CN110172142A - Acrylate-based client glycidol ether nitrate-tetrahydrofuran copolyether prepolymer - Google Patents
Acrylate-based client glycidol ether nitrate-tetrahydrofuran copolyether prepolymer Download PDFInfo
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- CN110172142A CN110172142A CN201910560608.2A CN201910560608A CN110172142A CN 110172142 A CN110172142 A CN 110172142A CN 201910560608 A CN201910560608 A CN 201910560608A CN 110172142 A CN110172142 A CN 110172142A
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- Prior art keywords
- acrylate
- glycidol ether
- based client
- ether nitrate
- prepolymer
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B45/00—Compositions or products which are defined by structure or arrangement of component of product
- C06B45/04—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive
- C06B45/06—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component
- C06B45/10—Compositions or products which are defined by structure or arrangement of component of product comprising solid particles dispersed in solid solution or matrix not used for explosives where the matrix consists essentially of nitrated carbohydrates or a low molecular organic explosive the solid solution or matrix containing an organic component the organic component containing a resin
-
- 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
- C08G65/26—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 from cyclic ethers and other compounds
- C08G65/2603—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 from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—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 from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—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 from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- 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
- C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Molecular Biology (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of acrylate-based client glycidol ether nitrate-tetrahydrofuran copolyether prepolymers, and structural formula is such as shown in (I):
Description
Technical field
The present invention relates to a kind of solid propellant adhesives, and in particular to a kind of acrylate-based client glycidol ether nitre
Acid esters-tetrahydrofuran copolyether prepolymer.
Background technique
End hydroxy butadiene (HTPB) is a kind of active terminal hydroxy group " distant pawl " type high-molecular compound, is had good
Good physicochemical property, glass transition temperature and viscosity are low, technique and mechanical property are good, can accommodate relatively high solid content etc.
Advantage is current adhesive solid propellant research and be most widely used.HTPB molecule chain end contains hydroxyl, can with it is different
Cyanate curing agent carries out heat cure and reacts to form polyurethane elastomer, is a kind of heat-curing type adhesive, but HTPB thermosetting
The problems such as to change that there are conditions of cure harsh, curing time is long, it is difficult to meet the needs of 3D printing rapid shaping.
3D printing technique based on photocuring has many advantages, such as that formed precision is high, curing rate is fast, good weatherability, extensively
Applied to the fields such as biology, medicine, mechanical, manufacture.In order to solve the above problem existing for HTPB adhesive heat cure, scientific research people
Member introduces acrylate group in HTPB molecular structure to assign the HTPB function of adhesive photocuring.Such as Yue Ting is " double
Hold the synthesis and its ultraviolet light solidification research of functionalized polybutadiene's rubber " Beijing University of Chemical Technology's Master's thesis, May 28 in 2015
A kind of acrylate-based client terminated polybutadiene liquid rubber is reported in day, structural formula is as follows:
The acrylate-based client terminated polybutadiene liquid rubber all has carbon-to-carbon double bond in strand both ends and chain, can lead to
It crosses addition photoinitiator and brings it about ultraviolet light curing reaction, be a kind of 3D printing material.But the material is free of energy group,
It is a kind of inert binder, and contains a large amount of double bonds in acrylate-based client polybutadiene strand, although its reactivity
It is lower, but can also participate in photocuring reaction on a small quantity makes the elastomer crosslinked network structure formed after solidifying be difficult to control, and reduces
The mechanical property of elastomer.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of background technique, one kind is provided and contains energy group, and
Carbon-to-carbon double bond is only located at the acrylate-based client glycidol ether nitrate-tetrahydrofuran copolyether prepolymer at strand both ends.
Insight of the invention is that first using trimethylolpropane as initiator, glycidol ether nitrate and tetrahydrofuran
For monomer, obtain taking into account the polyfunctionality terminal hydroxy group glycidol ether nitric acid of energy and flexible characteristic by cationic polymerization
Then ester-tetrahydrofuran copolyether is held its acrylate group for introducing photocuring through esterification with acryloyl chloride
Acrylate-based glycidol ether nitrate-tetrahydrofuran copolyether prepolymer.
In order to solve the above-mentioned technical problem, acrylate-based client glycidol ether nitrate-tetrahydrofuran of the invention is total
Polyether prepolymer, structural formula is such as shown in (I):
Wherein, m+n=5~20 are integer.
Acrylate-based client glycidol ether nitrate of the invention-tetrahydrofuran copolyether prepolymer synthetic route is such as
Under:
Wherein, m+n=5~20 are integer.
Acrylate-based client glycidol ether nitrate-tetrahydrofuran copolyether prepolymer synthetic method of the invention,
The following steps are included:
(1) terminal hydroxy group glycidol ether nitrate-tetrahydrofuran copolyether prepolymer synthesis
At room temperature, trimethylolpropane, methylene chloride and boron trifluoride etherate, stirring are added in reaction flask
After 30min, ice-water bath is cooled to 0~5 DEG C, starts the mix monomer that glycidol ether nitrate and tetrahydrofuran is added dropwise, is added dropwise
Time is 8~12h, and Na is added in the reaction was continued 20~30h after being added dropwise2CO3In aqueous solution and reaction is terminated, organic phase is washed
To neutrality, light yellow viscous liquid terminal hydroxy group glycidol ether nitrate-tetrahydrofuran copolyether prepolymer is obtained after concentration,
The molar ratio of middle boron trifluoride etherate and trimethylolpropane is 1.0~1.5:1.
(2) acrylate-based client glycidol ether nitrate-tetrahydrofuran copolyether prepolymer synthesis
At room temperature, terminal hydroxy group glycidol ether nitrate-tetrahydrofuran copolyether prepolymer, dichloro is added in reaction flask
Methane and triethylamine, stir evenly, and are then cooled to -10~0 DEG C, start the dichloromethane solution that acryloyl chloride is slowly added dropwise,
Time for adding is 6~10h, the reaction was continued 12 after being added dropwise~for 24 hours, water washing is added to neutrality, is obtained after organic phase concentration
Yellow viscous liquid acrylate-based client glycidol ether nitrate-tetrahydrofuran copolyether prepolymer；Wherein triethylamine, propylene
Acyl chlorides and terminal hydroxy group glycidol ether nitrate-tetrahydrofuran copolyether prepolymer molar ratio are 3.6~4.2:3.3~3.6:
1。
Advantages of the present invention:
Acrylate-based client glycidol ether nitrate-tetrahydrofuran copolyether prepolymer average functionality of the invention compared with
It is high, containing itrate group energy group and reactive double bond is only located at the end of strand, can be carried out photocuring, after solidification
Elastomer mechanical property with higher.With acrylate-based client glycidol ether nitrate of the invention-tetrahydrofuran copolymerization
Ether prepolymer is that the elastomer tensile strength that adhesive is formed after ultraviolet light solidifies is 13.6 MPa, and elongation at break is
650%.
Specific embodiment
Invention is further described in detail with reference to embodiments.
Test equipment:
Examination of infrared spectrum uses the 870 type Fourier Transform Infrared Spectrometer of Nexus of U.S. Nicolet company；
Nuclear magnetic resonance test uses 500 type magnetic nuclear resonance analyzer of Switzerland Bruker AV；
Molecular weight and its distribution tests use Britain PL company GPC-50 type gel permeation chromatograph；
Hydroxyl value test is using the acylated method of phthalic anhydride-pyridine；
Viscosity test uses CAP2000+ type cone and plate viscometer；
The test of decomposition peak's temperature uses DSC-2910 type differential thermal analysis scanner；
Mechanics of elastic bodies performance test uses 4505 type universal testing machine of U.S. Instron company Instron.
Embodiment 1
(1) terminal hydroxy group glycidol ether nitrate-tetrahydrofuran copolyether prepolymer synthesis
At room temperature, 2.68g trimethylolpropane, 60ml methylene chloride and 3.41g boron trifluoride are added in reaction flask
Etherate, after stirring 30min, ice-water bath is cooled to 3 DEG C, starts that 35.7g glycidol ether nitrate and 21.6g tetra- is added dropwise
The mix monomer of hydrogen furans, time for adding 10h, the reaction was continued after being added dropwise for 24 hours, and Na is added2CO3In aqueous solution and terminate
Reaction, organic phase are washed to neutrality, light yellow viscous liquid 56.2g are obtained after concentration.
Structural Identification:
IR (KBr, cm-1): 3447 (- OH), 1630,1281,870 (- ONO2), 1123 (C-O-C).
1H NMR(Acetone-d6, 500MHz), δ: 1.65,3.52~3.82,3.93,4.09,4.61~4.76.
Molecular chain conformation: Mn=2900, Mw=4205, Mw/Mn=1.45.
Hydroxyl value is 57.10mgKOH/g.
Compound synthesized by the above analysis data confirm that is terminal hydroxy group glycidol ether nitrate-tetrahydrofuran copolyether
Prepolymer.
(2) acrylate-based client glycidol ether nitrate-tetrahydrofuran copolyether prepolymer synthesis
At room temperature, in reaction flask be added 50g terminal hydroxy group glycidol ether nitrate-tetrahydrofuran copolyether prepolymer,
500ml methylene chloride and 6.81g triethylamine, stir evenly, are then cooled to -5 DEG C, start that acryloyl containing 5.38g is slowly added dropwise
The dichloromethane solution 20ml of chlorine, time for adding 8h, water washing is added to neutrality in the reaction was continued 20h after being added dropwise, organic
Yellow viscous liquid 53.4g is obtained after being mutually concentrated.
Structural Identification:
IR (KBr, cm-1): 1730 (- C=O), 1650 (- C=C), 1630,1281,870 (- ONO2), 1123 (C-O-C).
1H NMR(Acetone-d6, 500MHz), δ: 1.65,3.52~3.82,3.93,4.18,4.61~4.76,5.82,
6.11 6.40.
Molecular chain conformation: Mn=3050, Mw=4636, Mw/Mn=1.52.
Compound synthesized by the above analysis data confirm that is acrylate-based client glycidol ether nitrate-tetrahydrofuran
Copolyether prepolymer.
Acrylate-based client glycidol ether nitrate-tetrahydrofuran copolyether prepolymer performance test: appearance is yellow
Thick liquid, glass transition temperature are -56.8 DEG C, and viscosity is 6.5Pas when decomposition peak's temperature is 217.5 DEG C, 25 DEG C.
Acrylate-based client glycidol ether nitrate of the invention-tetrahydrofuran copolyether prepolymer application performance
(1) adhesive applications
Acrylate-based client glycidol ether nitrate-tetrahydrofuran copolyether prepolymer of the invention is a kind of liquid light
Curing type nitrate copolyether adhesive has many advantages, such as that energy is high, glass transition temperature is low, viscosity is low, thermal stability is good,
It is expected to be applied to 3D printing composite explosives and high-energy solid propellant field.
(2) mechanical property of elastomer
Using acrylate-based client glycidol ether nitrate-tetrahydrofuran copolyether prepolymer of the invention as adhesive,
Methyl acrylate is diluent, and 2,4,6- trimethylbenzoy-dipheny phosphine oxides (TPO) are photoinitiator, three according to
The ratio of 1g:3ml:0.03g is uniformly mixed, and solidification obtains cross-linked elastomer, mechanical property at room temperature under ultraviolet light
It can are as follows: tensile strength 13.6MPa, elongation at break 650%.
Claims (1)
1. a kind of acrylate-based client glycidol ether nitrate-tetrahydrofuran copolyether prepolymer, structural formula such as (I) institute
Show:
Wherein, m+n=5~20 are integer.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910560608.2A CN110172142A (en) | 2019-06-26 | 2019-06-26 | Acrylate-based client glycidol ether nitrate-tetrahydrofuran copolyether prepolymer |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087602A (en) * | 2019-12-16 | 2020-05-01 | 西南科技大学 | Alkenyl polyethylene glycol energetic bonding polymer, elastomer thereof and preparation method |
| CN111454444A (en) * | 2020-05-21 | 2020-07-28 | 西安近代化学研究所 | Acryloyloxy polyhydroxy nitrate polyether prepolymer |
| CN111718480A (en) * | 2020-06-30 | 2020-09-29 | 西安近代化学研究所 | Acryloyloxy polyether curing agent |
| CN113683473A (en) * | 2021-08-06 | 2021-11-23 | 山东大学 | Polyether-based composite solid propellant 3D printing ink and preparation method thereof |
| CN115490817A (en) * | 2022-10-10 | 2022-12-20 | 西安近代化学研究所 | Light-cured combustible polymer and application thereof |
| CN116253870A (en) * | 2022-09-09 | 2023-06-13 | 西安近代化学研究所 | Terminal acrylate polyglycidyl ether nitrate, preparation method and application |
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| CN108976405A (en) * | 2018-07-24 | 2018-12-11 | 西安近代化学研究所 | A kind of three-functionality-degree NIMMO-THF copolyether energetic binder and its synthetic method |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087602A (en) * | 2019-12-16 | 2020-05-01 | 西南科技大学 | Alkenyl polyethylene glycol energetic bonding polymer, elastomer thereof and preparation method |
| CN111454444A (en) * | 2020-05-21 | 2020-07-28 | 西安近代化学研究所 | Acryloyloxy polyhydroxy nitrate polyether prepolymer |
| CN111454444B (en) * | 2020-05-21 | 2022-10-25 | 西安近代化学研究所 | Acryloyloxy polyhydroxy nitrate polyether prepolymer |
| 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 |
| CN113683473A (en) * | 2021-08-06 | 2021-11-23 | 山东大学 | Polyether-based composite solid propellant 3D printing ink and preparation method thereof |
| CN113683473B (en) * | 2021-08-06 | 2022-03-15 | 山东大学 | Polyether-based composite solid propellant 3D printing ink and preparation method thereof |
| CN116253870A (en) * | 2022-09-09 | 2023-06-13 | 西安近代化学研究所 | Terminal acrylate polyglycidyl ether nitrate, preparation method and application |
| CN115490817A (en) * | 2022-10-10 | 2022-12-20 | 西安近代化学研究所 | Light-cured combustible polymer and application thereof |
| WO2024077952A1 (en) * | 2022-10-10 | 2024-04-18 | 西安近代化学研究所 | Photocurable and combustible polymer and use thereof |
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