CN112812259A - Light-cured adhesive for additive manufacturing and synthetic method thereof - Google Patents

Light-cured adhesive for additive manufacturing and synthetic method thereof Download PDF

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CN112812259A
CN112812259A CN202011567005.4A CN202011567005A CN112812259A CN 112812259 A CN112812259 A CN 112812259A CN 202011567005 A CN202011567005 A CN 202011567005A CN 112812259 A CN112812259 A CN 112812259A
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gap
acrylate
diisocyanate
pthf
meth
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蔺向阳
彭洋
郑文芳
刘征哲
张西亚
郭本月
史少芳
张弼凤
李恒
檀成
袁璟
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Nanjing University of Science and Technology
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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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
    • C06B21/0033—Shaping the mixture
    • 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
    • C06—EXPLOSIVES; MATCHES
    • C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
    • C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
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  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention discloses a photocuring energetic adhesive for additive manufacturing and a synthesis method thereof, belonging to the field of energetic materials. The invention uses the compound containing azide group (-N)3) The aliphatic polyether intermediate is used as a starting material, and then diisocyanate and hydroxy acrylate are used for blocking to obtain the bifunctional azido polyether urethane acrylate. The azido polyether type polyurethane acrylate has photocuring characteristic, low viscosity and proper matching activityThe release agent can be molded and manufactured by using a 3D printing technology, in addition, the polyether main chain and the terminal polyurethane have certain flexibility and good low-temperature mechanical property, the glass transition temperature is between-20 ℃ and-60 ℃, and the basic requirements of the propellant adhesive are met.

Description

Light-cured adhesive for additive manufacturing and synthetic method thereof
Technical Field
The invention relates to a photo-curing energetic adhesive and a synthesis method thereof, belonging to the field of energetic materials.
Background
The adhesive is a core component in the solid propellant, can provide energy for the solid propellant in a burning mode, is in a liquid state before curing, can be used as a dispersing phase for other solid fillers to be uniformly mixed so as to ensure stable burning, and has certain toughness as an elastomer after curing to provide good impact resistance for the solid propellant.
The traditional adhesive curing method is thermal curing, namely long-chain diol such as HTPB and GAP is used as a prepolymer, diisocyanate is added to crosslink and cure the prepolymer under the condition of heating. Although the traditional heat curing method is widely applied, the defects of long curing time, easy volatilization of solvent, easy initiation of many side reactions at high temperature and the like exist, and the solid propellant grain with a complex structure is difficult to manufacture due to the adoption of the casting molding method.
The photocuring adhesive has the advantages of high curing speed, high curing rate, normal-temperature or even low-temperature curing, no solvent volatilization and the like, can be used for manufacturing products with complex structures without a mold under the condition of matching with 3D printing technologies such as stereolithography SLA and Digital Light Processing (DLP), and has high printing precision which can reach millimeter or even micron level.
GAP is the first energetic adhesive synthesized in the 70's of the last century, has high energy level and proper low-temperature mechanical property, and has a certain application range. On the other hand, tetrahydrofuran is often used as a comonomer to improve the mechanical properties of the energy-containing adhesive, but also to reduce the energy level of the adhesive. Although early studies reported that substituted derivatives of tetrahydrofuran failed to undergo ring-opening homopolymerization, they could be copolymerized with other unstable cyclic ethers (e.g., propylene oxide derivatives). Dong et al successfully prepared PGAAT (GAP-r-PATHF), a random copolymer of azidoglycidyl ether and 3-azidotetrahydrofuran, which further improved the low temperature mechanical properties of GAP while maintaining energy levels, Tg＝－60℃。
Disclosure of Invention
The invention provides a photocuring energetic adhesive capable of realizing additive manufacturing of energetic materials such as explosives, solid propellants and the like and a synthesis method thereof, aims to solve the problem that photocuring forming of a traditional adhesive is difficult to realize, and also aims to solve the problems that the traditional thermosetting adhesive is incomplete in curing, solvent volatilization and side reaction are easily caused by high temperature, and a complex model cannot be manufactured.
In order to solve the technical problem, the invention provides a bifunctional azido polyether polyurethane acrylate which is obtained by firstly reacting an azido polyether intermediate with excessive diisocyanate to obtain a double-ended polyurethane prepolymer, and then adding (methyl) acrylic hydroxyl ester for further end capping. The concrete structure is as follows:
Figure BDA0002860947760000021
wherein R is1Represents one or two of-H and-Me;
R2represents-C2H4-、-C3H6-one or both;
R3represents toluene diisocyanate, isophorone diisocyanateOne or more of cyanate and hexamethylene diisocyanate.
Further, the azide polyether intermediate is one or more of GAP, GAP/PTHF and GAP/PATHF copolymer, and the structural general formula of the azide polyether intermediate is represented by (II):
Figure BDA0002860947760000022
further, the GAP homopolymer has the following structural formula:
Figure BDA0002860947760000023
further, the GAP/PTHF copolymer is one or more of random copolymer and block copolymer, including GAP-r-PTHF random copolyether, GAP-PTHF-GAP triblock copolyether, PTHF-GAP-PTHF triblock copolyether and the like. The general structural formula is as follows:
Figure BDA0002860947760000031
further, the GAP/PATHF copolymer is characterized by being GAP-r-PATHF random copolyether. The general structural formula is as follows:
Figure BDA0002860947760000032
further, the azide polyether intermediate has a number average molecular weight Mn＝500～5000g/mol。
Further, the diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate.
Further, the hydroxyl (meth) acrylate is one or more of hydroxyethyl (meth) acrylate and propyl (meth) acrylate.
The invention also provides a synthesis method of the bifunctional azido polyether polyurethane acrylate, which comprises the following steps:
step 1) at N2Under the atmosphere, carrying out reaction on an azide polyether intermediate and diisocyanate by taking dibutyltin dilaurate as a catalyst under the heating condition to obtain a double-end-capped polyurethane prepolymer, wherein the structural general formula of the double-end-capped polyurethane prepolymer is shown as (III):
Figure BDA0002860947760000033
and 2) adding (methyl) hydroxy acrylate into the polyurethane prepolymer, taking hydroquinone as a polymerization inhibitor, and further heating for reaction to obtain a target product.
Further, in the step 1), the heating condition is in a temperature range of 50 ℃ to 90 ℃.
Further, in the step 2), the temperature is further increased to react, wherein the temperature range is 80-120 ℃.
Use of the aforementioned difunctional azido polyether urethane acrylates for photocuring energy-containing adhesives for additive manufacturing.
Compared with the prior art, the invention has the advantages that: the novel energy-containing adhesive is synthesized, has photocuring characteristics, can realize normal-temperature or even low-temperature curing, avoids the problems of solvent volatilization, more curing side reactions and the like of the traditional thermosetting mode, and reduces potential safety hazards. In addition, the molding and manufacturing of fine (micrometer level) and complex structures can be realized by matching with 3D technology such as SLA (stereo lithography), DLP (digital light processing) and the like.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
In the composite solid propellant, the traditional thermosetting mode needs to use bifunctional or polyfunctional isocyanate as a curing agent, and the traditional thermosetting mode has the defects of toxicity, sensitivity to water vapor, easy solvent volatilization at high temperature, pollution caused by high temperature and the like.
In addition, azido polyether intermediate GAP1、GAP-co-PTHF2And GAP-r-PATHF3Other reagents are commercially available according to the methods described in the following documents 1 to 3.
1.(a)Eroglu,M.S.；Bostan,M.S.,GAP pre-polymer,as an energetic binder and high performance additive for propellants and explosives:A review.Organic Communications2017,10(3),135-143；(b)Murali Mohan,Y.；Padmanabha Raju,M.；Mohana Raju,K.,Synthesis,spectral and DSC analysis of glycidyl azide polymers containing different initiating diol units.Journal of Applied Polymer Science 2004,93(5),2157-2163.
2.(a) Mohan, y.m.; raju, K.M., Synthesis and Characterization of GAP-THF polymers International Journal of Polymeric Materials 2006,55(3), 203-217; (b) bayard, y.; chizari, M., Synthesis, Characterization and Stability of Triblock Copolymer Based on Tetrahydrofuran and Glycidylazine as binder. Polymer Science, Series B2018, 60(5), 621-; (c) mohonchang; slowly glowing; liu Ning; lu Xian Ming; liu Meng; wangwei, synthesis and characterization of GAP-PTMEG-GAP triblock copolyether the explosive and explosive letters 2020,43(04),388-391+398.
3.Dong,Q.；Li,Y.；Wu,F.；Li,H.；Liu,X.；Huang,C.,Synthesis,Characterization and Thermal Properties of Poly(glycidyl azide-r-3-azidotetrahydrofuran)as Azido Binder for Solid Rocket Propellants.Propellants,Explosives,Pyrotechnics 2017,42(10),1143-1148.。
Example 1
A method for synthesizing azide polyether urethane acrylate photocuring energetic adhesive comprises the following specific operation steps:
step 1) introducing N into a four-neck round-bottom flask with a magnetic heating stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermocouple2Removing water vapor in the atmosphere. Toluene diisocyanate (1.04g, about 6mmol) was added to the system, heated to 50 ℃ and then GAP (5g, about 3mmol) and dibutyltin dilaurate (0.012g, about 0.02%) as a catalyst were mixed and added dropwise from a dropping funnel at a constant pressure, and the system temperature was maintained at 50 ℃ for 2 hours.
And 2) determining the content of-NCO groups in the system by a di-n-butylamine titration method, stopping heating when the conversion rate reaches 50%, cooling to 40 ℃, adding hydroxyethyl acrylate (0.73g, about 6.3mmol) and polymerization inhibitor hydroquinone (0.02g, about 0.03%) into the system, heating to 80 ℃ for continuous reaction after the system is stable, tracking the content of-NCO groups after the reaction is carried out for a plurality of hours, stopping heating and cooling to room temperature after the content is less than 0.30%, thus obtaining the product azido polyether urethane acrylate, and storing in a dark place.
Example 2
A method for synthesizing azide polyether urethane acrylate photocuring energetic adhesive comprises the following specific operation steps:
step 1) introducing N into a four-neck round-bottom flask with a magnetic heating stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermocouple2Removing water vapor in the atmosphere. Isophorone diisocyanate (1.33g, about 6mmol) was added to the system, heated to 50 ℃, and then GAP (5g, about 3mmol) and the catalyst dibutyltin dilaurate (0.018g, about 0.03%) were mixed and added dropwise in a constant pressure dropping funnel, and the system temperature was maintained at 50 ℃ for reaction for 3 hours.
And 2) determining the content of-NCO groups in the system by a di-n-butylamine titration method, stopping heating when the conversion rate reaches 50%, cooling to 40 ℃, adding hydroxyethyl acrylate (0.73g, about 6.3mmol) and polymerization inhibitor hydroquinone (0.021g, about 0.03%) into the system, heating to 80 ℃ for continuous reaction after the system is stable, tracking the content of-NCO groups after the reaction is carried out for a plurality of hours, stopping heating and cooling to room temperature after the content is less than 0.30%, thus obtaining the product azido polyether urethane acrylate, and storing in a dark place.
Example 3
A method for synthesizing azide polyether urethane acrylate photocuring energetic adhesive comprises the following specific operation steps:
step 1) introducing N into a four-neck round-bottom flask with a magnetic heating stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermocouple2Removing water vapor in the atmosphere. Hexamethylene diisocyanate (1.01g, about 6mmol) was added to the system, heated to 80 ℃ and then GAP (5g, about 3mmol) and the catalyst dibutyltin dilaurate (0.018g, about 0.03%) were mixed and added dropwise in a constant pressure dropping funnel, and the system temperature was maintained at 80 ℃ for reaction for 5 hours.
And 2) measuring the content of-NCO groups in the system by a di-n-butylamine titration method, stopping heating when the conversion rate reaches 50%, cooling to 60 ℃, adding hydroxyethyl acrylate (0.73g, about 6.3mmol) and polymerization inhibitor hydroquinone (0.035g, about 0.05%) into the system, heating to 100 ℃ for continuous reaction after the system is stable, tracking the content of-NCO groups after the reaction is carried out for a plurality of hours, stopping heating and cooling to room temperature after the content is less than 0.30%, and obtaining the product azido polyether urethane acrylate which is stored in a dark place.
Example 4
A method for synthesizing azide polyether urethane acrylate photocuring energetic adhesive comprises the following specific operation steps:
step 1) introducing N into a four-neck round-bottom flask with a magnetic heating stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermocouple2Removing water vapor in the atmosphere. Toluene diisocyanate (1.04g, about 6mmol) was added to the system, heated to 50 ℃ and then GAP-r-PTHF random copolyether (6g, about 3mmol) and dibutyltin dilaurate (0.014g, about 0.02%) as a catalyst were mixed and added dropwise from a dropping funnel at a constant pressure, and the system temperature was maintained at 50 ℃ for 3 hours.
And 2) measuring the content of-NCO groups in the system by a di-n-butylamine titration method, stopping heating when the conversion rate reaches 50%, cooling to 40 ℃, adding hydroxyethyl acrylate (0.73g, about 6.3mmol) and polymerization inhibitor hydroquinone (0.023g, about 0.03%) into the system, heating to 80 ℃ for continuous reaction after the system is stable, tracking the content of-NCO groups after the reaction is carried out for a plurality of hours, stopping heating and cooling to room temperature after the content is less than 0.30%, thus obtaining the product azido polyether urethane acrylate, and storing in a dark place.
Example 5
A method for synthesizing azide polyether urethane acrylate photocuring energetic adhesive comprises the following specific operation steps:
step 1) introducing N into a four-neck round-bottom flask with a magnetic heating stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermocouple2Removing water vapor in the atmosphere. Isophorone diisocyanate (1.78g, about 8mmol) was added to the system, heated to 50 ℃, and then GAP-PTHF-GAP triblock copolyether (6g, about 4mmol) and dibutyltin dilaurate (0.023g, about 0.03%) as a catalyst were mixed and added dropwise from a constant pressure dropping funnel, and the system temperature was maintained at 50 ℃ for 4 hours.
And 2) measuring the content of-NCO groups in the system by a di-n-butylamine titration method, stopping heating when the conversion rate reaches 50%, cooling to 40 ℃, adding hydroxyethyl acrylate (0.98g, about 8.4mmol) and polymerization inhibitor hydroquinone (0.026g, about 0.03%) into the system, heating to 80 ℃ for continuous reaction after the system is stabilized, tracking the content of-NCO groups after the reaction is carried out for a plurality of hours, stopping heating and cooling to room temperature after the content is less than 0.30%, thus obtaining the product azido polyether urethane acrylate, and storing in a dark place.
Example 6
A method for synthesizing azide polyether urethane acrylate photocuring energetic adhesive comprises the following specific operation steps:
step 1) introducing N into a four-neck round-bottom flask with a magnetic heating stirrer, a reflux condenser, a constant-pressure dropping funnel and a thermocouple2Removing water vapor in the atmosphere. Hexamethylene diisocyanate (0.673g, about 4mmol) was added to the system, heated to 90 ℃ and then GAP-r-PATHF random copolyether (7g, about 2mmol) and dibutyltin dilaurate (0.023g, about 0.03%) as a catalyst were mixed and added dropwise from a constant pressure dropping funnel, and the system temperature was maintained at 90 ℃ for 6 hours.
And 2) determining the content of-NCO groups in the system by a di-n-butylamine titration method, stopping heating when the conversion rate reaches 50%, cooling to 60 ℃, adding hydroxybutyl acrylate (0.61g, about 4.2mmol) and polymerization inhibitor hydroquinone (0.041g, about 0.05%) into the system, heating to 110 ℃ for continuous reaction after the system is stable, tracking the content of-NCO groups after the reaction is carried out for a plurality of hours, stopping heating and cooling to room temperature after the content is less than 0.30%, thus obtaining the product azido polyether urethane acrylate, and storing in a dark place.
The azido polyether type polyurethane acrylate has photocuring characteristic and low viscosity, can be molded and manufactured by applying a 3D printing technology by matching with a proper reactive diluent, and in addition, the structure of the polyether main chain and the terminal urethane endows the azido polyether type polyurethane acrylate with certain flexibility and good low-temperature mechanical property, the glass transition temperature is between-20 ℃ and-60 ℃, and the basic requirement of a propellant adhesive is met.

Claims (10)

1. A photocurable energy-containing adhesive for additive manufacturing, wherein the energy-containing adhesive is azido polyether urethane acrylate, and the structural formula of the energy-containing adhesive is represented by the following general formula (i):
Figure FDA0002860947750000011
wherein R is1Represents one or two of-H and-Me;
R2represents-C2H4-、-C3H6-one or both;
R3represents one or more of toluene diisocyanate, isophorone diisocyanate and hexamethylene diisocyanate;
m and n are polymers.
2. The method of claim 1, wherein the target product is obtained by reacting the azido polyether intermediate with an excess of diisocyanate to obtain a double-capped polyurethane prepolymer, and then adding a hydroxy (meth) acrylate to further end-cap the double-capped polyurethane prepolymer.
3. The method of claim 2 wherein the azido polyether intermediate is one or more of GAP, GAP/PTHF, and GAP/PATHF copolymers, and has the general structural formula (II):
Figure FDA0002860947750000012
4. the method of claim 2, wherein the GAP/PTHF copolymer is one or both of a random copolymer and a block copolymer, and comprises GAP-r-PTHF random copolyether, GAP-PTHF-GAP triblock copolyether and PTHF-GAP-PTHF triblock copolyether, and has the following structural formula:
Figure FDA0002860947750000021
5. the method of claim 2 wherein the GAP/PATHF copolymer is a GAP-r-PATHF random copolyether having the general structural formula:
Figure FDA0002860947750000022
6. the process of claim 2 wherein the azidopolyether intermediate has a number average molecular weight Mn500 to 5000 g/mol.
7. The process of claim 2 wherein the double-capped polyurethane prepolymer is obtained by reacting the azido polyether intermediate with an excess of diisocyanate at a temperature in the range of 50 ℃ to 90 ℃.
8. The method of claim 2, wherein the target product is obtained by adding the hydroxy (meth) acrylate to further perform the end-capping reaction, wherein the reaction temperature is in the range of 80 ℃ to 120 ℃.
9. The method according to claim 2, wherein the diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate.
10. The method according to claim 2, wherein the hydroxy (meth) acrylate is one or more of hydroxyethyl (meth) acrylate and hydroxybutyl (meth) acrylate.
CN202011567005.4A 2020-12-25 2020-12-25 Light-cured adhesive for additive manufacturing and synthetic method thereof Pending CN112812259A (en)

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