CN102516434B - 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
Solid propellant 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 every 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 processing performance, high solid amount of filling, than curing reaction and good preservation performance more completely with and reducible cost advantage, have research widely to use at solid propellant 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 by the adding linking agent at present is a kind of method of improving its mechanical property, and modal linking agent is 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 refers to contain 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 energy tackiness agent, because azido group energy content height, its thermolysis is prior to main chain and independently carry out, so can not only increase the energy of prescription, and can also accelerate propelling agent to a certain extent and decompose, reduce quick-fried temperature, reduce the ablation to weapons with pipes, simultaneously can be for the preparation of the propelling agent of insensitive low signature.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 a most classical class " click " reaction, also claims Huisgen reaction.This type of reaction has high selectivity, the product yield height, and no coupling product generates (atom utilization height), 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, and 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 the 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 achieving the above object, the technical solution used in the present invention 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; Tetrahydrofuran (THF), (being that tetrahydrofuran (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 tetrahydrofuran (THF) (THF) is 4.4725g～6.6257g: 20mL, choose tetrahydrofuran (THF), with the solvent of tetrahydrofuran (THF) (THF) as reaction, hydroxy-terminated polybutadienes is dissolved in the tetrahydrofuran (THF) (THF), obtains hydroxy-terminated polybutadienes solution (the THF solution that namely contains HTPB);
Proportioning by potassium tert.-butoxide (t-BuOK) and tetrahydrofuran (THF) (THF) is 0.1515g～1.9635g: 20mL, choose tetrahydrofuran (THF), with the solvent of tetrahydrofuran (THF) (THF) as reaction, potassium tert.-butoxide is dissolved in the tetrahydrofuran (THF) (THF), obtain potassium tert.-butoxide solution (being t-BuOK solution);
Proportioning by acetylenic halide and tetrahydrofuran (THF) (THF) is 0.15mL～4.09mL: 60mL, choose tetrahydrofuran (THF), with the solvent of tetrahydrofuran (THF) (THF) as reaction, acetylenic halide is dissolved in the tetrahydrofuran (THF) (THF), obtain acetylenic halide solution (the THF solution that namely 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) add salt solution in the reaction solution B and extract, isolate water layer, keep tetrahydrofuran (THF) (THF) layer;
Water layer is extracted collected organic layer (being THF layer and EtOAc layer) with ethyl acetate (EtOAc); Collected organic layer with the saturated aqueous common salt extraction, discards water layer again, and the material that obtains is also laminated with above-mentioned reservation tetrahydrofuran (THF) (THF) 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 preparation method's of a kind of alkynyl polyhutadiene provided by the invention reaction equation as shown in Figure 1.
The structural formula of alkynyl polyhutadiene is:
In the structural formula, x and z represent the position of C=C on main chain, are to obtain by 1,4-addition, comprise cis and trans; Y represents the position of C=C on side chain, namely obtains by 1,2-addition; M is 1 or 2.
Beneficial effect of the present invention is: by 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 height, simple, the environmental protection of preparation technology, 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 the development field based on nitrine class energetic cleaning propelling agent, will have potential using value.
Description of drawings
Fig. 1 is the preparation method's of alkynyl polyhutadiene 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 the following examples.
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 will contain HTPB under ice bath, stirring condition 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.
Add the 80mL salt solution in the reaction solution B 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 is also laminated with above-mentioned reservation tetrahydrofuran (THF) (THF) again, obtains organic materials with ethyl acetate with water layer;
Organic materials is through anhydrous MgSO
4Drying, filtration, solvent flashing obtain alkynyl polyhutadiene (6.3723g, yield 99.1%).
By the infrared figure of alkynyl polyhutadiene product and the nuclear-magnetism figure of product, reaction has successfully connected alkynyl and has successfully connected propargyl as can be known.
Nitrine class energy-containing compound is specially poly-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 will contain HTPB under ice bath, stirring condition 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.
Add the 80mL salt solution in the reaction solution B 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 is also laminated with above-mentioned reservation tetrahydrofuran (THF) (THF) again, obtains organic materials with ethyl acetate with water layer;
Organic materials is through anhydrous MgSO
4Drying, filtration, solvent flashing obtain alkynyl polyhutadiene (6.5885g, yield 98.4%).
By the infrared figure of alkynyl polyhutadiene product and the nuclear-magnetism figure of product, reaction has successfully connected alkynyl and has successfully connected propargyl as can be known.
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 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 will contain HTPB under ice bath, stirring condition 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.
Add the 80mL salt solution in the reaction solution B 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 is also laminated with above-mentioned reservation tetrahydrofuran (THF) (THF) again, obtains organic materials with ethyl acetate with water layer;
Organic materials is through anhydrous MgSO
4Drying, filtration, solvent flashing obtain alkynyl polyhutadiene (6.3801g, yield 98.8%).
By the infrared figure of alkynyl polyhutadiene product and the nuclear-magnetism figure of product, reaction has successfully connected alkynyl and has successfully connected propargyl as can be known.
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 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 will contain HTPB under ice bath, stirring condition 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.
Add the 80mL salt solution in the reaction solution B 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 is also laminated with above-mentioned reservation tetrahydrofuran (THF) (THF) again, obtains organic materials with ethyl acetate with water layer;
Organic materials is through anhydrous MgSO
4Drying, filtration, solvent flashing obtain alkynyl polyhutadiene (6.2613g, yield 97.6%).
By the infrared figure of alkynyl polyhutadiene product and the nuclear-magnetism figure of product, reaction has successfully connected alkynyl and has successfully connected propargyl as can be known.
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 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 will contain HTPB under ice bath, stirring condition 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.
Add the 80mL salt solution in the reaction solution B 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 is also laminated with above-mentioned reservation tetrahydrofuran (THF) (THF) again, obtains organic materials with ethyl 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 herein peak 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 as shown in Figure 3, its peak shape and bibliographical information are in full accord, the chemical shift of each CH marks in figure among the HTPB, the 7.26ppm place is solvent C DCl
3Vibration peak, by 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 determines to increase.
Alkynyl polyhutadiene product
1H NMR spectrogram as shown in Figure 4 and Fig. 3 relatively, locate obvious increase/strengthened Liang Chufeng (Fig. 7 is more obvious) at 4.13ppm (e) and 2.42ppm (f), belong to methylene radical (e) on the propargyl and the vibration peak of terminal CH (f) respectively, the 7.26ppm place is CDCl
3Solvent peak.By 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 (being 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 will contain HTPB under ice bath, stirring condition 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.
Add the 80mL salt solution in the reaction solution B 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 is also laminated with above-mentioned reservation tetrahydrofuran (THF) (THF) again, obtains organic materials with ethyl acetate with water layer;
Organic materials is through anhydrous MgSO
4Drying, filtration, solvent flashing obtain alkynyl polyhutadiene (5.9733g, yield 97.4%).
By the infrared figure of alkynyl polyhutadiene product and the nuclear-magnetism figure of product, reaction has successfully connected alkynyl and has successfully connected propargyl as can be known.
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 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 will contain HTPB under ice bath, stirring condition 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.
Add the 80mL salt solution in the reaction solution B 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 is also laminated with above-mentioned reservation tetrahydrofuran (THF) (THF) again, obtains organic materials with ethyl 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 herein peak 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;
Hydroxy-terminated polybutadienes (HTPB, i.e. fourth hydroxyl) raw material nuclear-magnetism figure as shown in Figure 6, its peak shape and bibliographical information are in full accord, the chemical shift of each CH marks in figure among the HTPB, the 7.26ppm place is solvent C DCl
3Vibration peak, by 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 determines to increase.
Alkynyl polyhutadiene product
1H NMR spectrogram as shown in Figure 7 and Fig. 6 relatively, locate to increase significantly at 4.13ppm (e) and 2.42ppm (f)/strengthened Liang Chufeng, belong to methylene radical (e) on the propargyl and the vibration peak of terminal CH (f) respectively, the 7.26ppm place is CDCl
3Solvent peak.By 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 (being 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 will contain HTPB under ice bath, stirring condition 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.
Add the 80mL salt solution in the reaction solution B 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 is also laminated with above-mentioned reservation tetrahydrofuran (THF) (THF) again, obtains organic materials with ethyl acetate with water layer;
Organic materials is through anhydrous MgSO
4Drying, filtration, solvent flashing obtain alkynyl polyhutadiene (4.7841g, yield 99.3%).
By the infrared figure of alkynyl polyhutadiene product and the nuclear-magnetism figure of product, reaction has successfully connected alkynyl and has successfully connected propargyl as can be known.
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 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 will contain HTPB under ice bath, stirring condition 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.
Add the 80mL salt solution in the reaction solution B 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 is also laminated with above-mentioned reservation tetrahydrofuran (THF) (THF) again, obtains organic materials with ethyl acetate with water layer;
Organic materials is through anhydrous MgSO
4Drying, filtration, solvent flashing obtain alkynyl polyhutadiene (5.0382g, yield 96.3%).
By the infrared figure of alkynyl polyhutadiene product and the nuclear-magnetism figure of product, reaction has successfully connected alkynyl and has successfully connected propargyl as can be known.
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 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 will contain HTPB under ice bath, stirring condition 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.
Add the 80mL salt solution in the reaction solution B 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 is also laminated with above-mentioned reservation tetrahydrofuran (THF) (THF) again, obtains organic materials with ethyl acetate with water layer;
Organic materials is through anhydrous MgSO
4Drying, filtration, solvent flashing obtain alkynyl polyhutadiene (5.6429g, yield 99.2%).
By the infrared figure of alkynyl polyhutadiene product and the nuclear-magnetism figure of product, reaction has successfully connected alkynyl and has successfully connected propargyl as can be known.
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.
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 (as temperature, time etc.) with and interval value can both realize the present invention, do not enumerate embodiment one by one at this.
Claims (2)
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 vacuum-drying 2～8 h under 40～60 oC;
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 tetrahydrofuran (THF) is 4.4725g～6.6257g: 20mL, chooses tetrahydrofuran (THF), and hydroxy-terminated polybutadienes is dissolved in the tetrahydrofuran (THF), obtains hydroxy-terminated polybutadienes solution;
Proportioning by potassium tert.-butoxide and tetrahydrofuran (THF) is 0.1515g～1.9635g: 20mL, chooses tetrahydrofuran (THF), and potassium tert.-butoxide is dissolved in the tetrahydrofuran (THF), obtains potassium tert.-butoxide solution;
Proportioning by acetylenic halide and tetrahydrofuran (THF) is 0.15mL～4.09mL: 60mL, chooses tetrahydrofuran (THF), and acetylenic halide is dissolved in the tetrahydrofuran (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 oC to make its reaction 24～48 h, obtain reaction solution B;
4) add salt solution in the reaction solution B and extract, isolate water layer, keep the tetrahydrofuran (THF) layer;
Water layer is extracted collected organic layer with ethyl acetate; Collected organic layer with the saturated aqueous common salt extraction, discards water layer again, and the material that obtains is also laminated with above-mentioned reservation tetrahydrofuran (THF) again, obtains organic materials;
5) organic materials is through anhydrous MgSO
4Drying, filtration, solvent flashing obtain the alkynyl polyhutadiene;
The hydroxyl value of described hydroxy-terminated polybutadienes is between 0.4236～1.7658 mmol KOH/g.
2. the preparation method of a kind of alkynyl polyhutadiene according to claim 1, it 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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| US4156700A (en) * | 1975-08-11 | 1979-05-29 | Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of National Defence | Solid propellants containing polyether or polyester binders |
| EP2148846A1 (en) * | 2007-05-24 | 2010-02-03 | GRT, Inc. | Zone reactor incorporating reversible hydrogen halide capture and release |
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| WO2010085631A3 (en) * | 2009-01-23 | 2010-11-04 | Bridgestone Corporation | Polymers functionalized with polycyano compounds |
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| US4156700A (en) * | 1975-08-11 | 1979-05-29 | Her Majesty The Queen In Right Of Canada, As Represented By The Minister Of National Defence | Solid propellants containing polyether or polyester binders |
| CN101652405A (en) * | 2006-10-17 | 2010-02-17 | 国家淀粉及化学投资控股公司 | 1 of trinitride and alkynes, the cycloaddition of 3-dipole |
| EP2148846A1 (en) * | 2007-05-24 | 2010-02-03 | GRT, Inc. | Zone reactor incorporating reversible hydrogen halide capture and release |
| WO2010085631A3 (en) * | 2009-01-23 | 2010-11-04 | Bridgestone Corporation | Polymers functionalized with polycyano compounds |
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