CN102516434A - Preparation method of alkynyl polybutadiene - Google Patents
Preparation method of alkynyl polybutadiene Download PDFInfo
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Abstract
The invention relates to a preparation method of alkynyl polybutadiene and belongs to the technical field of novel materials. The preparation method of the alkynyl polybutadiene is characterized by comprising the following steps of: 1) pre-treating a raw material; 2) selecting the raw material, i.e. selecting hydroxyl-terminated polybutadiene, potassium tert-butoxide and halogenated alkyne according to the molar ratio being the total amount of OH in the hydroxyl-terminated polybutadiene to potassium tert-butoxide to halogenated alkyne equal to 1:(0.5-4):(0.5-4); 3) adding hydroxyl-terminated polybutadiene solution into potassium tert-butoxide solution A under the agitation and the ice bath conditions to obtain reaction liquid, adding halogenated alkyne solution into the reaction liquid under the N2 protection, the ice bath and the agitation conditions, keeping at a temperature of 0-25 DEG C and reacting for 24-48 hours to obtain reaction liquid B; 4) adding saline solution into the reaction liquid B to extract, separating out a water layer and keeping a tetrahydrofuran layer; and 5) drying with anhydrous MgSO4, filtering and volatilizing a solvent to obtain the alkynyl polybutadiene. The preparation method has the advantages of high efficiency, simplicity and environment friendliness.
Description
Technical field
The present invention relates to a kind of preparation method of alkynyl polyhutadiene, belong to technical field of novel materials.
Background technology
SP is not only one of emission energy of rocket and guided missile, but also is a member in the whole engine structure, and the performance of the energetic material of this densification plays decisive role to each item performance index of whole propulsion system.Polymkeric substance based on polyurethane chemistry is the most general tackiness agent in the solid compositepropellent; And hydroxy-terminated polybutadienes (HTPB) is the fourth hydroxyl; With its lower viscosity, good use characteristics, high solid amount of filling, than curing reaction and good preservation performance more completely with and reducible cost advantage, have extensive studies to use at SP and fiery explosive field.Yet, along with the continuous increase that Push Technology is required, to the fourth hydroxyl being the also progressively raising of mechanical properties of propellant requirement of tackiness agent.Making HTPB be cross-linked to form inierpeneirating network structure through the adding linking agent at present is a kind of method of improving its mechanical property, and modal linking agent is an isocyanates, and in addition, the application of linking agents such as alcamines, aziridines in fourth hydroxyl propelling agent also has report.
Nitrine class energy-containing compound is meant and contains azido group (N
3) material, and nitrine (N
3) be the higher state of energy level, so the nitrine compounds often has higher just generation heat, is one of maximum energetic material of research at present.When its conduct contains the ability tackiness agent; Because the azido group energy content is high, its thermolysis is prior to main chain and independently carry out, so can not only increase the energy of prescription; And can also quicken propelling agent to a certain extent and decompose; Reduce quick-fried temperature, reduce ablation, can be used to prepare simultaneously the propelling agent of insensitive low signature weapons with pipes.So some nitrine class energy-containing compounds can and be applied to the tackiness agent of propelling agent and fiery explosive.
The cycloaddition reaction of alkynyl and nitrine functional group can generate 1,2,3-triazoles class five-ring, is the most classical one type " click " reaction, also claims Huisgen reaction.This type of reaction has high selectivity, and product yield is high, and no coupling product generates (atom utilization is high), and has good reaction kinetics (technology is easy to control).Therefore; Based on 1 between the polyhutadiene of alkynylization and the nitrine class energy-containing compound; The 3-Dipolar Cycloaddition can make them crosslinked; Keep their performance advantages separately simultaneously, and crosslinked action can further improve its relevant mechanical property, therefore being expected to make up a kind of novel containing can tackiness agent.Because can have certain hydrophobicity by tackiness agent this novel containing; Be expected and be used with ADN oxygenants such as (AND); Can solve the problem that oxygenant AND absorbs water like this in application process, thereby realize preparation based on the energetic cleaning propelling agent of nitrine class and AND.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of alkynyl polyhutadiene, this method technology is simple, environmental protection.
For realizing above-mentioned purpose, the technical scheme that the present invention taked is: a kind of preparation method of alkynyl polyhutadiene is characterized in that it comprises the steps:
1) pre-treatment of raw material: hydroxy-terminated polybutadienes (HTPB, i.e. fourth hydroxyl) is at 40～60 ℃ of following vacuum-drying 2～8h; THF, (being that THF does not contain water) dewaters;
2) choosing of raw material: be hydroxy-terminated polybutadienes (HTPB in molar ratio; Be the fourth hydroxyl) in-total amount of OH: potassium tert.-butoxide (t-BuOK): acetylenic halide=1: 0.5～4: 0.5～4; Choose hydroxy-terminated polybutadienes (HTPB, i.e. fourth hydroxyl), potassium tert.-butoxide (t-BuOK), acetylenic halide;
3) proportioning by hydroxy-terminated polybutadienes and THF (THF) is 4.4725g～6.6257g: 20mL; Choose THF; With the solvent of THF (THF) as reaction; Hydroxy-terminated polybutadienes is dissolved in the THF (THF), obtains hydroxy-terminated polybutadienes solution (the THF solution that promptly contains HTPB);
Proportioning by potassium tert.-butoxide (t-BuOK) and THF (THF) is 0.1515g～1.9635g: 20mL; Choose THF; With the solvent of THF (THF) as reaction, potassium tert.-butoxide is dissolved in the THF (THF), obtain potassium tert.-butoxide solution (being t-BuOK solution);
Proportioning by acetylenic halide and THF (THF) is 0.15mL～4.09mL: 60mL; Choose THF; With the solvent of THF (THF) as reaction, acetylenic halide is dissolved in the THF (THF), obtain acetylenic halide solution (the THF solution that promptly contains acetylenic halide);
Under stirring, condition of ice bath, hydroxy-terminated polybutadienes solution is joined in the potassium tert.-butoxide solution A, obtain reaction solution, at N
2Under protection and ice bath, the agitation condition, in reaction solution A, add acetylenic halide solution, keep 0～25 ℃ to make its reaction 24～48h, obtain reaction solution B;
4) in reaction solution B, add salt solution and extract, isolate water layer, keep THF (THF) layer;
Water layer is extracted collected organic layer (being THF layer and EtOAc layer) with ETHYLE ACETATE (EtOAc); Collected organic layer with the saturated aqueous common salt extraction, discards water layer again, and the material that obtains merges with above-mentioned reservation THF (THF) layer again, obtains organic materials;
5) organic materials is through anhydrous MgSO
4Drying, filtration, solvent flashing obtain alkynyl polyhutadiene (the finished product).
The hydroxyl value of the described hydroxy-terminated polybutadienes of step 1) (HTPB, i.e. fourth hydroxyl) is between 0.4236～1.7658mmol KOH/g (i.e. 23.76～99.06mg KOH/g).
Described acetylenic halide is propine bromine, propine chlorine, 4-bromo-ethyl acetylene or 4-chloro-ethyl acetylene.
The preparing method's of a kind of alkynyl polyhutadiene provided by the invention reaction equation is as shown in Figure 1.
The structural formula of alkynyl polyhutadiene is:
In the structural formula, x and z represent that the position of C=C on main chain, is through 1, and the 4-addition obtains, and comprises cis and trans; Y representes the position of C=C on side chain, and promptly through 1, the 2-addition obtains; M is 1 or 2.
Beneficial effect of the present invention is: through being the proton that alkali is captured hydroxyl among the HTPB with the potassium tert.-butoxide, successfully connect alkynyl thereby slough halogen with the reaction of acetylenic halide class subsequently.The inventive method yield is high, preparation technology is simple, environmental protection; Products obtained therefrom is expected can be crosslinked with nitrine class energy-containing compound generation chemical reaction; Thereby improve the relevant mechanical property of propelling agent, in development field, will have the potential using value based on nitrine class energetic cleaning propelling agent.
Description of drawings
Fig. 1 is the preparing method's of alkynyl polyhutadiene a reaction equation;
Fig. 2 is raw material and the infrared figure of product of embodiment 5;
Fig. 3 is the raw material nuclear-magnetism figure of embodiment 5;
Fig. 4 is the product nuclear-magnetism figure of embodiment 5;
Fig. 5 is raw material and the infrared figure of product of embodiment 7;
Fig. 6 is the raw material nuclear-magnetism figure of embodiment 7;
Fig. 7 is the product nuclear-magnetism figure of embodiment 7.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to following embodiment.
Embodiment 1:
Hydroxy-terminated polybutadienes (HTPB, i.e. fourth hydroxyl) is at 40 ℃ of following vacuum-drying 2h; The hydroxy-terminated polybutadienes 6.3754g (in the hydroxy-terminated polybutadienes-total amount of OH is 2.70mmol) that takes by weighing hydroxyl value and be 0.4236mmol KOH/g is dissolved among the 20mL THF, obtains containing the THF solution of HTPB; Other gets 0.1515g t-BuOK (1.35mmol) and is dissolved among the THF of 20mL, obtains t-BuOK solution; The THF solution that under ice bath, stirring condition, will contain HTPB slowly adds in the t-BuOK solution, continues to stir 10min, obtains reaction solution A; Get propine bromine (80%w/w, the ca.9.2mol/L of 0.15mL; 1.38mmol; The mol ratio of hydroxy-terminated polybutadienes, potassium tert.-butoxide, propine bromine is 1.0: 0.5: 0.5) be dissolved among the THF of 60mL, at N
2Under protection and ice bath, the agitation condition, it slowly is transferred among the reaction solution A, keeps 0 ℃ to continue to stir 48h, obtain reaction solution B.
In reaction solution B, add the 80mL salt solution and extract, isolate water layer, keep the THF layer; (3 * 50mL) extract, and collected organic layer is THF layer and EtOAc layer, and organic layer with the extraction of 100mL saturated aqueous common salt, discards water layer again, and the material that obtains merges with above-mentioned reservation THF (THF) layer again, obtains organic materials with ETHYLE ACETATE with water layer;
Organic materials is through anhydrous MgSO
4Drying, filtration, solvent flashing obtain alkynyl polyhutadiene (6.3723g, yield 99.1%).
Through the infrared figure of alkynyl polyhutadiene product and the nuclear-magnetism figure of product, but principal reaction has successfully connected alkynyl and has successfully connected propargyl.
Nitrine class energy-containing compound is specially and gathers nitrine glycidyl ether (GAP), 3-azidomethyl-methyl oxetane homopolymer (PAMMO) or 3; 3-two azido-methyl oxa-fourth ring homopolymer (PBAMO), 1; 11-two nitrine-3; 6,9-trioxa undecane, 1, the triazo-compound of different structure such as 4-two (azido-methyl) benzene and functionality.Chemical reaction can take place and crosslinked with nitrine class energy-containing compound (being specially GAP, 1,4-two (azido-methyl) benzene) in products obtained therefrom, and obtaining a kind of novel containing can tackiness agent.
Embodiment 2:
Hydroxy-terminated polybutadienes (HTPB, i.e. fourth hydroxyl) is at 40 ℃ of following vacuum-drying 8h; The hydroxy-terminated polybutadienes 6.6257g (in the hydroxy-terminated polybutadienes-total amount of OH is 3.66mmol) that takes by weighing hydroxyl value and be 0.5524mmol KOH/g is dissolved among the 20mL THF, obtains containing the THF solution of HTPB; Other gets 0.2053g t-BuOK (1.83mmol) and is dissolved among the THF of 20mL, obtains t-BuOK solution; The THF solution that under ice bath, stirring condition, will contain HTPB slowly adds in the t-BuOK solution, continues to stir 10min, obtains reaction solution A; Get propine chlorine (70%w/w, the ca.9.2mol/L of 0.20mL; 1.84mmol; The mol ratio of hydroxyl, potassium tert.-butoxide, propine chlorine is 1.0: 0.5: 0.5) be dissolved among the THF of 60mL, at N
2Under protection and ice bath, the agitation condition, it slowly is transferred among the reaction solution A, keeps 15 ℃ to continue to stir 36h, obtain reaction solution B.
In reaction solution B, add the 80mL salt solution and extract, isolate water layer, keep the THF layer; (3 * 50mL) extract, and collected organic layer is THF layer and EtOAc layer, and organic layer with the extraction of 100mL saturated aqueous common salt, discards water layer again, and the material that obtains merges with above-mentioned reservation THF (THF) layer again, obtains organic materials with ETHYLE ACETATE with water layer;
Organic materials is through anhydrous MgSO
4Drying, filtration, solvent flashing obtain alkynyl polyhutadiene (6.5885g, yield 98.4%).
Through the infrared figure of alkynyl polyhutadiene product and the nuclear-magnetism figure of product, but principal reaction has successfully connected alkynyl and has successfully connected propargyl.
Chemical reaction can take place and crosslinked with nitrine class energy-containing compound (be specially GAP, 1,4-two (azido-methyl) benzene) in products obtained therefrom, and obtaining a kind of novel containing can tackiness agent.
Embodiment 3:
Hydroxy-terminated polybutadienes (HTPB, i.e. fourth hydroxyl) is at 40 ℃ of following vacuum-drying 6h; The hydroxy-terminated polybutadienes 6.3427g (in the hydroxy-terminated polybutadienes-total amount of OH is 4.37mmol) that takes by weighing hydroxyl value and be 0.6886mmol KOH/g is dissolved among the 20mL THF, obtains containing the THF solution of HTPB; Other gets 0.4903g t-BuOK (4.37mmol) and is dissolved among the THF of 20mL, obtains t-BuOK solution; The THF solution that under ice bath, stirring condition, will contain HTPB slowly adds in the t-BuOK solution, continues to stir 10min, obtains reaction solution A; Get the 4-bromine ethyl acetylene (2.21mmol of 0.2936g; The mol ratio of hydroxyl, potassium tert.-butoxide, propine chlorine is 1.0: 1.0: 0.5) be dissolved among the THF of 60mL, at N
2Under protection and ice bath, the agitation condition, it slowly is transferred among the reaction solution A, keeps 25 ℃ to continue to stir 24h, obtain reaction solution B.
In reaction solution B, add the 80mL salt solution and extract, isolate water layer, keep the THF layer; (3 * 50mL) extract, and collected organic layer is THF layer and EtOAc layer, with the extraction of 100mL saturated aqueous common salt, discard water layer again, and the material that obtains merges with above-mentioned reservation THF (THF) layer again, obtains organic materials with ETHYLE ACETATE with water layer;
Organic materials is through anhydrous MgSO
4Drying, filtration, solvent flashing obtain alkynyl polyhutadiene (6.3801g, yield 98.8%).
Through the infrared figure of alkynyl polyhutadiene product and the nuclear-magnetism figure of product, but principal reaction has successfully connected alkynyl and has successfully connected propargyl.
Chemical reaction can take place and crosslinked with nitrine class energy-containing compound (be specially GAP, 1,4-two (azido-methyl) benzene) in products obtained therefrom, and obtaining a kind of novel containing can tackiness agent.
Embodiment 4:
Hydroxy-terminated polybutadienes (HTPB, i.e. fourth hydroxyl) is at 50 ℃ of following vacuum-drying 5h; The hydroxy-terminated polybutadienes 6.1724g (in the hydroxy-terminated polybutadienes-total amount of OH is 4.67mmol) that takes by weighing hydroxyl value and be 0.7562mmol KOH/g is dissolved among the 20mL THF, obtains containing the THF solution of HTPB; Other gets 0.5240g t-BuOK (4.67mmol) and is dissolved among the THF of 20mL, obtains t-BuOK solution; The THF solution that under ice bath, stirring condition, will contain HTPB slowly adds in the t-BuOK solution, continues to stir 10min, obtains reaction solution A; Get the 4-chloro-ethyl acetylene (4.69mmol of 0.4154g; The mol ratio of hydroxyl, potassium tert.-butoxide, propine chlorine is 1.0: 1.0: 1.0) be dissolved among the THF of 60mL, at N
2Under protection and ice bath, the agitation condition, it slowly is transferred among the reaction solution A, keeps 0 ℃ to continue to stir 48h, obtain reaction solution B.
In reaction solution B, add the 80mL salt solution and extract, isolate water layer, keep the THF layer; (3 * 50mL) extract, and collected organic layer is THF layer and EtOAc layer, with the extraction of 100mL saturated aqueous common salt, discard water layer again, and the material that obtains merges with above-mentioned reservation THF (THF) layer again, obtains organic materials with ETHYLE ACETATE with water layer;
Organic materials is through anhydrous MgSO
4Drying, filtration, solvent flashing obtain alkynyl polyhutadiene (6.2613g, yield 97.6%).
Through the infrared figure of alkynyl polyhutadiene product and the nuclear-magnetism figure of product, but principal reaction has successfully connected alkynyl and has successfully connected propargyl.
Chemical reaction can take place and crosslinked with nitrine class energy-containing compound (be specially GAP, 1,4-two (azido-methyl) benzene) in products obtained therefrom, and obtaining a kind of novel containing can tackiness agent.
Embodiment 5:
Hydroxy-terminated polybutadienes (HTPB, i.e. fourth hydroxyl) is at 60 ℃ of following vacuum-drying 2h; The hydroxy-terminated polybutadienes 5.7060g (in the hydroxy-terminated polybutadienes-total amount of OH is 4.79mmol) that takes by weighing hydroxyl value and be 0.8399mmol KOH/g is dissolved among the 20mL THF, obtains containing the THF solution of HTPB; Other gets 1.1033g t-BuOK (9.83mmol) and is dissolved among the THF of 20mL, obtains t-BuOK solution; The THF solution that under ice bath, stirring condition, will contain HTPB slowly adds in the t-BuOK solution, continues to stir 10min, obtains reaction solution A; Get propine bromine (80%w/w, the ca.9.2mol/L of 1.10mL; 10.12mol; The mol ratio of hydroxyl, potassium tert.-butoxide, propine chlorine is 1.0: 2.1: 2.1) be dissolved among the THF of 60mL, at N
2Under protection and ice bath, the agitation condition, it slowly is transferred among the reaction solution A, keeps 0～25 ℃ to continue to stir 48h, obtain reaction solution B.
In reaction solution B, add the 80mL salt solution and extract, isolate water layer, keep the THF layer; (3 * 50mL) extract, and collected organic layer is THF layer and EtOAc layer, with the extraction of 100mL saturated aqueous common salt, discard water layer again, and the material that obtains merges with above-mentioned reservation THF (THF) layer again, obtains organic materials with ETHYLE ACETATE with water layer;
Organic materials is through anhydrous MgSO
4Drying, filtration, solvent flashing obtain alkynyl polyhutadiene (5.8645g, yield 99.6%).
Hydroxy-terminated polybutadienes (HTPB, i.e. fourth hydroxyl) raw material and the infrared figure of alkynyl polyhutadiene product are as shown in Figure 2.The hydroxyl of raw material HTPB is 3350cm at the absorption peak of characteristic area among Fig. 2
-1The place belongs to-stretching vibration peak of OH, and the peak here weakens in the reaction after product (PTPB), and at 3307cm
-1The CH stretching vibration peak of alkynyl has obviously appearred in the place, and proved response has successfully connected alkynyl;
Hydroxy-terminated polybutadienes (HTPB, i.e. fourth hydroxyl) raw material
1H NMR spectrogram is as shown in Figure 3, and its peak shape and bibliographical information are in full accord, and the chemical shift of each CH marks in figure among the HTPB, and the 7.26ppm place is solvent C DCl
3Vibration peak, through with product
1H NMR spectrogram relatively, (e among Fig. 4 f) belongs to methylene radical (e) and terminal CH (f) vibration peak on the propargyl respectively to the Liang Chufeng that confirms to increase.
Alkynyl polyhutadiene product
1As shown in Figure 4 and the Fig. 3 of H NMR spectrogram relatively locates obvious increase/strengthened Liang Chufeng (Fig. 7 is more obvious) at 4.13ppm (e) and 2.42ppm (f), belongs to methylene radical (e) and the vibration peak of terminal CH (f) on the propargyl respectively, and the 7.26ppm place is CDCl
3Solvent peak.Through comparison diagram 3 and the provable propargyl that successfully connects of Fig. 4.
Chemical reaction can take place and crosslinked with nitrine class energy-containing compound (be specially GAP, 1,4-two (azido-methyl) benzene) in products obtained therefrom, and obtaining a kind of novel containing can tackiness agent.
Embodiment 6:
Hydroxy-terminated polybutadienes (HTPB, i.e. fourth hydroxyl) is at 60 ℃ of following vacuum-drying 8h; The hydroxy-terminated polybutadienes 5.9029g (in the hydroxy-terminated polybutadienes-total amount of OH is 6.05mmol) that takes by weighing hydroxyl value and be 1.0251mmol KOH/g is dissolved among the 20mL THF, obtains containing the THF solution of HTPB; Other gets 0.6788g t-BuOK (6.05mmol) and is dissolved among the THF of 20mL, obtains t-BuOK solution; The THF solution that under ice bath, stirring condition, will contain HTPB slowly adds in the t-BuOK solution, continues to stir 10min, obtains reaction solution A; Get propine chlorine (70%w/w, the ca.9.2mol/L of 1.32mL; 12.14mmol; The mol ratio of hydroxyl, potassium tert.-butoxide, propine chlorine is 1.0: 1.0: 2.0) be dissolved among the THF of 60mL, at N
2Under protection and ice bath, the agitation condition, it slowly is transferred among the reaction solution A, keeps 10 ℃ to continue to stir 40h, obtain reaction solution B.
In reaction solution B, add the 80mL salt solution and extract, isolate water layer, keep the THF layer; (3 * 50mL) extract, and collected organic layer is THF layer and EtOAc layer, with the extraction of 100mL saturated aqueous common salt, discard water layer again, and the material that obtains merges with above-mentioned reservation THF (THF) layer again, obtains organic materials with ETHYLE ACETATE with water layer;
Organic materials is through anhydrous MgSO
4Drying, filtration, solvent flashing obtain alkynyl polyhutadiene (5.9733g, yield 97.4%).
Through the infrared figure of alkynyl polyhutadiene product and the nuclear-magnetism figure of product, but principal reaction has successfully connected alkynyl and has successfully connected propargyl.
Chemical reaction can take place and crosslinked with nitrine class energy-containing compound (be specially GAP, 1,4-two (azido-methyl) benzene) in products obtained therefrom, and obtaining a kind of novel containing can tackiness agent.
Embodiment 7:
Hydroxy-terminated polybutadienes (HTPB, i.e. fourth hydroxyl) is at 60 ℃ of following vacuum-drying 4h; The hydroxy-terminated polybutadienes 6.3427g (in the hydroxy-terminated polybutadienes-total amount of OH is 8.27mmol) that takes by weighing hydroxyl value and be 1.3033mmol KOH/g is dissolved among the 20mL THF, obtains containing the THF solution of HTPB; Other gets 1.8400g t-BuOK (16.40mmol) and is dissolved among the THF of 20mL, obtains t-BuOK solution; The THF solution that under ice bath, stirring condition, will contain HTPB slowly adds in the t-BuOK solution, continues to stir 10min, obtains reaction solution A; Get propine bromine (80%w/w, the ca.9.2mol/L of 1.00mL; 9.20mmol; The mol ratio of hydroxyl, potassium tert.-butoxide, propine chlorine is 1.0: 2.0: 1.1) be dissolved among the THF of 60mL, at N
2Under protection and ice bath, the agitation condition, it slowly is transferred among the reaction solution A, keeps 8 ℃ to continue to stir 42h, obtain reaction solution B.
In reaction solution B, add the 80mL salt solution and extract, isolate water layer, keep the THF layer; (3 * 50mL) extract, and collected organic layer is THF layer and EtOAc layer, with the extraction of 100mL saturated aqueous common salt, discard water layer again, and the material that obtains merges with above-mentioned reservation THF (THF) layer again, obtains organic materials with ETHYLE ACETATE with water layer;
Organic materials is through anhydrous MgSO
4Drying, filtration, solvent flashing obtain alkynyl polyhutadiene (6.4639g, yield 97.1%).
Hydroxy-terminated polybutadienes (HTPB, i.e. fourth hydroxyl) raw material and the infrared figure of alkynyl polyhutadiene product are as shown in Figure 5.The hydroxyl of raw material HTPB is 3350cm at the absorption peak of characteristic area among Fig. 5
-1The place belongs to-stretching vibration peak of OH, and the peak here significantly weakens in the reaction after product (PTPB), and at 3307cm
-1The CH stretching vibration peak of alkynyl has obviously appearred in the place, and proved response has successfully connected alkynyl;
Figure is as shown in Figure 6 for the raw material nuclear-magnetism for hydroxy-terminated polybutadienes (HTPB, i.e. fourth hydroxyl), and its peak shape and bibliographical information are in full accord, and the chemical shift of each CH marks in figure among the HTPB, and the 7.26ppm place is solvent C DCl
3Vibration peak, through with product
1H NMR spectrogram relatively, (e among Fig. 7 f) belongs to methylene radical (e) and terminal CH (f) vibration peak on the propargyl respectively to the Liang Chufeng that confirms to increase.
Alkynyl polyhutadiene product
1As shown in Figure 7 and the Fig. 6 of H NMR spectrogram relatively locates to increase significantly at 4.13ppm (e) and 2.42ppm (f)/strengthened Liang Chufeng, belongs to methylene radical (e) and the vibration peak of terminal CH (f) on the propargyl respectively, and the 7.26ppm place is CDCl
3Solvent peak.Through comparison diagram 6 and the provable propargyl that successfully connects of Fig. 7.
Chemical reaction can take place and crosslinked with nitrine class energy-containing compound (be specially GAP, 1,4-two (azido-methyl) benzene) in products obtained therefrom, and obtaining a kind of novel containing can tackiness agent.
Embodiment 8:
Hydroxy-terminated polybutadienes (HTPB, i.e. fourth hydroxyl) is at 50 ℃ of following vacuum-drying 2h; The hydroxy-terminated polybutadienes 4.4725g (in the hydroxy-terminated polybutadienes-total amount of OH is 6.64mmol) that takes by weighing hydroxyl value and be 1.4845mmol KOH/g is dissolved among the 20mL THF, obtains containing the THF solution of HTPB; Other gets 1.9635g t-BuOK (17.50mmol) and is dissolved among the THF of 20mL, obtains t-BuOK solution; The THF solution that under ice bath, stirring condition, will contain HTPB slowly adds in the t-BuOK solution, continues to stir 10min, obtains reaction solution A; Get the 4-chloro-ethyl acetylene (25.55mmol of 2.3510g; The mol ratio of hydroxyl, potassium tert.-butoxide, propine chlorine is 1.0: 2.6: 3.8) be dissolved among the THF of 60mL, at N
2Under protection and ice bath, the agitation condition, it slowly is transferred among the reaction solution A, keeps 0 ℃ to continue to stir 45h, obtain reaction solution B.
In reaction solution B, add the 80mL salt solution and extract, isolate water layer, keep the THF layer; (3 * 50mL) extract, and collected organic layer is THF layer and EtOAc layer, with the extraction of 100mL saturated aqueous common salt, discard water layer again, and the material that obtains merges with above-mentioned reservation THF (THF) layer again, obtains organic materials with ETHYLE ACETATE with water layer;
Organic materials is through anhydrous MgSO
4Drying, filtration, solvent flashing obtain alkynyl polyhutadiene (4.7841g, yield 99.3%).
Through the infrared figure of alkynyl polyhutadiene product and the nuclear-magnetism figure of product, but principal reaction has successfully connected alkynyl and has successfully connected propargyl.
Chemical reaction can take place and crosslinked with nitrine class energy-containing compound (be specially GAP, 1,4-two (azido-methyl) benzene) in products obtained therefrom, and obtaining a kind of novel containing can tackiness agent.
Embodiment 9:
Hydroxy-terminated polybutadienes (HTPB, i.e. fourth hydroxyl) is at 50 ℃ of following vacuum-drying 8h; The hydroxy-terminated polybutadienes 4.8236g (in the hydroxy-terminated polybutadienes-total amount of OH is 7.83mmol) that takes by weighing hydroxyl value and be 1.6228mmol KOH/g is dissolved among the 20mL THF, obtains containing the THF solution of HTPB; Other gets 3.5141g t-BuOK (31.32mmol) and is dissolved among the THF of 20mL, obtains t-BuOK solution; The THF solution that under ice bath, stirring condition, will contain HTPB slowly adds in the t-BuOK solution, continues to stir 10min, obtains reaction solution A; Get the 4-bromo-ethyl acetylene (15.64mmol of 2.0801g; The mol ratio of hydroxyl, potassium tert.-butoxide, propine chlorine is 1.0: 4.0: 2.0) be dissolved among the THF of 60mL, at N
2Under protection and ice bath, the agitation condition, it slowly is transferred among the reaction solution A, keeps 15 ℃ to continue to stir 45h, obtain reaction solution B.
In reaction solution B, add the 80mL salt solution and extract, isolate water layer, keep the THF layer; (3 * 50mL) extract, and collected organic layer is THF layer and EtOAc layer, with the extraction of 100mL saturated aqueous common salt, discard water layer again, and the material that obtains merges with above-mentioned reservation THF (THF) layer again, obtains organic materials with ETHYLE ACETATE with water layer;
Organic materials is through anhydrous MgSO
4Drying, filtration, solvent flashing obtain alkynyl polyhutadiene (5.0382g, yield 96.3%).
Through the infrared figure of alkynyl polyhutadiene product and the nuclear-magnetism figure of product, but principal reaction has successfully connected alkynyl and has successfully connected propargyl.
Chemical reaction can take place and crosslinked with nitrine class energy-containing compound (be specially GAP, 1,4-two (azido-methyl) benzene) in products obtained therefrom, and obtaining a kind of novel containing can tackiness agent.
Embodiment 10:
Hydroxy-terminated polybutadienes (HTPB, i.e. fourth hydroxyl) is at 50 ℃ of following vacuum-drying 7h; The hydroxy-terminated polybutadienes 5.3308g (in the hydroxy-terminated polybutadienes-total amount of OH is 9.41mmol) that takes by weighing hydroxyl value and be 1.7658mmol KOH/g is dissolved among the 20mL THF, obtains containing the THF solution of HTPB; Other gets 4.2232g t-BuOK (37.64mmol) and is dissolved among the THF of 20mL, obtains t-BuOK solution; The THF solution that under ice bath, stirring condition, will contain HTPB slowly adds in the t-BuOK solution, continues to stir 10min, obtains reaction solution A; Get propine bromine (80%w/w, the ca.9.2mol/L of 4.09mL; 37.63mmol; The mol ratio of hydroxyl, potassium tert.-butoxide, propine chlorine is 1.0: 4.0: 4.0) be dissolved among the THF of 60mL, at N
2Under protection and ice bath, the agitation condition, it slowly is transferred among the reaction solution A, keeps 0 ℃ to continue to stir 48h, obtain reaction solution B.
In reaction solution B, add the 80mL salt solution and extract, isolate water layer, keep the THF layer; (3 * 50mL) extract, and collected organic layer is THF layer and EtOAc layer, with the extraction of 100mL saturated aqueous common salt, discard water layer again, and the material that obtains merges with above-mentioned reservation THF (THF) layer again, obtains organic materials with ETHYLE ACETATE with water layer;
Organic materials is through anhydrous MgSO
4Drying, filtration, solvent flashing obtain alkynyl polyhutadiene (5.6429g, yield 99.2%).
Through the infrared figure of alkynyl polyhutadiene product and the nuclear-magnetism figure of product, but principal reaction has successfully connected alkynyl and has successfully connected propargyl.
Chemical reaction can take place and crosslinked with nitrine class energy-containing compound (be specially GAP, 1,4-two (azido-methyl) benzene) in products obtained therefrom, and obtaining a kind of novel containing can tackiness agent.
Each cited raw material of the present invention can both be realized the present invention; The bound value of each raw material with and interval value can both realize the present invention; The bound value of processing parameter of the present invention (like temperature, time etc.) with and interval value can both realize the present invention, do not enumerate embodiment one by one at this.
Claims (3)
1. the preparation method of an alkynyl polyhutadiene is characterized in that it comprises the steps:
1) pre-treatment of raw material: hydroxy-terminated polybutadienes is at 40～60 ℃ of following vacuum-drying 2～8h;
2) choosing of raw material: in molar ratio in the hydroxy-terminated polybutadienes-total amount of OH: potassium tert.-butoxide: acetylenic halide=1: 0.5～4: 0.5～4, choose hydroxy-terminated polybutadienes, potassium tert.-butoxide and acetylenic halide;
3) proportioning by hydroxy-terminated polybutadienes and THF is 4.4725g～6.6257g: 20mL, chooses THF, and hydroxy-terminated polybutadienes is dissolved in the THF, obtains hydroxy-terminated polybutadienes solution;
Proportioning by potassium tert.-butoxide and THF is 0.1515g～1.9635g: 20mL, chooses THF, and potassium tert.-butoxide is dissolved in the THF, obtains potassium tert.-butoxide solution;
Proportioning by acetylenic halide and THF is 0.15mL～4.09mL: 60mL, chooses THF, and acetylenic halide is dissolved in the THF, obtains acetylenic halide solution;
Under stirring, condition of ice bath, hydroxy-terminated polybutadienes solution is joined in the potassium tert.-butoxide solution A, obtain reaction solution, at N
2Under protection and ice bath, the agitation condition, in reaction solution A, add acetylenic halide solution, keep 0～25 ℃ to make its reaction 24～48h, obtain reaction solution B;
4) in reaction solution B, add salt solution and extract, isolate water layer, keep the THF layer;
Water layer is extracted collected organic layer with ETHYLE ACETATE; Collected organic layer with the saturated aqueous common salt extraction, discards water layer again, and the material that obtains merges with above-mentioned reservation THF layer again, obtains organic materials;
5) organic materials is through anhydrous MgSO
4Drying, filtration, solvent flashing obtain the alkynyl polyhutadiene.
2. the preparation method of a kind of alkynyl polyhutadiene according to claim 1 is characterized in that: the hydroxyl value described hydroxy-terminated polybutadienes of step 1)) is between 0.4236～1.7658mmol KOH/g.
3. the preparation method of a kind of alkynyl polyhutadiene according to claim 1 is characterized in that: described acetylenic halide is propine bromine, propine chlorine, 4-bromo-ethyl acetylene or 4-chloro-ethyl acetylene.
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| CN105315931A (en) * | 2014-05-30 | 2016-02-10 | 湖北航天化学技术研究所 | Solid rocket engine propellant lining layer material and preparation method thereof |
| CN106397639A (en) * | 2016-09-07 | 2017-02-15 | 西安近代化学研究所 | Synthesis method of alkynyl-terminated polybutadiene containing carbamate element |
| CN111233594A (en) * | 2019-12-12 | 2020-06-05 | 北京理工大学 | A is prepared from3Plasticized propynyl-terminated polybutadiene composite propellant and preparation method thereof |
| CN111517900A (en) * | 2019-12-12 | 2020-08-11 | 北京理工大学 | Composite propellant with propynyl-terminated polybutadiene as adhesive and preparation method thereof |
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| CN111517900A (en) * | 2019-12-12 | 2020-08-11 | 北京理工大学 | Composite propellant with propynyl-terminated polybutadiene as adhesive and preparation method thereof |
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