CN108587544B - Azido-terminated polycaprolactone adhesive and synthesis method thereof - Google Patents
Azido-terminated polycaprolactone adhesive and synthesis method thereof Download PDFInfo
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- CN108587544B CN108587544B CN201810264427.0A CN201810264427A CN108587544B CN 108587544 B CN108587544 B CN 108587544B CN 201810264427 A CN201810264427 A CN 201810264427A CN 108587544 B CN108587544 B CN 108587544B
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- 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
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses an azido-terminated polycaprolactone adhesive and a synthesis method thereof, wherein the structural formula of the azido-terminated polycaprolactone adhesive is shown as (I). The synthesis process comprises the following steps: and (2) performing addition reaction on polycaprolactone diol and chloroethyl isocyanate to obtain chlorine-terminated polycaprolactone, and performing azide reaction on the chlorine-terminated polycaprolactone and sodium azide to obtain azido-terminated polycaprolactone. The synthesis method is simple, and the azido-terminated polycaprolactone adhesive can endow the polytriazole elastomer with higher mechanical properties.
Description
Technical Field
The invention relates to an azido-terminated polycaprolactone adhesive and a synthesis method thereof, and the compound can be used as an adhesive of a solid propellant, belonging to the technical field of high polymer materials.
Background
The composite solid propellant is prepared by taking high polymer or prepolymer as a binder and adding solid oxidizer, metal fuel and other components. The modern composite solid propellant generally adopts hydroxyl-terminated polyester or polyether as an adhesive to form an isocyanate curing system with a polyisocyanate curing agent, and a polyurethane elastomer is prepared through a curing reaction between the hydroxyl-terminated polyester or polyether and an isocyanate group to serve as a matrix for bearing a solid filler. Because the polyurethane elastomer has small shrinkage rate during curing, the acting force of hydrogen bonds between carbamate groups as hard chain segments is strong, and the micro-phase separation is easy, so that the elastomer has excellent mechanical properties and becomes one of the more important varieties in the composite solid propellant. However, the isocyanate curing system has harsh curing conditions and is sensitive to moisture, and isocyanate groups can react with water or organic acid rapidly to generate CO2The gas holes are easily formed in the propellant, and the mechanical property, the storage property and the safety of the propellant are influencedAnd (4) full performance.
In order to solve the problems of the isocyanate curing system, researchers develop a novel curing system for preparing the polytriazole elastomer by curing the terminal azido-based adhesive and the polyacetylene curing agent. For example, Byoung-Sun Min et al, Triazol Crosslinked Polymer Formed by the cyclic addition of Azide End-Capped Polymer with a chiral acidic Current, Macromolecular Research, 2012, 2 (4): 429-432 discloses an azide-PCP adhesive and the high temperature mechanical property of the polytriazole elastomer formed after the azide-PCP adhesive is solidified, the azide-PCP is synthesized by taking polycaprolactone diol as a raw material and carrying out two-step reactions of sulfoacid esterification and azidation, and the structural formula of the azide-PCP is as follows:
in the synthesis process of the azide-PCP, toxic reagents such as pyridine, paratoluensulfonyl chloride and the like are needed in the first step of reaction, and the post-treatment is troublesome; the research on the high-temperature mechanical property of the polytriazole elastomer formed after curing discovers that: when azide-PCP is selected as an adhesive and dipropynyl succinate (BPS) is selected as a curing agent, when the dosage of a cross-linking agent is 20%, the prepared polytriazole elastomer has the best mechanical property, the maximum elongation is 734%, the maximum tensile strength is 620KPa (0.62MPa), and the mechanical properties of the elastomer such as the tensile strength and the like are relatively low.
Disclosure of Invention
The invention aims to overcome the defects of the background technology and provide the terminal azido-based polycaprolactone adhesive which can endow the polytriazole elastomer with higher mechanical property and the synthetic method thereof.
The conception of the invention is as follows: the low mechanical properties of the polytriazole elastomers prepared with azide-PCP as the binder are due to the weak interaction between the hard segment polytriazole groups and the low hard segment content. In order to improve the mechanical properties of the elastomer, the invention envisages: the carbamate groups are introduced into two ends of the molecular chain of the azide-PCP adhesive, so that on one hand, the content of hard chain segments is increased, on the other hand, the stronger hydrogen bond function among the carbamate groups can play a role in physical crosslinking, and the microphase separation of the elastomer is promoted, so that the mechanical property of the elastomer is improved.
In order to solve the technical problems, the structural formula of the azido-terminated polycaprolactone adhesive is as follows:
wherein m + n is 6-60 and is an integer.
The synthetic route of the azido-terminated polycaprolactone adhesive is as follows:
wherein m + n is 6-60 and is an integer.
The synthesis method of the azido-terminated polycaprolactone adhesive comprises the following steps:
sequentially adding polycaprolactone diol, dibutyltin dilaurate and 2-chloroethyl isocyanate into a three-neck flask provided with a mechanical stirring and reflux condenser tube and a thermometer, heating to 80-85 ℃, reacting for 8-12 h under stirring, then adding dimethylformamide and sodium azide into the reaction system, heating to 90-95 ℃, and reacting for 18-24 h. Cooling to room temperature after the reaction is finished, adding water for precipitation, dissolving the precipitate with dichloromethane, washing with water, separating out an organic phase, and evaporating under reduced pressure to remove the dichloromethane as a solvent to obtain an azido-terminated polycaprolactone (AUPCL for short) adhesive; wherein the molar ratio of the 2-chloroethyl isocyanate to the polycaprolactone diol is 2:1, the mass ratio of the dibutyltin dilaurate to the polycaprolactone diol is 0.001-0.0001: 1, and the molar ratio of the sodium azide to the polycaprolactone diol is 2.1-2.4: 1.
The invention has the advantages that:
the AUPCL adhesive can be prepared by a one-pot method, and the synthesis method is simple; besides two terminal azido groups, the AUPCL adhesive of the invention introduces carbamate groups with stronger hydrogen bond function at two ends of a molecular chain, and can improve the content of hard chain segments and the microphase separation degree when used for synthesizing polytriazole elastomer, thereby improving the mechanical property of the elastomer, wherein the tensile strength of the polytriazole elastomer prepared by taking the AUPCL adhesive of the invention as a raw material is 1.36MPa at 60 ℃, and the elongation at break is 745%; in contrast, the polytriazole elastomer prepared from the azide-PCP adhesive is 0.62MPa in tensile strength at 60 ℃ and 734% in elongation at break.
Detailed Description
The present invention will be described in further detail with reference to examples.
Testing an instrument:
(1) number average molecular weight
Equipment: GPC-50 gel permeation chromatography of PL corporation, UK;
GPC test conditions: the chromatographic column is series connected by PLGel MIXED-E; the mobile phase is THF; the column temperature was 40 ℃; detector
Is a refractive index detector.
(2) Mechanical property of elastomer
Equipment: universal materials testing machine model Instron 4505, Instron corporation, usa;
the test method comprises the following steps: according to the GB/T528-1998 method.
Example 1
30g (0.03mol) of polycaprolactone diol, 0.015g of dibutyltin dilaurate and 6.33g of 2-chloroethyl isocyanate are sequentially added into a three-necked bottle provided with a mechanical stirring, reflux condenser tube and thermometer, the temperature is raised to 80 ℃, the reaction is carried out for 10 hours under stirring, then 100mL of dimethylformamide and 4.29g of sodium azide are added into the reaction system, and the temperature is raised to 90 ℃ for 20 hours. After the reaction, the temperature is reduced to room temperature, water is added for precipitation, 60mL of dichloromethane is used for dissolving the precipitate, the precipitate is washed with water, an organic phase is separated, and the solvent dichloromethane is evaporated under reduced pressure to obtain 35.6g of light yellow solid.
Characterization data:
IR，νmax(cm-1)：3368(－NH－)，2945、2865、2797(－CH2－)，2101、1282(-N3) 1740, 1192, 1097 (ester group)。
1H NMR(CDCl3，500MHz)：1.49～1.55，1.63～1.73，2.30～2.39，4.02～4.31，5.35～5.50。
The number average molecular weight was 1220, and the azide group content was 1.62 mmol/g.
The above data indicate that the synthesized compound is an azido terminated polycaprolactone adhesive.
Example 2
60g (0.03mol) of polycaprolactone diol, 0.03g of dibutyltin dilaurate and 6.33g of 2-chloroethyl isocyanate are sequentially added into a three-necked flask provided with a mechanical stirring, reflux condenser tube and thermometer, the temperature is raised to 82 ℃, the reaction is carried out for 10 hours under stirring, then 150mL of dimethylformamide and 4.48g of sodium azide are added into the reaction system, and the temperature is raised to 90 ℃ for 20 hours. After the reaction, the temperature is reduced to room temperature, water is added for precipitation, 120mL of dichloromethane is used for dissolving the precipitate, the precipitate is washed with water, an organic phase is separated, and the solvent dichloromethane is evaporated under reduced pressure to obtain 66.1g of light yellow solid.
Number average molecular weight 2215, and azide group content 0.89 mmol/g.
Example 3
In a three-necked flask provided with a mechanical stirring, reflux condenser tube and thermometer, 90g (0.03mol) of polycaprolactone diol, 0.03g of dibutyltin dilaurate and 6.33g of 2-chloroethyl isocyanate are sequentially added, the temperature is raised to 82 ℃, the reaction is carried out for 10 hours under stirring, then 200mL of dimethylformamide and 4.48g of sodium azide are added into the reaction system, and the temperature is raised to 95 ℃ for reaction for 24 hours. After the reaction, the temperature is reduced to room temperature, water is added for precipitation, 200mL of dichloromethane is used for dissolving the precipitate, the precipitate is washed with water, an organic phase is separated, and the solvent dichloromethane is evaporated under reduced pressure to obtain 95.8g of light yellow solid.
The number average molecular weight was 3221, and the azide group content was 0.61 mmol/g.
The application performance of the azido-terminated polycaprolactone adhesive
The AUPCL adhesive is used as a raw material, is mixed with a curing agent of dipropynyl succinate and a cross-linking agent of triazo-polycaprolactone, is heated and cured, and when the addition of the cross-linking agent is 20 percent of the mass fraction of the adhesive, the prepared polytriazole elastomer has the following mechanical properties at 60 ℃: the tensile strength was 1.36MPa, and the elongation at break was 745%.
Claims (2)
1. The azido-terminated polycaprolactone adhesive is characterized by having the following structural formula:
wherein m + n is 6-60 and is an integer.
2. A method for synthesizing the azido-terminated polycaprolactone adhesive of claim 1, which is characterized by comprising the following steps:
sequentially adding polycaprolactone diol, dibutyltin dilaurate and 2-chloroethyl isocyanate into a three-necked flask provided with a mechanical stirring and reflux condenser tube and a thermometer, heating to 80-85 ℃, reacting for 8-12 h under stirring, then adding dimethylformamide and sodium azide into the reaction system, heating to 90-95 ℃, reacting for 18-24 h, cooling to room temperature after the reaction is finished, adding water for precipitation, dissolving the precipitate with dichloromethane, washing with water, separating out an organic phase, and evaporating the solvent dichloromethane under reduced pressure to obtain the terminal azido-based polycaprolactone adhesive; wherein the molar ratio of the 2-chloroethyl isocyanate to the polycaprolactone diol is 2:1, the mass ratio of the dibutyltin dilaurate to the polycaprolactone diol is 0.001-0.0001: 1, and the molar ratio of the sodium azide to the polycaprolactone diol is 2.1-2.4: 1.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702536A (en) * | 2012-05-14 | 2012-10-03 | 华东理工大学 | Synthetic method of triblock polymer |
| CN104995229A (en) * | 2013-02-08 | 2015-10-21 | Sika技术股份公司 | Synthesis of polyurethane polymers via copper azide-alkyne click chemistry for coatings, adhesives, sealants and elastomer applications |
| CN105175707A (en) * | 2015-10-23 | 2015-12-23 | 西安近代化学研究所 | Alkynyl-terminated curing agent and preparation method thereof |
| EP3115348A1 (en) * | 2015-07-07 | 2017-01-11 | BAE Systems PLC | Cast explosive composition |
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- 2018-03-28 CN CN201810264427.0A patent/CN108587544B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702536A (en) * | 2012-05-14 | 2012-10-03 | 华东理工大学 | Synthetic method of triblock polymer |
| CN104995229A (en) * | 2013-02-08 | 2015-10-21 | Sika技术股份公司 | Synthesis of polyurethane polymers via copper azide-alkyne click chemistry for coatings, adhesives, sealants and elastomer applications |
| EP3115348A1 (en) * | 2015-07-07 | 2017-01-11 | BAE Systems PLC | Cast explosive composition |
| CN105175707A (en) * | 2015-10-23 | 2015-12-23 | 西安近代化学研究所 | Alkynyl-terminated curing agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 1,2,3-Triazole Crosslinked Polymers as Binders for Solid Rocket Propellants;Dong-Hoon Lee等;《Journal of Applied Polymer Science》;20140805;第131卷(第15期);第1-9页 * |
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