm up to 50~90 DEG C after mixing evenly, the reaction was continued 3~for 24 hours, Colorless viscous shape liquid is obtained as end chloro ethylene oxide-tetrahydrofuran block co-polyether;Wherein, terminal hydroxy group ethylene oxide-four Hydrogen furans block co-polyether and 2- chloroethyl isocyanate molar ratio are 1:2~4, terminal hydroxy group ethylene oxide-tetrahydrofuran block Copolyether and tin dilaurate tetrabutyl alkene molar ratio are 1:1 × 10-3~4 × 10-3
Step 2: the synthesis of endlap nitrogen hexadecyl ethylene oxide-tetrahydrofuran block co-polyether
End chloro ethylene oxide-tetrahydrofuran block co-polyether, N,N-dimethylformamide and nitrine is added in reaction flask Change sodium, be to slowly warm up to 50~90 DEG C after mixing evenly, reacts 12~72h, reaction system is down to room temperature, is removed under reduced pressure molten Agent, obtaining orange-yellow viscous liquid is endlap nitrogen hexadecyl ethylene oxide-tetrahydrofuran block co-polyether, wherein end chloro ring Oxidative ethane-tetrahydrofuran block co-polyether and sodium azide molar ratio are 1:2~6, sodium azide and n,N-Dimethylformamide Mass volume ratio be the grams per milliliter of 1:10~100.
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CN111718480A (en) * 2020-06-30 2020-09-29 西安近代化学研究所 Acryloyloxy polyether curing agent
CN113501963A (en) * 2021-08-04 2021-10-15 南京理工大学 3-azidomethyl-3-methyloxetane-tetrahydrofuran energetic copolyether with alternating multi-block structure and synthesis method thereof
CN115160560A (en) * 2022-08-09 2022-10-11 西北工业大学 Block copolymer and preparation method and application thereof
CN115521455A (en) * 2021-06-25 2022-12-27 北京理工大学 Preparation method of polytriazole polyether elastomer

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111718480A (en) * 2020-06-30 2020-09-29 西安近代化学研究所 Acryloyloxy polyether curing agent
CN111718480B (en) * 2020-06-30 2022-06-10 西安近代化学研究所 Terminal acryloxy polyether curing agent
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CN115521455B (en) * 2021-06-25 2023-06-30 北京理工大学 Preparation method of polytriazole polyether elastomer
CN113501963A (en) * 2021-08-04 2021-10-15 南京理工大学 3-azidomethyl-3-methyloxetane-tetrahydrofuran energetic copolyether with alternating multi-block structure and synthesis method thereof
CN113501963B (en) * 2021-08-04 2023-03-14 南京理工大学 3-azidomethyl-3-methyloxetane-tetrahydrofuran energetic copolyether with alternating multi-block structure and synthesis method thereof
CN115160560A (en) * 2022-08-09 2022-10-11 西北工业大学 Block copolymer and preparation method and application thereof
CN115160560B (en) * 2022-08-09 2024-06-04 西北工业大学 Block copolymer and preparation method and application thereof

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