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 PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/321—Polymers modified by chemical after-treatment with inorganic compounds
- C08G65/325—Polymers modified by chemical after-treatment with inorganic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
- C08G65/33351—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group acyclic
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
- C09J171/02—Polyalkylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
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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
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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Cited By (4)
| 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 |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05221769A (en) * | 1992-02-10 | 1993-08-31 | Daicel Chem Ind Ltd | High energy binder base composite propellant |
| CN104995229A (en) * | 2013-02-08 | 2015-10-21 | Sika技术股份公司 | Synthesis of polyurethane polymers via copper azide-alkyne click chemistry for coatings, adhesives, sealants and elastomer applications |
| CN105175707A (en) * | 2015-10-23 | 2015-12-23 | 西安近代化学研究所 | Alkynyl-terminated curing agent and preparation method thereof |
| CN106366306A (en) * | 2016-09-07 | 2017-02-01 | 西安近代化学研究所 | Acetylene-terminated ethylene oxide tetrahydrofuran copolyether containing carbamic acid ester units and synthesis method thereof |
-
2018
- 2018-09-13 CN CN201811067949.8A patent/CN109161012B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05221769A (en) * | 1992-02-10 | 1993-08-31 | Daicel Chem Ind Ltd | High energy binder base composite propellant |
| CN104995229A (en) * | 2013-02-08 | 2015-10-21 | Sika技术股份公司 | Synthesis of polyurethane polymers via copper azide-alkyne click chemistry for coatings, adhesives, sealants and elastomer applications |
| CN105175707A (en) * | 2015-10-23 | 2015-12-23 | 西安近代化学研究所 | Alkynyl-terminated curing agent and preparation method thereof |
| CN106366306A (en) * | 2016-09-07 | 2017-02-01 | 西安近代化学研究所 | Acetylene-terminated ethylene oxide tetrahydrofuran copolyether containing carbamic acid ester units and synthesis method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JINXIAN ZHAI ET AL.: ""Study on bulk preparation and properties of click chemistry end-crosslinked copolyether elastomers "", 《EUROPEAN POLYMER JOURNAL》 * |
Cited By (8)
| 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 |
| CN115521455A (en) * | 2021-06-25 | 2022-12-27 | 北京理工大学 | Preparation method of polytriazole polyether elastomer |
| 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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