CN115368868A - Photocuring allyl energetic adhesive and preparation method thereof - Google Patents
Photocuring allyl energetic adhesive and preparation method thereof Download PDFInfo
- Publication number
- CN115368868A CN115368868A CN202210820328.2A CN202210820328A CN115368868A CN 115368868 A CN115368868 A CN 115368868A CN 202210820328 A CN202210820328 A CN 202210820328A CN 115368868 A CN115368868 A CN 115368868A
- Authority
- CN
- China
- Prior art keywords
- reaction
- solution
- photocuring
- dmf
- adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- 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
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a photocuring allyl energetic adhesive and a preparation method thereof, and the structural formula is as follows:
wherein n =4 to 10 is an integer, and m =2 to 5 is an integer. The photocuring allyl energetic adhesive contains more photocuring groups, can be rapidly cured within 10s under the condition of ultraviolet irradiation, and can be completely cured within 1 min. The photocurable allylic energetic adhesive of the present invention contains an energy group-triazole ring and does not reduce energy levels compared to GAP adhesives.
Description
Technical Field
The invention belongs to the technical field of solid propellants, relates to an adhesive, and particularly relates to a photocuring allyl energetic adhesive and a preparation method thereof.
Background
The binder, which acts as the "heart" of what is known as the solid propellant, is one of the most critical components affecting the performance of the solid propellant. The solid propellant is an energy-containing composite material which is formed by mixing an adhesive serving as a matrix with energy-containing solid particles (an oxidizer, metal fuel and the like), wherein the adhesive is a key component and has important influence on the processing technology, the mechanical property and the energy characteristic of the propellant. With the continuous development of the solid propellant, the comprehensive performance requirements of people on the propellant are continuously improved. In order to meet the high energy requirements of propellants, it has been necessary to increase the energy of the solid propellant charge on the one hand and of the propellant binder on the other hand, for which energetic polymer binders have to be used. Energetic polymer binders are currently the most widely used energetic polymers based on GAP. The adhesive GAP is an energetic prepolymer with a side chain containing azide groups and a main chain of a polyether structure, the prepolymer has positive heat of formation, high energy level and can improve the burning rate of a propellant, the GAP is a light yellow viscous liquid, the heat of formation (+ 957 kJ/kg) is 1.27-1.3g/cm, and the density is 3 The nitrogen content is 38-41%, and the glass transition temperature is about-50 ℃.
Such as Pang Aimin et al GAP propellant mechanical properties preliminary study, solid rocket technology, 1995, 18 (2): 31-34 discloses the molecular structure characteristics of typical GAP adhesive and the mechanical property of polyurethane elastomer film formed after curing, wherein the molecular structure of GAP is simply as follows:
GAP is usually obtained by taking epoxy chloropropane as a raw material through two steps of reactions of cationic ring-opening polymerization and azidation, and due to the limitation of the first step of polymerization reaction, GAP with high molecular weight is difficult to obtain, the molecular weight of GAP is generally about 3000, GAP is taken as an adhesive, N-100 is taken as a curing agent, when the R value is 1.2, the maximum tensile strength of the prepared polyurethane elastomer film at room temperature is 0.53MPa, the elongation at break is 56.5%, the mechanical property is low, and the curing speed is slow in the charge curing process, so that great difficulty is brought to the adjustment of the mechanical property of a formula.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a photocuring allyl energy-containing adhesive and a preparation method thereof, and solve the technical problem that the curing rate and the mechanical property of the adhesive in the prior art need to be further improved.
In order to solve the technical problems, the invention adopts the following technical scheme:
a photocurable allylic energetic binder having the structural formula:
wherein n =4 to 10 is an integer, and m =2 to 5 is an integer.
The invention also provides a preparation method of the photocuring allylic energy-containing adhesive, which is carried out according to the following synthesis steps:
weighing azido polyether, propiolic alcohol acrylate, cuI catalyst and DMF solvent, adding into a reaction vessel, stirring and reacting at room temperature, pouring ice water into reaction liquid after the reaction is finished, extracting with ethyl acetate, filtering, washing, drying and concentrating to obtain hydroxyl polyether;
step two, dissolving hydroxyl polyether in DMF at 0 ℃, then dropwise adding the hydroxyl polyether into a NaH + DMF solution, stirring the solution at 0 ℃, then adding bromopropylene into the reaction solution, and intermittently stirring the reaction solution at room temperature to react; after the reaction is finished, quenching the reaction by using ice water at the temperature of 0 ℃, extracting the reaction solution by using chloroform and saturated saline solution, and then separating, drying and concentrating to obtain a target product, namely the photocuring allyl energy-containing adhesive.
The invention also has the following technical characteristics:
specifically, the method comprises the following synthetic steps:
step one, weighing 1g of azido polyether, 1.23g of propiolic acrylate, 0.01g of catalyst CuI and 10ml of DMF solvent, adding the weighed materials into a reaction vessel, stirring the materials at room temperature for reaction for 6 hours, pouring ice water into reaction liquid after the reaction is finished for quenching the reaction and dissolving water-soluble substances in the reaction liquid, extracting the water-soluble substances with ethyl acetate, and filtering, washing, drying and concentrating the reaction liquid to obtain hydroxyl polyether;
step two, 1.83g of hydroxyl polyether is dissolved in 1.8ml of DMF at 0 ℃, then dropwise added into a solution of 0.8gNaH +14ml of DMF and stirred at 0 ℃ for 30min, then 2.3g of bromopropylene is added into the reaction liquid and the reaction is carried out for 20h under intermittent stirring at room temperature; after the reaction is finished, quenching the reaction by using ice water at the temperature of 0 ℃, extracting the reaction solution by using chloroform and saturated saline solution, and then separating, drying and concentrating to obtain a target product, namely the photocuring allyl energy-containing adhesive.
Compared with the prior art, the invention has the following technical effects:
the photocuring allyl energetic adhesive contains more photocuring groups, can be rapidly cured within 10s under the condition of ultraviolet irradiation, and can be completely cured within 1 min.
(II) the photocurable allylic energy-containing adhesives of the invention contain an energy group-triazole ring and do not have a reduced energy level compared to GAP adhesives.
And (III) the allyl bonding group introduced on the branched chain in the adhesive improves the crosslinking density of an adhesive matrix and improves the mechanical property of the solid propellant.
(IV) the photocuring allyl energy-containing adhesive has a simple synthesis method, has high molecular weight, contains allyl groups in branched chains, and can endow an elastomer with high mechanical properties.
(IV) the maximum tensile strength of the elastomer prepared by using the photocuring allyl energetic adhesive of the invention as a raw material is 0.71MPa, and the elongation at break is 276%, while the maximum tensile strength of the polyurethane elastomer prepared by using GAP as a raw material in the reference is 0.53MPa, and the elongation at break is 56.5%.
Drawings
FIG. 1 is a molecular weight distribution diagram obtained by GPC (gel permeation chromatography) at 1-fold and 8-fold times.
FIG. 2 is a DSC (differential scanning calorimetry) thermogram.
The present invention will be explained in further detail with reference to examples.
Detailed Description
It should be noted that all the raw materials in the present invention, unless otherwise specified, are all those known in the art, i.e., all the raw materials in the present invention are commercial raw materials. For example, the N-100 curing agent is a known commercial N-100 curing agent.
The overall technical concept of the invention is as follows:
through long-term research of the application, the following findings are obtained: (1) the reason why the GAP-based solid propellant is slow in curing speed: on the one hand, the attached curing groups are fewer, and on the other hand, the curing groups are hydroxyl groups (thermosetting groups), and the curing speed of the thermosetting groups is slower than that of the photocuring groups. (2) The GAP-based solid propellant has low mechanical performance due to the large-CH in the side chain 2 N 3 The existence of the group does not contain other curing groups, does not contribute to the crosslinking density of the GAP adhesive matrix, and causes less bonding action points and weak bonding function.
In order to solve the problems of slow curing rate and poor mechanical property of the GAP adhesive, the technical concept of the invention is as follows:
(A) The photocuring group is introduced into the GAP adhesive to replace the thermosetting group to obtain a photocuring bonding system, and the main chain and the branched chain of the adhesive can participate in the curing process simultaneously during ultraviolet irradiation, so that the composite material can be cured quickly.
(B) Because the allyl group is introduced into the position of the original azide group, the allyl group and the main chain group show good synergistic effect, the curing depth and the crosslinking density of a molded sample are improved, the curing hardness can be enhanced, the shrinkage rate is reduced, the adhesive force in the writing process is improved, and the molded sample has good comprehensive performance.
(C) The number of main chain atoms is increased by a chain extension method. And the introduction of the energy-containing group is also carried out simultaneously with the introduction of the photocuring group so as not to affect the energy level of the adhesive.
Testing an instrument:
(1) Infrared spectrum:
the infrared spectra were measured using a Nexus 870 Fourier transform Infrared spectrometer from Nicolet, USA.
(2) Nuclear magnetic resonance:
the nuclear magnetization was measured with an AVANCE AV500 nuclear magnetic resonance apparatus from Bruker, germany.
(3) Number average molecular weight:
equipment: gel permeation chromatograph model GPC-50 from PL corporation, UK.
GPC test conditions: the chromatographic column is series connected by PLGel MIXED-E; the mobile phase is DMF; the column temperature was 35 ℃; the detector is a differential refractive detector.
(4) Mechanical properties:
equipment: universal materials testing machine model Instron 4505, from Instron corporation, usa.
The test method comprises the following steps: the stretching rate is 100mm/min, according to GJB770B-2005 method 413.1.
The present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention fall within the protection scope of the present invention.
The embodiment is as follows:
this example provides a photocurable allylic energetic binder having the formula:
wherein n =4 to 10 is an integer, and m =2 to 5 is an integer.
The preparation of the photocurable allylic energetic binder of this example is as follows.
The method is carried out according to the following synthetic route:
the method is carried out according to the following synthesis steps:
step one, weighing 1g of azido polyether, 1.23g of propiolic acrylate, 0.01g of catalyst CuI and 10ml of DMF solvent, adding the weighed materials into a reaction vessel, stirring the materials at room temperature for reaction for 6 hours, pouring ice water into reaction liquid after the reaction is finished for quenching the reaction and dissolving water-soluble substances in the reaction liquid, extracting the materials by using ethyl acetate, and then filtering, washing, drying and concentrating the reaction liquid to obtain hydroxyl polyether (compound 1) with the yield of 88%.
After the experimental process is stable, the method can be gradually amplified to 8 times of the original sample feeding amount, and the yield is basically unchanged.
Step two, 1.83g of hydroxyl polyether (compound 1) is dissolved in 1.8ml of DMF at 0 ℃, then dropwise added to a solution of 0.8gNaH +14ml of DMF and stirred at 0 ℃ for 30min, then 2.3g of bromopropylene is added to the reaction solution and the reaction is intermittently stirred at room temperature for 20h; after the reaction, the reaction was quenched with ice water at 0 ℃, and the reaction solution was extracted with chloroform and a saturated saline solution, followed by liquid separation, drying and concentration to obtain the target product (compound 2), i.e., a photocurable allylic energy-containing adhesive, in a yield of 93%.
After the experimental process is stable, the method can be gradually amplified to 8 times of the original sample feeding amount, and the yield is basically unchanged.
And (3) structural identification:
IR(KBr，cm -1 ): 3044 (= CH, stretching vibration), 1758 (O = C, stretching vibration), 1621 (C = C, stretching vibration), 1124 (C-O-C, stretching vibration), 958 (= CH, out-of-plane deforming vibration), 927 (= CH) (= CH 2 Out-of-plane deformation vibration).
1 H NMR: it should be noted that, the target product prepared in this example is too polar and insoluble in deuterated reagents commonly used in the nmr characterization process, so that accurate identification cannot be obtained 1 H NMR data.
Molecular weight and molecular weightCloth: m n ＝8312，M w ＝11296，M w /M n ＝1.36。
The molecular weight distribution diagram of the target product prepared in this example and the target product obtained by enlarging the amount of the whole target product in this example by 8 times by GPC is shown in fig. 1, and it can be seen from fig. 1 that the productivity is enlarged and the molecular weight distribution of the target product is relatively stable.
Glass transition temperature T g : FIG. 2 is a DSC thermogram, and from FIG. 2, it can be seen that T of the objective product prepared in this example g ＝-67.6℃。
Viscosity: as shown in table 1, the viscosity decreased with increasing temperature.
TABLE 1 viscosity as a function of temperature
| Temperature of | 20 |
40 |
60℃ |
| viscosity/(Pa. S) | 33.6 | 10.8 | 3.9 |
The above identification data confirms that the target product synthesized in this example is a target compound photocured allylic energetic binder of the present application.
And (3) application performance testing:
(1) Miscibility test with isocyanate curing agent:
n-100 is selected as a curing agent, and the miscibility and reactivity of the photocuring allyl energetic adhesive and the curing agent are examined.
The adhesive has good miscibility with the N-100 curing agent, the mixed solution is clear and transparent, and the formed mixed solution can be stably subjected to curing reaction at the temperature of 55 ℃.
(2) Mechanical property test of the elastomer:
the adhesive with the number average molecular weight of 7208 is used as a raw material, mixed with a curing agent N-100 and heated for curing, and when the R value is 1.2, the prepared polyurethane elastomer has the following mechanical properties: the maximum tensile strength was 0.71MPa, and the elongation at break was 276%.
Claims (3)
1. A photocurable allylic energetic adhesive characterized by the structural formula:
wherein n =4 to 10 is an integer, and m =2 to 5 is an integer.
2. The method of preparing a photocurable allylic energetic binder of claim 1 carried out according to the following synthetic steps:
weighing azido polyether, propiolic alcohol acrylate, cuI catalyst and DMF solvent, adding into a reaction container, stirring at room temperature for reaction, pouring ice water into reaction liquid after the reaction is finished, extracting with ethyl acetate, filtering, washing, drying and concentrating to obtain hydroxyl polyether;
step two, dissolving hydroxyl polyether in DMF at 0 ℃, then dropwise adding the hydroxyl polyether into a NaH + DMF solution, stirring the solution at 0 ℃, then adding bromopropylene into the reaction solution, and intermittently stirring the reaction solution at room temperature to react; after the reaction is finished, quenching the reaction by using ice water at the temperature of 0 ℃, extracting the reaction solution by using chloroform and saturated saline solution, and then separating, drying and concentrating to obtain a target product, namely the photocuring allyl energy-containing adhesive.
3. The method of preparing a photocurable allylic energetic binder of claim 2 carried out according to the following synthetic steps:
step one, weighing 1g of azido polyether, 1.23g of propiolic acrylate, 0.01g of catalyst CuI and 10ml of DMF solvent, adding the weighed materials into a reaction vessel, stirring the materials at room temperature for reaction for 6 hours, pouring ice water into reaction liquid after the reaction is finished for quenching the reaction and dissolving water-soluble substances in the reaction liquid, extracting the water-soluble substances with ethyl acetate, and filtering, washing, drying and concentrating the reaction liquid to obtain hydroxyl polyether;
step two, 1.83g of hydroxyl polyether is dissolved in 1.8ml of DMF at 0 ℃, then dropwise added to a solution of 0.8g of NaH +14ml of DMF and stirred at 0 ℃ for 30min, then 2.3g of bromopropylene is added to the reaction solution and the reaction is carried out at room temperature for 20h with intermittent stirring; after the reaction is finished, quenching the reaction by using ice water at the temperature of 0 ℃, extracting the reaction solution by using chloroform and saturated saline solution, and then separating, drying and concentrating to obtain a target product, namely the photocuring allyl energy-containing adhesive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210820328.2A CN115368868B (en) | 2022-07-12 | 2022-07-12 | Photo-curing allyl type energetic adhesive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210820328.2A CN115368868B (en) | 2022-07-12 | 2022-07-12 | Photo-curing allyl type energetic adhesive and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115368868A true CN115368868A (en) | 2022-11-22 |
| CN115368868B CN115368868B (en) | 2023-07-18 |
Family
ID=84062166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210820328.2A Active CN115368868B (en) | 2022-07-12 | 2022-07-12 | Photo-curing allyl type energetic adhesive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115368868B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115180994A (en) * | 2022-07-12 | 2022-10-14 | 西安近代化学研究所 | Photo-thermal dual-curing allyl energetic adhesive and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993019132A2 (en) * | 1992-03-19 | 1993-09-30 | Dsm N.V. | Binder composition for powder coatings based on unsaturated polyesters |
| DE4324322A1 (en) * | 1993-07-20 | 1995-01-26 | Thera Ges Fuer Patente | Flexibilised epoxy resin compositions which cure with photoinitiation, their preparation and use |
| CN107674628A (en) * | 2017-11-06 | 2018-02-09 | 西安近代化学研究所 | A kind of three block type alkenyl polyether adhesive and its synthetic method |
| CN108822288A (en) * | 2018-06-05 | 2018-11-16 | 西安近代化学研究所 | A kind of alkenyl polyether is containing can nitric acid ester adhesive and its synthetic method |
| EP3808787A1 (en) * | 2019-10-16 | 2021-04-21 | Margarita Zimmer | Photocurable adhesive composition for mascara extension |
-
2022
- 2022-07-12 CN CN202210820328.2A patent/CN115368868B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993019132A2 (en) * | 1992-03-19 | 1993-09-30 | Dsm N.V. | Binder composition for powder coatings based on unsaturated polyesters |
| DE4324322A1 (en) * | 1993-07-20 | 1995-01-26 | Thera Ges Fuer Patente | Flexibilised epoxy resin compositions which cure with photoinitiation, their preparation and use |
| CN107674628A (en) * | 2017-11-06 | 2018-02-09 | 西安近代化学研究所 | A kind of three block type alkenyl polyether adhesive and its synthetic method |
| CN108822288A (en) * | 2018-06-05 | 2018-11-16 | 西安近代化学研究所 | A kind of alkenyl polyether is containing can nitric acid ester adhesive and its synthetic method |
| EP3808787A1 (en) * | 2019-10-16 | 2021-04-21 | Margarita Zimmer | Photocurable adhesive composition for mascara extension |
Non-Patent Citations (1)
| Title |
|---|
| 徐国财: "紫外光固化粘合剂的发展", 化学与粘合, no. 01 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115180994A (en) * | 2022-07-12 | 2022-10-14 | 西安近代化学研究所 | Photo-thermal dual-curing allyl energetic adhesive and preparation method thereof |
| CN115180994B (en) * | 2022-07-12 | 2023-06-09 | 西安近代化学研究所 | Photo-thermal dual-curing allyl type energetic adhesive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115368868B (en) | 2023-07-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110183645B (en) | Photo-curing nitrate polyether and synthetic method thereof | |
| CN107674628B (en) | Three-block type alkenyl polyether adhesive and synthesis method thereof | |
| CN107739588B (en) | Polyalkenyl-terminated copolyether adhesive and synthesis method thereof | |
| CN110982010B (en) | Neutral macromolecular bonding agent and preparation method thereof | |
| CN115368868B (en) | Photo-curing allyl type energetic adhesive and preparation method thereof | |
| Wei et al. | Design of photoinitiator-functionalized hydrophilic nanogels with uniform size and excellent biocompatibility | |
| CN107446074B (en) | Polyhydroxy polybutadiene adhesive and synthesis method thereof | |
| Buchheit et al. | Functionalized acrylic polyhydroxy urethanes as molecular tool box for photocurable thermosets and 3D printing | |
| Zhang et al. | Synthesis and Characterization of Novel Azido Polymers: Hyperbranched Poly‐3‐azidomethyl‐3‐hydroxymethyl Oxetane | |
| JPH04120124A (en) | Production of epoxy resin having high molecular weight | |
| CN115180994B (en) | Photo-thermal dual-curing allyl type energetic adhesive and preparation method thereof | |
| CN109837053B (en) | Polyene polytetrahydrofuran adhesive and synthesis method thereof | |
| CN110577629B (en) | Degradable epoxy resin and preparation method thereof | |
| CN110016120B (en) | Synthesis method of linear epoxy resin containing multiple glycidyl ether groups | |
| CN109320694B (en) | Preparation method of stereocomplex polylactic acid | |
| CN111574705B (en) | Dual-curing nitrate polyether and synthetic method thereof | |
| CN116284681A (en) | Preparation method and application of high-temperature-resistant polyurethane resin | |
| CN117050704A (en) | Six-functional photo-curing energy-containing adhesive for printing and forming and synthesis method | |
| Zhang et al. | The effect of a novel of hyperbranched cross-linking agent on the mechanical of hydroxyl-terminated polybutadiene based solid propellant | |
| CN115028829B (en) | 1,2, 3-triazole-4-methylene nitrate modified azide adhesive, synthesis method and application | |
| CN108586724A (en) | A kind of three-functionality-degree PNIMMO energetic binders and its synthetic method | |
| Toncheva-Moncheva et al. | Thiol–ene coupling reaction achievement and monitoring by “in situ” UV irradiation NMR spectroscopy | |
| CN117050706A (en) | Six-functionality photo-thermal dual-curing energetic adhesive and synthesis method thereof | |
| CN114989414B (en) | Photo-thermal composite curing polytetrahydrofuran oligomer | |
| CN117430802B (en) | Preparation method of polyhydroxy acrylic ester macromer, method for preparing polymer polyol by using polyhydroxy acrylic ester macromer and application of polyhydroxy acrylic ester macromer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |