CN102757362A - Acrylate monomer and preparation method thereof - Google Patents
Acrylate monomer and preparation method thereof Download PDFInfo
- Publication number
- CN102757362A CN102757362A CN2012102542570A CN201210254257A CN102757362A CN 102757362 A CN102757362 A CN 102757362A CN 2012102542570 A CN2012102542570 A CN 2012102542570A CN 201210254257 A CN201210254257 A CN 201210254257A CN 102757362 A CN102757362 A CN 102757362A
- Authority
- CN
- China
- Prior art keywords
- acrylate monomer
- preparation
- esterification
- reaction
- addition
- 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.)
- Pending
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an acrylate monomer and a preparation method thereof, and belongs to the technical field of chemosynthesis and propelling agent application. Acrylonitrile and aminoethanol are subjected to the addition reaction to obtain an intermediate product; the intermediate product is in esterification reaction with unsaturated carboxylic acid to obtain N,N-dinitrile propyl aminoethyl acrylic ester or N,N-dinitrile propyl aminoethyl methyl acrylic ester; and nitrile groupings contained in the monomer can provide a stronger adsorption effect and an more excellent bonding effect. The synthetized product can be used as a polymer bonding agent functional monomer, and provides nitrile alkyl groups absorbed on the surfaces of grains of a solid propellant oxidizing agent. The acrylate monomer has the advantages that the raw materials are very available, the preparation process is easy to realize, and the popularization and the application are facilitated.
Description
Technical field
The present invention relates to a kind of acrylate monomer and preparation method thereof, this acrylate monomer can be used as polymer-type linking agent function monomer, belongs to chemosynthesis, propelling agent applied technical field.
Background technology
Composite solidpropellant be a kind of be parent with the polymkeric substance, solid particulate is that containing of filler can composite high-molecular material.Its mechanical property influence factor is a lot, wherein, guarantees that the effective adhesive that has of solid particulate and adhesive interface is the prerequisite that composite solidpropellant obtains good mechanical property.In order to improve the cohesive strength between the oxygenant and adhesive interface in the SP, add ten thousand/several linking agents in the propellant formulation of being everlasting to the ppt consumption.
From the sixties in 20th century, big quantity research has been carried out in the agent of Chinese scholars para-linkage.Find some small molecules polar compounds, can link to each other with an inorganic oxidizer that the other end is crosslinked through some chemical reaction and binder precursor, thereby strengthen the interfacial layer bonding, improve the mechanical property of propelling agent through an end.
At present, SP uses the small molecules linking agent to be mostly to the effective small molecules polar compound of ammoniumper chlorate (AP), like aziridines, alkanolamine derivative class etc.Wherein use the most extensive with aziridines (like three-(2-methylaziridine) phosphorus oxide, code name MAPO).It is generally acknowledged; Its mechanism of action is because phosphorus oxide functional group (≡ P=O) has stronger polarity; Thereby preferentially by the ammoniumper chlorate surface adsorption; Form one deck aziridines film, aziridine group open loop homopolymerization under the ammoniumper chlorate katalysis, form parcel an ammonium perchlorate oxidiser particle and with the high-modulus tear resistant layer of matrix tackiness agent chemical bond-linking, thereby improve the SP mechanical property significantly.This type linking agent can make that the COMPOSITE SOLID PROPELLANT slurry viscosity significantly descends, combustionproperty is stable, but this compounds of great majority is at room temperature unstable, needs low-temperature storage.
Many itrile groups polyamine compounds is the small molecules linking agent kind that the bonding effect is arranged to nitramine.Wherein the most representative kind is vinyl cyanide and triethylene tetramine/Racemic glycidol or TEPA/Racemic glycidol adduct (TEPANOL; Code name HX-878); Utilize itrile group and the absorption of oxidant with solid particle surface in the adduct; And hydroxyl and isocyanate curing agent that Racemic glycidol provides are crosslinked, so this type linking agent is applicable to nitramine oxidant with solid propelling agent bonding.
Up to nineteen ninety, U.S. scientist Chung S kim has proposed a kind of polymer-type macromole linking agent (NPBA) first in U.S. Pat P4915755, and the breakthrough of the property changed has just appearred in the development of this analog assistant.NPBA is formed by vinyl cyanide, propenoate and the copolymerization of vinylformic acid hydroxyl ester, is applied to the compositepropellent system of filling RDX (RDX) or octogen (HMX), finds that NPBA forms interfacial film between nitramine oxygenant and nitric ether.
Yet; The NPBA NPBA comes with some shortcomings; Made by vinyl cyanide and multiple acrylic ester copolymer like the NPBA neutral polymer, defectives such as hydroxyl skewness appear in the vinyl cyanide reactivity ratio during reaction in copolymer structure much larger than vinylformic acid hydroxyl ester reactivity ratio.In addition, after acrylonitrile compolymer got into main polymer chain, itrile group directly was connected with main chain, and the steric hindrance of main chain influences itrile group and the absorption of nitramine oxygenant.
Summary of the invention
In order to overcome the deficiency of traditional polymer type linking agent, the present invention provides a kind of technology to be prone to realize, contains unsaturated double-bond, has novel acrylic ester monomer of Raolical polymerizable property and preparation method thereof.
The technical scheme that the present invention adopts provides a kind of acrylate monomer, and it is N, N-dintrile propyl group aminoethyl propenoate or N, and N-dintrile propyl group aminoethyl methacrylic ester, structural formula is:
Wherein, R is hydrogen or methyl.
A kind of preparation method of acrylate monomer comprises addition reaction, addition aftertreatment, esterification and post-esterification treatment, and concrete steps are following:
(1) addition reaction
By weight, 1 part of monoethanolamine is dissolved in 1～5 part of zero(ppm) water, drips 1～5 part of vinyl cyanide again, carry out addition reaction, temperature of reaction is 0～35 ℃, and the reaction times is 1～24 hour;
(2) addition aftertreatment
With the first underpressure distillation in water distilling apparatus of the reaction solution after the addition reaction, remove and anhydrate and unreacted raw material, reduced vacuum rectifying again obtains the adduct midbody;
(3) esterification
By weight, 1 part of adduct midbody and 0.3～2 part of unsaturated carboxylic acid are dissolved in the branch aqua, are heated to reflux water-dividing, esterification 2～24 hours;
(4) post-esterification treatment
With the first underpressure distillation in water distilling apparatus of the mixture after the esterification, remove unreacted raw material, reduced vacuum rectifying again, product is a kind of acrylate monomer.
Described unsaturated carboxylic acid is a kind of in the acrylic or methacrylic acid.
In described addition aftertreatment and the post-esterification treatment step, the underpressure distillation condition is 110 ℃ of temperature, vacuum tightness 10mmHg.
In the described addition post-processing step, reduced vacuum rectifying condition is 160 ℃ of temperature, vacuum tightness 2～3mmHg.
In the described post-esterification treatment step, reduced vacuum rectifying condition is 180 ℃ of temperature, vacuum tightness 1～2mmHg.
Described minute aqua is a kind of in benzene, toluene and the hexanaphthene.
Nitrile group-containing linking agent monomer provided by the invention is compared with the used monomer vinyl cyanide of traditional NPBA, has significant beneficial effect to be:
1, technical scheme of the present invention is with vinyl cyanide and monoethanolamine addition; The midbody that obtains obtains N with vinylformic acid (or methylacrylic acid) esterification again; N-dintrile propyl group aminoethyl propenoate (or N, N-dintrile propyl group aminoethyl methacrylic ester), the synthetic product belongs to acrylate monomer; Its unsaturated double-bond that has has Raolical polymerizable property, the polarity itrile group in the monomer structure can with the oxygenant particle surface physical adsorption in the SP.
2, acrylate monomer provided by the invention is realized random copolymerization easily with other propenoate, and obtain structure can the comonomer feed ratio linking agent polymkeric substance of control, reaction is control easily.The itrile group that provides by function monomer on the random copolymerization product side group can with the oxygenant particle surface physical adsorption in the composite solidpropellant; And multipolymer is when using as linking agent in composite solidpropellant; The multipolymer side group is submissiveer through the polarity itrile group that the vinyl cyanide chain link provides than traditional polymer type linking agent; The kindliness of side group makes can improve the easier and nitramine oxygenant absorption of nitrile alkyl bonding action, thereby better mechanical property is provided.
Description of drawings
Fig. 1 is the N by the preparation of the embodiment of the invention 1 technical scheme, the infrared spectrogram of N-dintrile propyl group aminoethyl methacrylic ester;
Fig. 2 is the N that the embodiment of the invention 2 technical schemes provide, the infrared spectrogram of the macromole linking agent for preparing after the copolymerization of N-dintrile propyl group aminoethyl acrylate monomer.
Embodiment
Below in conjunction with embodiment and accompanying drawing technical scheme of the present invention is done further to set forth.
Embodiment one
1, N, N-dintrile propyl group aminoethyl methacrylic ester is synthetic
Four-hole boiling flask equipment mechanical stirring, reflux condensing tube, TM and feed hopper add the frozen water cooling.Add earlier monoethanolamine 305 grams, zero(ppm) water 1060 grams, be cooled to 0～15 ℃ after, drip vinyl cyanide 583 grams at a slow speed.Exothermic heat of reaction, the control drop rate makes reacting liquid temperature be no more than 35 ℃, adds continued nature stirring reaction 3 hours.
Behind the stopped reaction, reaction solution is transferred in the water distilling apparatus, earlier under temperature is 110 ℃, vacuum tightness 10mmHg, removes water and unreacted raw material under reduced pressure, bullion totally 813.1 grams.Bullion is rectifying under 160 ℃, vacuum tightness 2～3mmHg in temperature, receives boiling point and be 152～154 ℃ that (the colorless liquid midbody of vacuum tightness 2～3mmHg) is totally 748.6 grams, GC purity 97.6%, yield 89.6%.
Induction stirring has been equipped in the above-mentioned midbody adding of 167.0g, and the there-necked flask equipment of water trap and reflux condensation mode is under the nitrogen protection; Add hexanaphthene 230 grams and methylacrylic acid 103.2 grams, be heated to backflow, divide the water reaction; Coreaction 24 hours divides water outlet 15 grams, obtains the red-brown reaction solution.Reaction mixture is earlier after temperature is that straight run distillation is removed unreacted raw material under 110 ℃, vacuum tightness 10mmHg; In temperature is rectifying under 180 ℃, vacuum tightness 1mmHg condition; Receiving boiling point is 176～178 ℃ of (colorless liquid product N of 1～2mmHg); N-dintrile propyl group aminoethyl methacrylic ester 160.5 grams, yield 68.1%.Its reaction formula is:
Wherein, R is a methyl.
Referring to accompanying drawing 1, it is the N of present embodiment preparation, the infrared spectrogram of N-dintrile propyl group aminoethyl methacrylic ester, and in the infrared absorption curve of Fig. 1,2950 and 2850cm
-1Be respectively methyl and methylene radical absorption peak in the monomer molecule structure, 2250cm
-1Be the itrile group charateristic avsorption band in the monomer structure, 1740cm
-1Be the ester group absorption peak.Be that (liquid-film method ν) shows product IR: 2950 (CH
3), 2850 (CH
2-), 2250 (C ≡ N), 1740 (C-=O) cm
-1Ultimate analysis (%): C
12H
17N
3O
2Calculated value: C61.28, H7.23, N17.87; Measured value: C61.51, H7.39, N18.32.Ir spectra proof product has comprised the charateristic avsorption band of each functional group of monomer.
2, N, the copolymerization of N-dintrile propyl group aminoethyl methacrylic ester
In the there-necked flask that induction stirring, reflux condensing tube and TM are housed; Add methyl alcohol 25.0 grams, N; N-dintrile propyl group aminoethyl methacrylic ester 17.2 grams, TEB 3K 1.8 grams, Hydroxyethyl acrylate 0.6 gram; Positive Dodecyl Mercaptan 0.3 gram mixes and heat temperature raising to 65 ℃.Divide and add 0.3 gram BPO for 2 times.Being incubated 65 ℃ of reactions 5 hours, after reaction finishes, is that underpressure distillation removes methyl alcohol under the 10mmHg in 60 ℃, vacuum tightness, be distilled to do not have solvent to distillate till.At last orange heavy-gravity N, N-dintrile propyl group aminoethyl methacrylic ester copolymerization product 16.6 gram, yield is 84.7%.
Embodiment two
1, N, N-dintrile propyl group aminoethyl propenoate is synthetic
Four-hole boiling flask equipment mechanical stirring, reflux condensing tube, TM and feed hopper add the frozen water cooling.Add earlier monoethanolamine 305 grams, zero(ppm) water 980 grams, be cooled to 0～15 ℃ after, drip vinyl cyanide 583 grams at a slow speed.Exothermic heat of reaction, the control drop rate makes reacting liquid temperature be no more than 35 ℃, adds continued nature stirring reaction 6 hours.
Behind the stopped reaction, reaction solution is transferred in the water distilling apparatus, earlier under temperature is 110 ℃, the condition of vacuum tightness 10mmHg, removes water and unreacted raw material under reduced pressure, bullion totally 802.2 grams.Bullion is rectifying under 160 ℃, the condition of vacuum tightness 2～3mmHg in temperature, receives boiling point and be 152～154 ℃ that (the colorless liquid midbody of vacuum tightness 2～3mmHg) is totally 760.6 grams, GC purity 97.6%, yield 91.1%.(liquid-film method ν) shows: 3426 (OH), 2886 (CH by IR
2-), 2249 (C ≡ N), 1149 (C-N-C) cm
-1Ultimate analysis (%): C
11H
15N
3O
2Calculated value: C57.49, H7.78, N25.15; Measured value: C57.79, H7.66, N24.86.Its reaction formula is:
Wherein, R is a hydrogen.
Induction stirring has been equipped in the above-mentioned midbody adding of 250.5g, and the there-necked flask equipment of water trap and reflux condensation mode is under the nitrogen protection; Add toluene 320 grams and vinylformic acid 130.0 grams, be heated to backflow, divide the water reaction; Coreaction 6 hours divides water outlet 25 grams, obtains orange-yellow reaction solution.Reaction mixture is earlier after temperature is that straight run distillation is removed unreacted raw material under 110 ℃, vacuum tightness 10mmHg condition; In temperature is rectifying under 180 ℃, vacuum tightness 1mmHg; Receiving boiling point is 181～183 ℃ of (colorless liquid product N of 1～2mmHg); N-dintrile propyl group aminoethyl propenoate 267.9 grams, yield 80.8%.Product ultimate analysis (%): C
11H
15N
3O
2Calculated value: C59.73, H6.79, N19.00; Measured value: C60.11, H6.71, N19.21.
2, N, N-dintrile propyl group aminoethyl acrylic ester copolymer
Take by weighing the N for preparing, N-dintrile propyl group aminoethyl acrylate monomer 545.3g, TEB 3K 55.8g, Hydroxyethyl acrylate 20.9g obtain mix monomer with three kinds of monomers mixing in beaker, and be subsequent use.
In the there-necked flask that induction stirring, reflux condensing tube, TM and feed hopper are housed, add ethanol 780g, positive Dodecyl Mercaptan 8.5g, Diisopropyl azodicarboxylate 6.2g, stirring and dissolving.Be warming up to 70 ℃, drip the above-mentioned mix monomer for preparing, added in 30 minutes.Add 78 ℃ of reactions of back insulation 2 hours.
After reaction finishes, be that underpressure distillation desolventizes under the 10mmHg in 60 ℃, vacuum tightness, distillation time be distilled to do not have solvent to distillate again till.At last orange thickness macromole linking agent product 601.9g, yield is 96.8%.
Referring to accompanying drawing 2, it is the N of present embodiment preparation, the infrared spectrogram of N-dintrile propyl group aminoethyl Yodo Sol GH 28; In the infrared absorption curve of Fig. 2,3420cm
-1The pendant hydroxyl group absorption peak that provides for Hydroxyethyl acrylate copolymerization chain link, 2930 and 2860cm
-1Be respectively methyl and methylene radical absorption peak in each monomer chain link, 2250cm
-1Be N, the itrile group charateristic avsorption band that N-dintrile propyl group aminoethyl propenoate chain link provides, 1730cm
-1It then is carbonyl absorption peak in the various propenoate chain link structures.Be that infrared (liquid-film method ν) shows product: 3420 (OH), 2930 (CH
3), 2860 (CH
2-), 2250 (C ≡ N), 1730 (C=O) cm
-1IR spectroscopy shows that the linking agent macromole is four kinds of monomeric multipolymers.
Prepared N, N-dintrile propyl group aminoethyl propenoate has unsaturated double-bond Raolical polymerizable property, and the macromole linking agent that copolymerization obtains can be applicable to the propelling agent technical field.
Claims (7)
1. an acrylate monomer is characterized in that it is N, N-dintrile propyl group aminoethyl propenoate or N, and N-dintrile propyl group aminoethyl methacrylic ester, structural formula is:
Wherein, R is hydrogen or methyl.
2. the preparation method of an acrylate monomer as claimed in claim 1 comprises addition reaction, addition aftertreatment, esterification and post-esterification treatment, it is characterized in that concrete steps are following:
(1) addition reaction
By weight, 1 part of monoethanolamine is dissolved in 1～5 part of zero(ppm) water, drips 1～5 part of vinyl cyanide again, carry out addition reaction, temperature of reaction is 0～35 ℃, and the reaction times is 1～24 hour;
(2) addition aftertreatment
With the first underpressure distillation in water distilling apparatus of the reaction solution after the addition reaction, remove and anhydrate and unreacted raw material, reduced vacuum rectifying again obtains the adduct midbody;
(3) esterification
By weight, 1 part of adduct midbody and 0.3～2 part of unsaturated carboxylic acid are dissolved in the branch aqua, are heated to reflux water-dividing, esterification 2～24 hours;
(4) post-esterification treatment
With the first underpressure distillation in water distilling apparatus of the mixture after the esterification, remove unreacted raw material, reduced vacuum rectifying again, product is a kind of acrylate monomer.
3. the preparation method of a kind of acrylate monomer according to claim 2 is characterized in that: described unsaturated carboxylic acid is a kind of in the acrylic or methacrylic acid.
4. the preparation method of a kind of acrylate monomer according to claim 2, it is characterized in that: in described addition aftertreatment and the post-esterification treatment step, the underpressure distillation condition is 110 ℃ of temperature, vacuum tightness 10mmHg.
5. the preparation method of a kind of acrylate monomer according to claim 2, it is characterized in that: in the described addition post-processing step, reduced vacuum rectifying condition is 160 ℃ of temperature, vacuum tightness 2～3mmHg.
6. the preparation method of a kind of acrylate monomer according to claim 2, it is characterized in that: in the described post-esterification treatment step, reduced vacuum rectifying condition is 180 ℃ of temperature, vacuum tightness 1～2mmHg.
7. the preparation method of a kind of acrylate monomer according to claim 2 is characterized in that: described minute aqua is a kind of in benzene, toluene and the hexanaphthene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102542570A CN102757362A (en) | 2012-07-20 | 2012-07-20 | Acrylate monomer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102542570A CN102757362A (en) | 2012-07-20 | 2012-07-20 | Acrylate monomer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102757362A true CN102757362A (en) | 2012-10-31 |
Family
ID=47052046
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012102542570A Pending CN102757362A (en) | 2012-07-20 | 2012-07-20 | Acrylate monomer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102757362A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114213668A (en) * | 2021-12-15 | 2022-03-22 | 天元航材(营口)科技股份有限公司 | Preparation method of HX-878 |
| CN114956921A (en) * | 2022-06-30 | 2022-08-30 | 哈尔滨工业大学 | Magnetically deformable solid rocket mixed gel propellant and preparation method thereof |
| CN115073247A (en) * | 2021-12-22 | 2022-09-20 | 湖北航天化学技术研究所 | Bonding type phase change coating agent and synthesis method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4915755A (en) * | 1987-10-02 | 1990-04-10 | Kim Chung S | Filler reinforcement of polyurethane binder using a neutral polymeric bonding agent |
| US5530092A (en) * | 1992-01-13 | 1996-06-25 | Dsm N.V. | Dendritic macromolecule and the preparation thereof |
-
2012
- 2012-07-20 CN CN2012102542570A patent/CN102757362A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4915755A (en) * | 1987-10-02 | 1990-04-10 | Kim Chung S | Filler reinforcement of polyurethane binder using a neutral polymeric bonding agent |
| US5530092A (en) * | 1992-01-13 | 1996-06-25 | Dsm N.V. | Dendritic macromolecule and the preparation thereof |
Non-Patent Citations (3)
| Title |
|---|
| 《Zhurnal Organicheskoi Khimii》 19711231 Bodnaryuk, F. N. et al Esters of alpha,beta-unsaturated acids with functional groups in the alkoxy radical. XII. Cyanoethylaminoalkyl esters of acrylic and methacrylic acids 第2129-2132页 1-7 第7卷, 第10期 * |
| BODNARYUK, F. N. ET AL: "Esters of α,β-unsaturated acids with functional groups in the alkoxy radical. XII. Cyanoethylaminoalkyl esters of acrylic and methacrylic acids", 《ZHURNAL ORGANICHESKOI KHIMII》, vol. 7, no. 10, 31 December 1971 (1971-12-31), pages 2129 - 2132 * |
| CA: "34508-92-4", 《STN-REGISTRY》, 16 November 1984 (1984-11-16) * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114213668A (en) * | 2021-12-15 | 2022-03-22 | 天元航材(营口)科技股份有限公司 | Preparation method of HX-878 |
| CN115073247A (en) * | 2021-12-22 | 2022-09-20 | 湖北航天化学技术研究所 | Bonding type phase change coating agent and synthesis method and application thereof |
| CN114956921A (en) * | 2022-06-30 | 2022-08-30 | 哈尔滨工业大学 | Magnetically deformable solid rocket mixed gel propellant and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102977260B (en) | Macromolecule bonding agent and preparation method thereof | |
| CN104761994B (en) | A kind of preparation method of photo-curable silicone modified epoxy paint film | |
| CN101775137B (en) | Water-based non-isocyanate polyurethane and preparation method thereof | |
| CN101982512B (en) | Silicone acrylate coating resin and preparation method thereof | |
| CN102757362A (en) | Acrylate monomer and preparation method thereof | |
| CN101899163B (en) | Method for preparing self-emulsifiable non-ionic water-borne novolac epoxy resin emulsion | |
| CN109810210B (en) | Alkynyl neutral polymer bonding agent, preparation method and propellant | |
| CN110172142A (en) | Acrylate-based client glycidol ether nitrate-tetrahydrofuran copolyether prepolymer | |
| US20100140542A1 (en) | Benzoxazine containing compositions of matter and curable compositions made therewith | |
| CN108003275A (en) | It is a kind of suitable for macromolecular bonding agent of polytriazoles crosslinking curing system and its preparation method and application | |
| CN107629082A (en) | A kind of novel siliceous benzoxazine and preparation method thereof | |
| CN102675642A (en) | Method for preparing solid organic silicon resin by utilizing chlorosilane high-boiling residue | |
| CN105503756B (en) | A kind of multiple tooth shape structural macromolecules bonding agent and preparation method thereof | |
| CN112574335B (en) | Modified hydroxyl-terminated polybutadiene and preparation method and application thereof | |
| JPH0581584B2 (en) | ||
| Wu et al. | Catalyst‐Free Four‐Component Polymerization of Propiolic Acids, Benzylamines, Organoboronic Acids, and Formaldehyde toward Functional Poly (propargylamine) s | |
| CN102875777A (en) | Novel epoxy hardener and preparation method thereof | |
| Wang et al. | Novel geminal dinitro esters as energetic plasticizers for GAP binder | |
| US3183216A (en) | Boron-containing polymer and method of making the same | |
| CN102399352A (en) | Thermoplastic elastomer containing energy and its synthetic method | |
| CN102690619A (en) | Preparation method of compound type curing agent applied to urea resin | |
| CN1376662A (en) | Free radical and cation hybridized trigger for optical solidification and its preparing process and application | |
| CN108461308B (en) | A kind of graphene/poly ion liquid composite material and preparation method and application | |
| CN106279242A (en) | A kind of three-functionality-degree acrylate monomer of silicone-containing structure and preparation method thereof | |
| Kaplan et al. | Lanthanide–imidazole complexes as latent curing agents for epoxy resins |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20121031 |