CN102516434B - Preparation method of alkynyl polybutadiene - Google Patents

Abstract

The invention relates to a preparation method of alkynylated polybutadiene, which belongs to the technical field of new materials. A preparation method of alkynylated polybutadiene is characterized in that it comprises the steps of: 1) pretreatment of raw materials; 2) selection of raw materials: the total amount of -OH in hydroxyl-terminated polybutadiene by molar ratio : Potassium tert-butoxide: haloalkyne=1: 0.5～4: 0.5～4, select hydroxyl-terminated polybutadiene, potassium tert-butoxide and haloalkyne; 3) under stirring and ice bath conditions, the hydroxyl-terminated Add the polybutadiene solution to the potassium tert-butoxide solution A to obtain the reaction solution, and add the halogenated alkyne solution to the reaction solution A under the protection of _N2, ice bath and stirring, and keep it at 0-25°C to make it react 24 to 48 hours to obtain the reaction solution B; 4) add salt water to the reaction solution B for extraction, separate the water layer, and keep the tetrahydrofuran layer; 5) dry over anhydrous MgSO ₄ , filter, and evaporate the solvent to obtain the alkynylated polybutylene Diene. The method of the invention has high efficiency, simple preparation process and environmental protection.

Description

A kind of preparation method of alkynylated polybutadiene

technical field

The invention relates to a preparation method of alkynylated polybutadiene, which belongs to the technical field of new materials.

Background technique

Solid propellant is not only one of the launch energy sources of rockets and missiles, but also a component of the entire engine structure. The performance of this dense energetic material plays a decisive role in the performance indicators of the entire propulsion system. Polymers based on polyurethane chemistry are the most versatile binders in solid composite propellants, and hydroxyl-terminated polybutadiene (HTPB), namely hydroxybutylene, is known for its low viscosity, good process performance, and high solid loading Quantity, relatively complete curing reaction and good storage performance, as well as its cost-reducing advantages, have a wide range of research applications in the fields of solid propellants and explosives. However, with the continuous increase in the requirements for propulsion technology, the requirements for the mechanical properties of the propellant with hydroxybutyl alcohol as the binder are also gradually increased. At present, cross-linking HTPB to form an interpenetrating network structure by adding a bonding agent is a method to improve its mechanical properties. The most common bonding agent is isocyanate. The application in pharmaceuticals has also been reported.

Azide energetic compounds refer to substances containing azide groups (-N ₃ ), and azide (-N ₃ ) is in a state of higher energy level, so azide compounds often have higher positive heat of formation , is one of the most studied energetic materials. When it is used as an energetic binder, due to the high energy content of the azide group, its thermal decomposition is carried out prior to the main chain and independently, so it can not only increase the energy of the formula, but also accelerate the decomposition of the propellant to a certain extent. Reduce the explosion temperature, reduce the ablation of barrel weapons, and can be used to prepare insensitive propellants with low characteristic signals. Therefore, some azide energetic compounds can and have been used as binders for propellants and propellants.

The cycloaddition reaction of alkynyl and azide functional groups can generate 1,2,3-triazole five-membered rings, which is the most classic type of "click" reaction, also known as Huisgen reaction. This type of reaction has high selectivity, high product yield, no by-product formation (high atom utilization), and good reaction kinetics (process is easy to control). Therefore, based on the 1,3-dipolar cycloaddition reaction between alkynylated polybutadiene and azide energetic compounds, they can be crosslinked while retaining their respective performance advantages, while crosslinking can Further improving its related mechanical properties, it is expected to be able to construct a new type of energetic adhesive. Since this new type of energetic adhesive has a certain degree of hydrophobicity, it is expected to be used in conjunction with oxidants such as ammonium dinitramide (AND), which can solve the problem of water absorption of the oxidant AND during the application process, thereby realizing azide-based and AND preparation of high-energy clean propellants.

Contents of the invention

The object of the present invention is to provide a kind of preparation method of alkynylated polybutadiene, and this method process is simple, environmental protection.

In order to achieve the above object, the technical solution adopted in the present invention is: a kind of preparation method of alkynylated polybutadiene, it is characterized in that it comprises the steps:

1) Pretreatment of raw materials: Hydroxyl-terminated polybutadiene (HTPB, ie, butylated hydroxyl) is vacuum-dried at 40-60°C for 2-8 hours; tetrahydrofuran is removed from water (ie, tetrahydrofuran does not contain water);

2) Selection of raw materials: The total amount of -OH in hydroxyl-terminated polybutadiene (HTPB, ie, butylated hydroxyl) in molar ratio: Potassium tert-butoxide (t-BuOK):halogenated alkyne=1:0.5～4: 0.5 to 4, select hydroxyl-terminated polybutadiene (HTPB, that is, butylated hydroxyl), potassium tert-butoxide (t-BuOK), and halogenated alkynes;

3) According to the proportion of hydroxyl-terminated polybutadiene and tetrahydrofuran (THF) is 4.4725g ~ 6.6257g: 20mL, choose tetrahydrofuran, use tetrahydrofuran (THF) as the solvent for the reaction, dissolve the hydroxyl-terminated polybutadiene in tetrahydrofuran ( THF) to obtain a hydroxyl-terminated polybutadiene solution (that is, a THF solution containing HTPB);

According to the proportion of potassium tert-butoxide (t-BuOK) and tetrahydrofuran (THF) is 0.1515g ~ 1.9635g: 20mL, tetrahydrofuran is selected, and tetrahydrofuran (THF) is used as a solvent for the reaction, potassium tert-butoxide is dissolved in tetrahydrofuran (THF ), obtain potassium tert-butoxide solution (i.e. t-BuOK solution);

According to the proportion of haloalkyne and tetrahydrofuran (THF) is 0.15mL ~ 4.09mL: 60mL, tetrahydrofuran is selected, and tetrahydrofuran (THF) is used as the solvent for the reaction, and haloalkyne is dissolved in tetrahydrofuran (THF) to obtain haloalkyne Solution (i.e. THF solution containing haloalkynes);

Under the conditions of stirring and ice bathing, the hydroxyl-terminated polybutadiene solution was added to the potassium tert-butoxide solution A to obtain a reaction solution, and under the conditions of _N2 protection, ice bathing and stirring, halogenated Alkyne solution, kept at 0-25°C to react for 24-48 hours to obtain reaction solution B;

4) adding brine to the reaction solution B for extraction, separating the water layer, and retaining the tetrahydrofuran (THF) layer;

The aqueous layer was extracted with ethyl acetate (EtOAc), and the organic layer was collected (i.e. the THF layer and the EtOAc layer); the organic layer was collected and then extracted with saturated brine, the aqueous layer was discarded, and the obtained material was mixed with the above-mentioned reserved tetrahydrofuran (THF ) layers are merged to obtain an organic material;

5) The organic material is dried through anhydrous MgSO ₄ , filtered, and the solvent is volatilized to obtain alkynylated polybutadiene (final product).

The hydroxyl value of the hydroxyl-terminated polybutadiene (HTPB, ie, butylated hydroxyl) in step 1) is between 0.4236-1.7658 mmol KOH/g (ie, 23.76-99.06 mg KOH/g).

The halogenated alkyne is propyne bromide, propyne chloride, 4-bromo-1-butyne or 4-chloro-1-butyne.

The reaction equation of the preparation method of a kind of alkynylated polybutadiene provided by the present invention is shown in Figure 1.

The structural formula of alkynylated polybutadiene is:

In the structural formula, x and z indicate that the position of C=C is on the main chain, which is obtained by 1,4-addition, including cis and trans; y indicates that the position of C=C is on the side chain, that is, through 1 , obtained by 2-addition; m is 1 or 2.

The beneficial effect of the present invention is that the proton of the hydroxyl group in HTPB is taken away by using potassium tert-butoxide as the base, and then reacted with halogenated alkynes to remove the halogen, thereby successfully connecting the alkynyl group. The method of the invention has high yield, simple preparation process and environmental protection, and the obtained product is expected to be able to chemically react with azide energetic compounds to cross-link, thereby improving the relevant mechanical properties of the propellant. There will be potential application value in the field of development.

Description of drawings

Fig. 1 is the reaction equation of the preparation method of alkynylated polybutadiene;

Fig. 2 is the raw material of embodiment 5 and product infrared figure;

Fig. 3 is the raw material NMR figure of embodiment 5;

Fig. 4 is the product NMR figure of embodiment 5;

Fig. 5 is the raw material of embodiment 7 and product infrared figure;

Fig. 6 is the raw material NMR figure of embodiment 7;

Fig. 7 is the NMR figure of the product of embodiment 7.

Detailed ways

In order to better understand the present invention, the content of the present invention is further illustrated below in conjunction with the examples, but the content of the present invention is not limited to the following examples.

Example 1:

Hydroxyl-terminated polybutadiene (HTPB, ie, hydroxybutyl) was vacuum-dried at 40°C for 2h; weighed 6.3754g of hydroxyl-terminated polybutadiene with a hydroxyl value of 0.4236mmol KOH/g (-OH in hydroxyl-terminated polybutadiene The total amount of 2.70mmol) was dissolved in 20mL THF to obtain a THF solution containing HTPB; another 0.1515g t-BuOK (1.35mmol) was dissolved in 20mL of THF to obtain a t-BuOK solution; Slowly add the THF solution containing HTPB into the t-BuOK solution under the conditions, and continue to stir for 10 minutes to obtain the reaction solution A; take 0.15mL of propargyl bromide (80%w/w, ca.9.2mol/L; 1.38mmol; Hydroxyl-terminated polybutadiene, potassium tert-butoxide, and _propargyl bromide in a molar ratio of 1.0:0.5:0.5) were dissolved in 60 mL of THF, and slowly transferred to In the reaction solution A, keep stirring at 0° C. for 48 h to obtain the reaction solution B.

Add 80mL of salt water to the reaction solution B for extraction, separate the aqueous layer, and keep the THF layer; extract the aqueous layer with ethyl acetate (3×50mL), collect the organic layer, namely the THF layer and the EtOAc layer, and then use 100mL of the organic layer Extraction with saturated brine, discarding the water layer, and then combining the obtained material with the above-mentioned retained tetrahydrofuran (THF) layer to obtain an organic material;

The organic material was dried over anhydrous MgSO ₄ , filtered, and the solvent was evaporated to obtain alkynylated polybutadiene (6.3723 g, yield 99.1%).

Through the infrared image of the alkynylated polybutadiene product and the NMR image of the product, it can be known that the reaction has successfully connected an alkynyl group and a propargyl group.

The azide energetic compound is specifically polyazidoglycidyl ether (GAP), 3-azidomethylbutylene oxide homopolymer (PAMMO) or 3,3-diazidomethyloxetane homopolymer Azide compounds with different structures and functionalities such as PBAMO, 1,11-diazide-3,6,9-trioxaundecane, 1,4-bis(azidomethyl)benzene, etc. The obtained product can be cross-linked by chemical reaction with an azide energetic compound (specifically GAP, 1,4-bis(azidomethyl)benzene) to obtain a novel energetic adhesive.

Example 2:

Hydroxyl-terminated polybutadiene (HTPB, ie, hydroxybutyl) was vacuum-dried at 40°C for 8 hours; weighed 6.6257g of hydroxyl-terminated polybutadiene with a hydroxyl value of 0.5524mmol KOH/g (-OH in hydroxyl-terminated polybutadiene The total amount of 3.66mmol) was dissolved in 20mL THF to obtain a THF solution containing HTPB; another 0.2053g t-BuOK (1.83mmol) was dissolved in 20mL of THF to obtain a t-BuOK solution; Slowly add the THF solution containing HTPB into the t-BuOK solution under the conditions, and continue to stir for 10 minutes to obtain the reaction solution A; take 0.20 mL of propargyl chloride (70% w/w, ca. 9.2 mol/L; 1.84 mmol; The molar ratio of hydroxyl group, potassium tert-butoxide, and propargyl chloride is 1.0:0.5:0.5) was dissolved in 60mL of THF, and was slowly transferred to the reaction solution A under _N2 protection, ice bath and stirring conditions, Keep stirring at 15°C for 36h to obtain reaction solution B.

Add 80mL of salt water to the reaction solution B for extraction, separate the aqueous layer, and keep the THF layer; extract the aqueous layer with ethyl acetate (3×50mL), collect the organic layer, namely the THF layer and the EtOAc layer, and then use 100mL of the organic layer Extraction with saturated brine, discarding the water layer, and then combining the obtained material with the above-mentioned retained tetrahydrofuran (THF) layer to obtain an organic material;

The organic material was dried over anhydrous MgSO ₄ , filtered, and the solvent was evaporated to obtain alkynylated polybutadiene (6.5885 g, yield 98.4%).

Through the infrared image of the alkynylated polybutadiene product and the NMR image of the product, it can be known that the reaction has successfully connected an alkynyl group and a propargyl group.

The obtained product can be cross-linked by chemical reaction with an azide energetic compound (specifically GAP, 1,4-bis(azidomethyl)benzene) to obtain a novel energetic adhesive.

Example 3:

Hydroxy-terminated polybutadiene (HTPB, ie, hydroxybutyl) was vacuum-dried at 40°C for 6h; weighed 6.3427g of hydroxyl-terminated polybutadiene with a hydroxyl value of 0.6886mmol KOH/g (-OH in hydroxyl-terminated polybutadiene The total amount of 4.37mmol) was dissolved in 20mL THF to obtain a THF solution containing HTPB; another 0.4903g t-BuOK (4.37mmol) was dissolved in 20mL of THF to obtain a t-BuOK solution; Under the conditions, the THF solution containing HTPB was slowly added to the t-BuOK solution, and the stirring was continued for 10 min to obtain the reaction solution A; 0.2936 g of 4-bromo-1-butyne (2.21 mmol; hydroxyl, potassium tert-butoxide, propyne The molar ratio of chlorine is 1.0:1.0:0.5) was dissolved in 60mL of THF, under _N2 protection, ice bath and stirring conditions, it was slowly transferred to the reaction solution A, kept at 25°C and continued to stir for 24h to obtain the reaction Liquid B.

Add 80mL of salt water to the reaction solution B for extraction, separate the water layer, and keep the THF layer; extract the water layer with ethyl acetate (3×50mL), collect the organic layer, namely the THF layer and the EtOAc layer, and then wash it with 100mL of saturated salt Water extraction, discarding the water layer, and then combining the obtained material with the above-mentioned reserved tetrahydrofuran (THF) layer to obtain an organic material;

The organic material was dried over anhydrous MgSO ₄ , filtered, and the solvent was evaporated to obtain alkynylated polybutadiene (6.3801 g, yield 98.8%).

Through the infrared image of the alkynylated polybutadiene product and the NMR image of the product, it can be known that the reaction has successfully connected an alkynyl group and a propargyl group.

The obtained product can be cross-linked by chemical reaction with an azide energetic compound (specifically GAP, 1,4-bis(azidomethyl)benzene) to obtain a novel energetic adhesive.

Example 4:

Hydroxyl-terminated polybutadiene (HTPB, ie, hydroxybutyl) was vacuum-dried at 50°C for 5h; weighed 6.1724g of hydroxyl-terminated polybutadiene with a hydroxyl value of 0.7562mmol KOH/g (-OH in hydroxyl-terminated polybutadiene The total amount of 4.67mmol) was dissolved in 20mL THF to obtain a THF solution containing HTPB; another 0.5240g t-BuOK (4.67mmol) was dissolved in 20mL of THF to obtain a t-BuOK solution; Under the conditions, the THF solution containing HTPB was slowly added to the t-BuOK solution, and the stirring was continued for 10 min to obtain the reaction solution A; 0.4154 g of 4-chloro-1-butyne (4.69 mmol; hydroxyl, potassium tert-butoxide, propane The molar ratio of alkyne chloride is 1.0:1.0:1.0) was dissolved in 60mL of THF, under the condition of _N2 protection, ice bath and stirring, it was slowly transferred to the reaction solution A, kept at 0°C and continued to stir for 48h to obtain Reaction solution B.

Add 80mL of salt water to the reaction solution B for extraction, separate the water layer, and keep the THF layer; extract the water layer with ethyl acetate (3×50mL), collect the organic layer, namely the THF layer and the EtOAc layer, and then wash it with 100mL of saturated salt Water extraction, discarding the water layer, and then combining the obtained material with the above-mentioned reserved tetrahydrofuran (THF) layer to obtain an organic material;

The organic material was dried over anhydrous MgSO ₄ , filtered, and the solvent was evaporated to obtain alkynylated polybutadiene (6.2613 g, yield 97.6%).

Through the infrared image of the alkynylated polybutadiene product and the NMR image of the product, it can be known that the reaction has successfully connected an alkynyl group and a propargyl group.

The obtained product can be cross-linked by chemical reaction with an azide energetic compound (specifically GAP, 1,4-bis(azidomethyl)benzene) to obtain a novel energetic adhesive.

Example 5:

Hydroxy-terminated polybutadiene (HTPB, ie, hydroxybutyl) was vacuum-dried at 60°C for 2 hours; weighed 5.7060 g of hydroxyl-terminated polybutadiene with a hydroxyl value of 0.8399 mmol KOH/g (-OH in hydroxyl-terminated polybutadiene The total amount of 4.79mmol) was dissolved in 20mL THF to obtain a THF solution containing HTPB; another 1.1033g t-BuOK (9.83mmol) was dissolved in 20mL of THF to obtain a t-BuOK solution; Slowly add the THF solution containing HTPB into the t-BuOK solution under the conditions, and continue to stir for 10 minutes to obtain the reaction solution A; take 1.10 mL of propargyl bromide (80% w/w, ca.9.2mol/L; 10.12mol; The molar ratio of hydroxyl group, potassium tert-butoxide, and propargyl chloride is 1.0:2.1:2.1) was dissolved in 60mL of THF, and was slowly transferred to reaction solution A under _N2 protection, ice bath and stirring conditions, Keep stirring at 0-25°C for 48 hours to obtain reaction solution B.

Add 80mL of salt water to the reaction solution B for extraction, separate the water layer, and keep the THF layer; extract the water layer with ethyl acetate (3×50mL), collect the organic layer, namely the THF layer and the EtOAc layer, and then wash it with 100mL of saturated salt Water extraction, discarding the water layer, and then combining the obtained material with the above-mentioned reserved tetrahydrofuran (THF) layer to obtain an organic material;

The organic material was dried over anhydrous MgSO ₄ , filtered, and the solvent was evaporated to obtain alkynylated polybutadiene (5.8645 g, yield 99.6%).

The infrared images of hydroxyl-terminated polybutadiene (HTPB, ie, butylated hydroxyl) raw materials and alkynylated polybutadiene products are shown in Figure 2. In Fig. 2, the absorption peak of the hydroxyl group of the raw material HTPB in the characteristic area is 3350cm ^-1 , which belongs to the stretching vibration peak of -OH, and the peak here in the product after the reaction (PTPB) weakens, and it appears clearly at 3307cm ^-1 The CH stretching vibration peak of the alkynyl group proves that the reaction has successfully attached the alkynyl group;

Hydroxyl-terminated polybutadiene (HTPB, i.e. butyl hydroxy) raw material ¹ H NMR spectrogram is shown in Figure 3, and its peak shape is completely consistent with literature reports, and the chemical shift of each CH in HTPB is marked in the figure, and the place at 7.26ppm is The vibration peak of the solvent CDCl ₃ was compared with the product ¹ H NMR spectrum, and the two additional peaks (e, f in Figure 4) were determined to be assigned to the methylene group (e) on the propargyl group and the terminal CH (f ) vibration peak.

Alkynylated polybutadiene product ¹ H NMR spectrogram is as shown in Figure 4, compares with Figure 3, clearly increases/enhances two peaks at 4.13ppm (e) and 2.42ppm (f) (Figure 7 is more obvious ), which belong to the vibration peaks of the methylene group (e) on the propargyl group and the terminal CH (f) respectively, and the solvent peak of CDCl ₃ at 7.26ppm. By comparing Figure 3 and Figure 4, it can be proved that the propargyl group was successfully attached.

The obtained product can be cross-linked by chemical reaction with an azide energetic compound (specifically GAP, 1,4-bis(azidomethyl)benzene) to obtain a novel energetic adhesive.

Embodiment 6:

Hydroxyl-terminated polybutadiene (HTPB, ie, hydroxybutyl) was vacuum-dried at 60°C for 8 hours; weighed 5.9029 g of hydroxyl-terminated polybutadiene with a hydroxyl value of 1.0251 mmol KOH/g (-OH in hydroxyl-terminated polybutadiene The total amount of 6.05mmol) was dissolved in 20mL THF to obtain a THF solution containing HTPB; another 0.6788g t-BuOK (6.05mmol) was dissolved in 20mL of THF to obtain a t-BuOK solution; Slowly add the THF solution containing HTPB into the t-BuOK solution under the conditions, and continue to stir for 10 minutes to obtain the reaction solution A; take 1.32mL of propargyl chloride (70%w/w, ca.9.2mol/L; 12.14mmol; Hydroxyl, potassium tert-butoxide, and propargyl chloride in a molar ratio of 1.0:1.0:2.0) were dissolved in 60 mL of THF, and slowly transferred to reaction solution A under _N2 protection, ice bath, and stirring conditions, Keep stirring at 10°C for 40 h to obtain reaction solution B.

Add 80mL of salt water to the reaction solution B for extraction, separate the water layer, and keep the THF layer; extract the water layer with ethyl acetate (3×50mL), collect the organic layer, namely the THF layer and the EtOAc layer, and then wash it with 100mL of saturated salt Water extraction, discarding the water layer, and then combining the obtained material with the above-mentioned reserved tetrahydrofuran (THF) layer to obtain an organic material;

The organic material was dried over anhydrous MgSO ₄ , filtered, and the solvent was evaporated to obtain alkynylated polybutadiene (5.9733 g, yield 97.4%).

Through the infrared image of the alkynylated polybutadiene product and the NMR image of the product, it can be known that the reaction has successfully connected an alkynyl group and a propargyl group.

The obtained product can be cross-linked by chemical reaction with an azide energetic compound (specifically GAP, 1,4-bis(azidomethyl)benzene) to obtain a novel energetic adhesive.

Embodiment 7:

Hydroxyl-terminated polybutadiene (HTPB, ie butyl hydroxyl) was vacuum-dried at 60°C for 4h; weighed 6.3427g of hydroxyl-terminated polybutadiene with a hydroxyl value of 1.3033mmol KOH/g (-OH in hydroxyl-terminated polybutadiene The total amount of 8.27mmol) was dissolved in 20mL THF to obtain a THF solution containing HTPB; another 1.8400g t-BuOK (16.40mmol) was dissolved in 20mL of THF to obtain a t-BuOK solution; Slowly add the THF solution containing HTPB into the t-BuOK solution under the conditions, and continue to stir for 10 minutes to obtain the reaction solution A; take 1.00 mL of propargyl bromide (80% w/w, ca.9.2mol/L; 9.20mmol; The molar ratio of hydroxyl group, potassium tert-butoxide and propargyl chloride is 1.0:2.0:1.1) was dissolved in 60mL of THF, and it was slowly transferred to the reaction solution A under _N2 protection, ice bath and stirring conditions, Keep stirring at 8°C for 42h to obtain reaction solution B.

Add 80mL of salt water to the reaction solution B for extraction, separate the water layer, and keep the THF layer; extract the water layer with ethyl acetate (3×50mL), collect the organic layer, namely the THF layer and the EtOAc layer, and then wash it with 100mL of saturated salt Water extraction, discarding the water layer, and then combining the obtained material with the above-mentioned reserved tetrahydrofuran (THF) layer to obtain an organic material;

The organic material was dried over anhydrous MgSO ₄ , filtered, and the solvent was evaporated to obtain alkynylated polybutadiene (6.4639 g, yield 97.1%).

The infrared images of hydroxyl-terminated polybutadiene (HTPB, ie, butylated hydroxyl) raw materials and alkynylated polybutadiene products are shown in Figure 5. In Figure 5, the hydroxyl group of the raw material HTPB has an absorption peak at 3350 cm ^-1 in the characteristic area, which belongs to the stretching vibration peak of -OH, and the peak here in the post-reaction product (PTPB) is significantly weakened, and it clearly appears at 3307 cm ^-1 The CH stretching vibration peak of the alkynyl group was obtained, which proved that the reaction was successfully connected to the alkynyl group;

The NMR diagram of hydroxyl-terminated polybutadiene (HTPB, namely hydroxybutylene) raw material is shown in Figure 6, and its peak shape is completely consistent with that reported in the literature. The chemical shifts of each CH in HTPB are marked in the figure, and the place at 7.26ppm is the solvent CDCl ₃ By comparing with the product ¹ H NMR spectrum, it is determined that the two additional peaks (e, f in Figure 7) are respectively assigned to the vibration peaks of methylene (e) and terminal CH (f) on the propargyl group .

The ¹ H NMR spectrum of the alkynylated polybutadiene product is shown in Figure 7. Compared with Figure 6, two peaks are clearly increased/enhanced at 4.13ppm (e) and 2.42ppm (f), which belong to The vibration peak of the methylene group (e) on the propargyl group and the terminal CH (f), and the solvent peak of CDCl ₃ at 7.26ppm. By comparing Figure 6 and Figure 7, it can be proved that the propargyl group was successfully attached.

The obtained product can be cross-linked by chemical reaction with an azide energetic compound (specifically GAP, 1,4-bis(azidomethyl)benzene) to obtain a novel energetic adhesive.

Embodiment 8:

Hydroxyl-terminated polybutadiene (HTPB, ie, hydroxybutyl) was vacuum-dried at 50°C for 2h; weighed 4.4725g of hydroxyl-terminated polybutadiene with a hydroxyl value of 1.4845mmol KOH/g (-OH in hydroxyl-terminated polybutadiene The total amount of 6.64mmol) was dissolved in 20mL THF to obtain a THF solution containing HTPB; another 1.9635g t-BuOK (17.50mmol) was dissolved in 20mL of THF to obtain a t-BuOK solution; Under the conditions, the THF solution containing HTPB was slowly added to the t-BuOK solution, and the stirring was continued for 10 minutes to obtain the reaction solution A; 2.3510 g of 4-chloro-1-butyne (25.55 mmol; hydroxyl, potassium tert-butoxide, propane The molar ratio of alkyne chloride is 1.0:2.6:3.8) was dissolved in 60mL of THF, under the condition of _N2 protection, ice bath and stirring, it was slowly transferred to the reaction solution A, kept at 0°C and continued to stir for 45h to obtain Reaction solution B.

Add 80mL of salt water to the reaction solution B for extraction, separate the water layer, and keep the THF layer; extract the water layer with ethyl acetate (3×50mL), collect the organic layer, namely the THF layer and the EtOAc layer, and then wash it with 100mL of saturated salt Water extraction, discarding the water layer, and then combining the obtained material with the above-mentioned reserved tetrahydrofuran (THF) layer to obtain an organic material;

The organic material was dried over anhydrous MgSO ₄ , filtered, and the solvent was evaporated to obtain alkynylated polybutadiene (4.7841 g, yield 99.3%).

Through the infrared image of the alkynylated polybutadiene product and the NMR image of the product, it can be known that the reaction has successfully connected an alkynyl group and a propargyl group.

The obtained product can be cross-linked by chemical reaction with an azide energetic compound (specifically GAP, 1,4-bis(azidomethyl)benzene) to obtain a novel energetic adhesive.

Embodiment 9:

Hydroxyl-terminated polybutadiene (HTPB, ie, butyl hydroxyl) was vacuum-dried at 50°C for 8h; weighed 4.8236g of hydroxyl-terminated polybutadiene with a hydroxyl value of 1.6228mmol KOH/g (-OH in hydroxyl-terminated polybutadiene The total amount of 7.83mmol) was dissolved in 20mL THF to obtain a THF solution containing HTPB; another 3.5141g t-BuOK (31.32mmol) was dissolved in 20mL of THF to obtain a t-BuOK solution; Under the conditions, the THF solution containing HTPB was slowly added to the t-BuOK solution, and the stirring was continued for 10 min to obtain the reaction solution A; 2.0801 g of 4-bromo-1-butyne (15.64 mmol; hydroxyl, potassium tert-butoxide, propane The molar ratio of alkyne chloride is 1.0:4.0:2.0) was dissolved in 60mL of THF, under the condition of _N2 protection, ice bath and stirring, it was slowly transferred to the reaction solution A, kept at 15°C and continued to stir for 45h to obtain Reaction solution B.

Add 80mL of salt water to the reaction solution B for extraction, separate the water layer, and keep the THF layer; extract the water layer with ethyl acetate (3×50mL), collect the organic layer, namely the THF layer and the EtOAc layer, and then wash it with 100mL of saturated salt Water extraction, discarding the water layer, and then combining the obtained material with the above-mentioned reserved tetrahydrofuran (THF) layer to obtain an organic material;

The organic material was dried over anhydrous MgSO ₄ , filtered, and the solvent was evaporated to obtain alkynylated polybutadiene (5.0382 g, yield 96.3%).

Through the infrared image of the alkynylated polybutadiene product and the NMR image of the product, it can be known that the reaction has successfully connected an alkynyl group and a propargyl group.

The obtained product can be cross-linked by chemical reaction with an azide energetic compound (specifically GAP, 1,4-bis(azidomethyl)benzene) to obtain a novel energetic adhesive.

Example 10:

Hydroxy-terminated polybutadiene (HTPB, ie, hydroxybutyl) was vacuum-dried at 50°C for 7 hours; weighed 5.3308g of hydroxyl-terminated polybutadiene with a hydroxyl value of 1.7658mmol KOH/g (-OH in hydroxyl-terminated polybutadiene The total amount of 9.41mmol) was dissolved in 20mL THF to obtain a THF solution containing HTPB; another 4.2232g t-BuOK (37.64mmol) was dissolved in 20mL of THF to obtain a t-BuOK solution; Slowly add the THF solution containing HTPB into the t-BuOK solution under the conditions, and continue to stir for 10 minutes to obtain the reaction solution A; take 4.09mL of propargyl bromide (80%w/w, ca.9.2mol/L; 37.63mmol; The molar ratio of hydroxyl group, potassium tert-butoxide, and propargyl chloride is 1.0:4.0:4.0) was dissolved in 60mL of THF, and was slowly transferred to the reaction solution A under _N2 protection, ice bath and stirring conditions, Keep stirring at 0°C for 48h to obtain reaction solution B.

Add 80mL of salt water to the reaction solution B for extraction, separate the water layer, and keep the THF layer; extract the water layer with ethyl acetate (3×50mL), collect the organic layer, namely the THF layer and the EtOAc layer, and then wash it with 100mL of saturated salt Water extraction, discarding the water layer, and then combining the obtained material with the above-mentioned reserved tetrahydrofuran (THF) layer to obtain an organic material;

The organic material was dried over anhydrous MgSO ₄ , filtered, and the solvent was evaporated to obtain alkynylated polybutadiene (5.6429 g, yield 99.2%).

Through the infrared image of the alkynylated polybutadiene product and the NMR image of the product, it can be known that the reaction has successfully connected an alkynyl group and a propargyl group.

The obtained product can be cross-linked by chemical reaction with an azide energetic compound (specifically GAP, 1,4-bis(azidomethyl)benzene) to obtain a novel energetic adhesive.

Each raw material enumerated in the present invention can realize the present invention, and the upper and lower limit value of each raw material and its interval value can realize the present invention, and the upper and lower limit value of process parameter (such as temperature, time etc.) of the present invention and its interval value The present invention can be realized, and the embodiments are not listed one by one here.

Claims (2)

1. a preparation method of alkynylated polybutadiene is characterized in that it comprises the steps: 1) Pretreatment of raw materials: hydroxy-terminated polybutadiene is vacuum-dried at 40-60 oC for 2-8 h; 2) Selection of raw materials: The total amount of -OH in hydroxyl-terminated polybutadiene is based on the molar ratio: potassium tert-butoxide: halogenated alkyne = 1:0.5～4:0.5～4, select hydroxyl-terminated polybutadiene, Potassium tert-butoxide and haloalkynes; 3) According to the proportion of hydroxyl-terminated polybutadiene and tetrahydrofuran is 4.4725g ~ 6.6257g: 20mL, choose tetrahydrofuran, and dissolve hydroxyl-terminated polybutadiene in tetrahydrofuran to obtain a hydroxyl-terminated polybutadiene solution; According to the ratio of potassium tert-butoxide to tetrahydrofuran is 0.1515g-1.9635g: 20mL, choose tetrahydrofuran, dissolve potassium tert-butoxide in tetrahydrofuran to obtain potassium tert-butoxide solution; According to the proportion of haloalkynes and tetrahydrofuran being 0.15mL to 4.09mL: 60mL, choose tetrahydrofuran, and dissolve haloalkynes in tetrahydrofuran to obtain haloalkyne solutions; Under the conditions of stirring and ice bathing, the hydroxyl-terminated polybutadiene solution was added to the potassium tert-butoxide solution A to obtain a reaction solution, and under the conditions of _N2 protection, ice bathing and stirring, halogenated Alkyne solution, kept at 0-25 oC to react for 24-48 hours to obtain reaction solution B; 4) Add saline to the reaction solution B for extraction, separate the water layer, and keep the THF layer; Extracting the aqueous layer with ethyl acetate, collecting the organic layer; collecting the organic layer and then extracting it with saturated brine, discarding the aqueous layer, and combining the obtained material with the above-mentioned retained tetrahydrofuran layer to obtain an organic material; 5) The organic material is dried with anhydrous MgSO ₄ , filtered, and the solvent is evaporated to obtain alkynylated polybutadiene; The hydroxyl value of the hydroxyl-terminated polybutadiene is between 0.4236 and 1.7658 mmol KOH/g. 2. the preparation method of a kind of alkynylated polybutadiene according to claim 1 is characterized in that: described haloalkyne is propyne bromide, propyne chloride, 4-bromo-1-butyne or 4-Chloro-1-butyne.

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