CN110511311A - High molecular material for explosive modification and preparation method thereof and explosive modification method - Google Patents

High molecular material for explosive modification and preparation method thereof and explosive modification method Download PDF

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Publication number
CN110511311A
CN110511311A CN201910555480.0A CN201910555480A CN110511311A CN 110511311 A CN110511311 A CN 110511311A CN 201910555480 A CN201910555480 A CN 201910555480A CN 110511311 A CN110511311 A CN 110511311A
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explosive
high molecular
molecular material
modification
acrylate
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Inventor
欧阳晓平
张乾
陈卫星
刘乃亮
李珺鹏
刘坤
罗一鸣
王浩
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Xian University of Technology
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Xian University of Technology
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    • CCHEMISTRY; METALLURGY
    • C06EXPLOSIVES; MATCHES
    • C06BEXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00Compositions characterised by non-explosive or non-thermic constituents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F126/00Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F126/06Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F126/10N-Vinyl-pyrrolidone
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02Monomers containing only one unsaturated aliphatic radical
    • C08F212/04Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06Hydrocarbons
    • C08F212/08Styrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C08F226/10N-Vinyl-pyrrolidone

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses the high molecular materials of a kind of pair of explosive modification, the material is characterized in containing pyrrolidone group in molecule, it can be copolymerized by vinyl pyrrolidone and other polymerized monomers, or itself homopolymerization is prepared, it can also be with other macromolecule resins such as epoxy resin, acrylic resin cooperation, as explosive modified material, it can be mixed in the form of a powder with explosive, or it is mixed in a heated condition with explosive, the invention also discloses method of this macromolecule modified material for explosive modification: can directly mix or heating melting mixes, wherein explosive material and the mass ratio of modified material are arbitrary proportion, the invention also discloses the methods of a kind of pair of explosive modification, using the high molecular material as additive, it is mixed with explosive material, it is had an impact so as to the performance to explosive material, Such as mechanical performance, the compatibility of color and other components, detonation performance etc..

Description

High molecular material for explosive modification and preparation method thereof and explosive modification method
Technical field
The invention belongs to explosive modification technical fields, are related to a kind of high molecular material for explosive modification, further relate to one Preparation method of the kind for the high molecular material of explosive modification, a kind of method for further relating to explosive modification.
Background technique
TNT explosive has been widely used already, however due to being generated in the problems of own, such as production Toxic waste, the stability etc. in transport, storage and use, people attempt to find his substitute, such as 2,4- dinitrobenzene Methyl ether (DNAN), (DNTF) etc..Castexplosive is one of their important application, and most widely used at present military mixed Explosive is closed, high explosive solid phase particles are added to and form the system that flowable state carries out the composite explosives of casting dress in melting explosive matrix Claim.For castexplosive due to convenient filling, performance is good, is chiefly used in shell, grenade, guided missile warhead etc., in military composite explosives In occupy an important position.High molecular material has a wide range of applications in explosive field, can be to sense using high polymer binder High explosive is spent to be bonded, wrapped up, then by the forming methods such as founding, be conveniently made have excellent performance, safety High composite explosives.However the introducing of high molecular material is also influenced by factors, and good stability and blunt is not only required Sense effect also requires macromolecule and the good compatibility of other components and interface performance, and selection is improper still to will affect explosive Safety, detonation property, mechanical property etc., therefore be suitable for doing the high molecular weight species of adhesive and few.Thermoplasticity high score Sub- material is heated to soften since there is no crosslinkings between molecule, highly beneficial for the recycling of fusion casting type explosive, has Help the modification to explosive, it is therefore necessary to a kind of novel high polymer material is prepared, for the modification to explosive.
Summary of the invention
It is with good stability the object of the present invention is to provide a kind of high molecular material for explosive modification;
It is a further object of the present invention to provide a kind of preparation method of high molecular material for explosive modification, solve existing The problem low for the high molecular material stability of explosive modification for thering is technology to prepare
It is a further object of the present invention to provide the methods of a kind of pair of explosive modification, can improve explosive material and other components Compatibility.
The technical scheme adopted by the invention is that a kind of high molecular material for explosive modification, including arbitrary proportion are anti- The polymer of the n-vinyl pyrrolidone and general monomeric answered, the molecule of the n-vinyl pyrrolidone (being abbreviated as NVP) Structural formula are as follows:, the general structure of the general monomeric are as follows:
, the general structure of the polymer are as follows:.
General monomeric includes styrene, butadiene, vinyl acetate, acrylic acid, methyl acrylate, ethyl acrylate, third Olefin(e) acid propyl ester, butyl acrylate, polyalkylene glycol acrylate ester, hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylic acid-N, N- bis- Methylamino ethyl ester, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid Butyl ester, methacrylic acid macrogol ester, hydroxyethyl methacrylate, hydroxy propyl methacrylate, methacrylic acid-N, N- bis- One of methylamino ethyl ester, acrylamide, n-isopropyl acrylamide, maleic anhydride, maleamic acid or various of monomer.
A kind of preparation method of the high molecular material for explosive modification, is specifically implemented according to the following steps:
Step 1, the n-vinyl pyrrolidone and general monomeric for weighing any mass fraction respectively are added equipped with solvent In reaction vessel, it is uniformly mixed and obtains mixed solution;
Step 2, the initiator of certain mass score is added into mixed solution obtained in step 1, and is uniformly mixed;
Step 2 is obtained mixed solution and carries out deoxygenation processing, obtains the mixture of deoxidation by step 3;
The mixture of step 4, the deoxidation that step 3 is obtained is heated with certain rate, and constant temperature is kept for a period of time After be cooled to room temperature;
Step 5, revolving are removed by the unreacted monomer of solvent Buddhist monk in step 4 treated product;
Step 6 weighs the impurity removal reagents of certain mass score to by step 5 treated product according to mass fraction It is washed, removes remaining other impurities, obtain the high molecular material for explosive modification.
Step 1 solvent is n,N-Dimethylformamide, and the mass fraction of solvent is the total mass fraction of mixed solution 60%~80%;
General monomeric includes styrene, butadiene, vinyl acetate (being abbreviated as VAc), acrylic acid, methyl acrylate, third Olefin(e) acid ethyl ester, propyl acrylate, butyl acrylate, polyalkylene glycol acrylate ester, hydroxy-ethyl acrylate, hydroxypropyl acrylate, third Olefin(e) acid-N, TMSDMA N dimethylamine base ethyl ester, methacrylic acid, methyl methacrylate (being abbreviated as MMA), ethyl methacrylate, first Base propyl acrylate, butyl methacrylate, methacrylic acid macrogol ester, hydroxyethyl methacrylate, methacrylic acid Hydroxypropyl acrylate, methacrylic acid-N, TMSDMA N dimethylamine base ethyl ester, acrylamide, n-isopropyl acrylamide, maleic anhydride, Malaysia acyl One of amino acid or various of monomer.
Initiator in step 2 is azodiisobutyronitrile, and the mass fraction of initiator is mix monomer quality in step 1 The 0.1%~1% of score.
Deoxygenation processing is carried out to the mixture that step 2 obtains using bubbling argon in step 3, the processing time is 10min.
The rate of heat addition is 5 DEG C/min in step 4, and heating target temperature is 70 DEG C -90 DEG C, thermostatic hold-time 1h- 24h。
It is 30min-120min that the time is rotated in step 5, and impurity removal reagents include ethyl alcohol, toluene, impurity removal reagents in step 6 Mass fraction be 0.5~1 times of mix monomer mass fraction in step 1.
A kind of method of pair of explosive modification, using a kind of high molecular material for explosive modification of claim 2, specifically It carries out in accordance with the following steps:
The first step weighs the high molecular material of the claim 2 of arbitrary proportion respectively according to mass fraction and contains DNAN Explosive, and mixed, obtain the mixture of high molecular material and explosive;
Second step, the mixture that the first step is obtained are placed in container, and are heated to certain temperature with certain rate, are made DNAN in mixture is in a molten state, and maintains certain time;
Third step, by second step, treated that mixture is poured out, and is cooled to room temperature in air, obtains modified fried Medicine.
The rate of heat addition is 5 DEG C/min in second step, and heating target temperature is 110 DEG C -130 DEG C, makes DNAN in molten condition Maintain 10min-1h.
The invention has the advantages that disclosing a kind of high molecular material for explosive modification, which can It to be mixed in the form of a powder with explosive, or is mixed in a heated condition with explosive, available explosive material (being not limited to) has 2,4 dinitroanisols (DNAN), 3,4- dinitrofurfuryl furosemide (DNTF), 1,3,3- trinitroazetidine (TNAZ), it also discloses method of this macromolecule modified material for explosive modification: can directly mix or heating melting Mixing.Wherein explosive material and the mass ratio of modified material are arbitrary proportion, also disclose the method for a kind of pair of explosive modification, adopt It is mixed with the high molecular material with explosive material, is had an impact so as to the performance to explosive material, such as mechanical performance, The compatibility of color and other components, detonation performance etc..
Detailed description of the invention
Fig. 1 is the high molecular material infrared ray measurement spectrogram that embodiment 1 obtains;
Fig. 2 is the high molecular material infrared ray measurement spectrogram that embodiment 2 obtains;
Fig. 3 is the high molecular material infrared ray measurement spectrogram that embodiment 3 obtains;
Fig. 4 is the high molecular material infrared ray measurement spectrogram that embodiment 4 obtains;
Fig. 5 is the high molecular material infrared ray measurement spectrogram that embodiment 5 obtains;
Fig. 6 is the high molecular material infrared ray measurement spectrogram that embodiment 6 obtains.
Specific embodiment
The present invention is described in detail With reference to embodiment.
The present invention provides a kind of high molecular material for explosive modification, the N- vinyl including arbitrary proportion reaction The polymer of pyrrolidones and general monomeric.The molecular structural formula of n-vinyl pyrrolidone is as follows:, the structure of general monomeric is logical Formula are as follows:, the general structure of polymer are as follows:
General monomeric includes styrene, butadiene, vinyl acetate, acrylic acid, methyl acrylate, ethyl acrylate, third Olefin(e) acid propyl ester, butyl acrylate, polyalkylene glycol acrylate ester, hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylic acid-N, N- bis- Methylamino ethyl ester, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid Butyl ester, methacrylic acid macrogol ester, hydroxyethyl methacrylate, hydroxy propyl methacrylate, methacrylic acid-N, N- bis- One of methylamino ethyl ester, acrylamide, n-isopropyl acrylamide, maleic anhydride, maleamic acid or various of monomer.
The present invention also provides a kind of preparation methods of high molecular material for explosive modification, specifically according to the following steps Implement:
Step 1, the n-vinyl pyrrolidone and general monomeric for weighing any mass fraction respectively are added equipped with solvent In reaction vessel, it is uniformly mixed and obtains mixed solution;
Step 2, the initiator of certain mass score is added into mixed solution obtained in step 1, and is uniformly mixed;
Step 2 is obtained mixed solution and carries out deoxygenation processing, obtains the mixture of deoxidation by step 3;
The mixture of step 4, the deoxidation that step 3 is obtained is heated with certain rate, and constant temperature is kept for a period of time After be cooled to room temperature;
Step 5, revolving are removed by the unreacted monomer of solvent Buddhist monk in step 4 treated product;
Step 6 takes the impurity removal reagents of certain mass score to treated that product washs by step 5, removes Remaining other impurities obtain the high molecular material for explosive modification.
Solvent is n,N-Dimethylformamide in step 1, and the mass fraction of solvent is the total mass fraction of mixed solution 60%~80%;
General monomeric includes styrene, butadiene, vinyl acetate, acrylic acid, methyl acrylate, ethyl acrylate, third Olefin(e) acid propyl ester, butyl acrylate, polyalkylene glycol acrylate ester, hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylic acid-N, N- bis- Methylamino ethyl ester, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid Butyl ester, methacrylic acid macrogol ester, hydroxyethyl methacrylate, hydroxy propyl methacrylate, methacrylic acid-N, N- bis- One of methylamino ethyl ester, acrylamide, n-isopropyl acrylamide, maleic anhydride, maleamic acid or various of monomer.
Initiator in step 2 is azodiisobutyronitrile, and the mass fraction of initiator is mix monomer quality in step 1 The 0.1%~1% of score.
Deoxygenation processing is carried out to the mixture that step 2 obtains using bubbling argon in step 3, the processing time is 10min.
The rate of heat addition is 5 DEG C/min in step 4, and heating target temperature is 70 DEG C -90 DEG C, thermostatic hold-time 1h- 24h。
It is 30min-120min that the time is rotated in step 5, and impurity removal reagents include ethyl alcohol, toluene, impurity removal reagents in step 6 Mass fraction be 0.5~1 times of mix monomer mass fraction in step 1.
A kind of method of pair of explosive modification, using a kind of high molecular material for explosive modification of claim 2, specifically It carries out in accordance with the following steps:
The first step weighs the high molecular material of the claim 2 of arbitrary proportion respectively according to mass fraction and contains DNAN Explosive, and mixed, obtain the mixture of high molecular material and explosive;
Second step, the mixture that the first step is obtained are placed in container, and are heated to certain temperature with certain rate, are made DNAN in mixture is in a molten state, and maintains certain time;
Third step, by second step, treated that mixture is poured out, and is cooled to room temperature in air, obtains modified fried Medicine.
The rate of heat addition is 5 DEG C/min in second step, and heating target temperature is 110 DEG C -130 DEG C, makes DNAN in molten condition Maintain 10min-1h.
Embodiment 1
A kind of preparation method of the high molecular material for explosive modification, specifically follows the steps below:
Step 1 weighs 95 parts of n-vinyl pyrrolidone according to mass fraction, is added and 145 parts of N, N- dimethyl are housed In the reaction vessel of formamide, the n,N-Dimethylformamide solution of n-vinyl pyrrolidone is obtained;
Step 2, into step 1 according to 0.24 part of azodiisobutyronitrile of mass fraction addition in weighed raw material, and It is uniformly mixed;
Step 2 is obtained mixed solution and carries out deoxygenation processing using bubbling argon by step 3, and the processing time is 10min, Obtain the mixed solution of deoxidation;
The mixed solution for the deoxidation that step 3 obtains is heated to 70 DEG C with the rate of heat addition of 5 DEG C/min by step 4, and Constant temperature keeps 1h, then cooled to room temperature;
Step 5, revolving 30min are removed by n,N-Dimethylformamide in step 4 treated product;
Step 6 weighs 120 parts of toluene according to mass fraction and carries out precipitation purification to by step 5 treated product, Obtain the high molecular material for explosive modification.
Obtained high molecular material is measured using infrared ray, infrared spectrum as shown in Figure 1, elemental analysis result such as Under:
Element N C H
Percentage composition (%) 11.37 60.61 8.55
As shown in Figure 1, wave number 1660cm-1It is nearby the stretching vibration absworption peak of-C=O in pyrrolidone ring on NVP.Knot Elemental analysis is closed as a result, containing group in the high molecular material that can be determined, meets the general structure of subject polymer.
Embodiment 2
A kind of preparation method of the high molecular material for explosive modification, specifically follows the steps below:
Step 1 weighs 45 parts of n-vinyl pyrrolidone according to mass fraction, and 45 parts of vinyl acetate, addition is equipped with In the reaction vessel of 210 parts of n,N-Dimethylformamide, the N of n-vinyl pyrrolidone and vinyl acetate, N- diformazan are obtained Base formamide mixed solution;
Step 2 is added 1.5 parts of azodiisobutyronitrile according to mass fraction in mixed solution into step 1, and mixes equal It is even;
Step 2 is obtained mixed solution and carries out deoxygenation processing using bubbling argon by step 3, and the processing time is 10min, Obtain the mixed solution of deoxidation;
The mixed solution for the deoxidation that step 3 obtains is heated to 80 DEG C with the rate of heat addition of 5 DEG C/min by step 4, and Constant temperature keeps 12h, then cooled to room temperature;
Step 5, revolving 75min are removed by the n,N-Dimethylformamide in step 4 treated product and not instead The vinyl acetate answered;
Step 6 weighs 225 parts of toluene according to mass fraction and carries out precipitation purification to by step 5 treated product, Obtain the high molecular material for explosive modification.
Obtained high molecular material is measured using infrared ray, infrared spectrum is as shown in Fig. 2, elemental analysis result Are as follows:
Element N C H
Percentage composition (%) 7.55 58.16 7.95
As shown in Fig. 2, wave number 1661cm-1It is nearby the stretching vibration absworption peak of-C=O in pyrrolidone ring on NVP, wave Number 1731cm-1It is nearby the stretching vibration absworption peak of-C=O in ester group on VAc.In conjunction with elemental analysis as a result, may thereby determine that Contain group in obtained high molecular material, meets the general structure of subject polymer.
Embodiment 3
A kind of preparation method of the high molecular material for explosive modification, specifically follows the steps below:
Step 1 takes 1 part of n-vinyl pyrrolidone, and 49 parts of styrene, 45 parts of methyl methacrylate, addition is equipped with In the reaction vessel of 380 parts of n,N-Dimethylformamide, n-vinyl pyrrolidone, styrene and methyl methacrylate are obtained N,N-dimethylformamide mixed solution;
Step 2, the mixed solution into step 1 are mixed according to 4.7 parts of azodiisobutyronitrile of addition in mass fraction It closes uniform;
Step 2 is obtained mixture and carries out deoxygenation processing using bubbling argon by step 3, and the processing time is 10min, is obtained To the mixture of deoxidation;
The mixture for the deoxidation that step 3 obtains is heated to 90 DEG C with the rate of heat addition of 5 DEG C/min by step 4, and permanent Temperature is kept for 24 hours, then cooled to room temperature;
Step 5, revolving 120min are removed by the n,N-Dimethylformamide, not anti-in step 4 treated product Answer styrene and methyl methacrylate;
Step 6 weighs 470 parts of toluene according to mass fraction and carries out precipitation purification to by step 5 treated product, Obtain the high molecular material for explosive modification.
Obtained high molecular material is measured using infrared ray, infrared spectrum as shown in figure 3, elemental analysis result such as Under:
Element N C H
Percentage composition (%) 0.30 79.46 8.12
As shown in figure 3, the flexible vibration that wherein wave number 1723cm-1 is nearby-C=O in the ester group of methyl methacrylate Dynamic absorption peak, wave number 696cm-1 and 758cm-1 are nearby the monosubstituted characteristic absorption peak of the benzene on styrene ,-the C=on NVP It is seldom capped that O may be because that it feeds intake.In conjunction with elemental analysis as a result, containing base in the high molecular material that can be determined Group, meets the general structure of subject polymer.
Embodiment 4
A kind of preparation method of the high molecular material for explosive modification, specifically follows the steps below:
Step 1 takes 10 parts of n-vinyl pyrrolidone, and the reaction vessel that 20 parts of n,N-Dimethylformamide are housed is added In, obtain the n,N-Dimethylformamide solution of n-vinyl pyrrolidone;
0.08 part of azodiisobutyronitrile is added into step 1, and is being uniformly mixed for step 2 in weighed raw material;
Step 2 is obtained mixed solution and carries out deoxygenation processing using bubbling argon by step 3, and the processing time is 10min, Obtain the mixed solution of deoxidation;
The mixed solution for the deoxidation that step 3 obtains is heated to 70 DEG C with the rate of heat addition of 5 DEG C/min by step 4, and Constant temperature keeps 6h, then cooled to room temperature;
Step 5, revolving 30min are removed by n,N-Dimethylformamide in step 4 treated product;
Step 6 takes 20 parts of toluene to carry out precipitation purification to by step 5 treated product, obtains changing for explosive The high molecular material of property.
Obtained high molecular material is measured using infrared ray, infrared spectrum as shown in figure 4, elemental analysis result such as Under:
Element N C H
Percentage composition (%) 11.28 59.80 8.59
As shown in figure 4, wherein wave number 1661cm-1Nearby the stretching vibration for-C=O in pyrrolidone ring on NVP absorbs Peak.In conjunction with elemental analysis as a result, containing group in the polymer that can be determined, meet the general structure of subject polymer.
Embodiment 5
A kind of preparation method of the high molecular material for explosive modification, specifically follows the steps below:
Step 1 takes 15 parts of n-vinyl pyrrolidone, 10 parts of styrene, is added and 75 parts of N, N- dimethyl formyl are housed In the reaction vessel of amine, the n,N-Dimethylformamide mixed solution of n-vinyl pyrrolidone and styrene is obtained;
0.75 part of azodiisobutyronitrile is added into step 1, and is uniformly mixed for step 2 in mixed solution;
Step 2 is obtained mixed solution and carries out deoxygenation processing using bubbling argon by step 3, and the processing time is 10min, Obtain the mixed solution of deoxidation;
The mixed solution for the deoxidation that step 3 obtains is heated to 80 DEG C with the rate of heat addition of 5 DEG C/min by step 4, and Constant temperature keeps 12h, then cooled to room temperature;
Step 5, revolving 100min are removed by the n,N-Dimethylformamide in step 4 treated product and not instead The styrene answered;
Step 6 takes 85 parts of toluene to carry out precipitation purification to by step 5 treated product, obtains changing for explosive The high molecular material of property.
Obtained high molecular material is measured using infrared ray, infrared spectrum as shown in figure 5, elemental analysis result such as Under:
Element N C H
Percentage composition (%) 3.04 85.81 7.87
As shown in figure 5, wherein wave number 1682cm-1It is nearby the stretching vibration absworption peak of-C=O in pyrrolidone ring on NVP Wave number, 696cm-1And 756cm-1It is nearby the monosubstituted characteristic absorption peak of the benzene on styrene.As a result, it can in conjunction with elemental analysis Contain group to determine in obtained high molecular material, meets the general structure of subject polymer.
Embodiment 6
A kind of preparation method of the high molecular material for explosive modification, specifically follows the steps below:
Step 1 weighs 30 parts of n-vinyl pyrrolidone according to mass fraction, and 30 parts of styrene, methyl methacrylate 30 parts, be added equipped with 135 parts of n,N-Dimethylformamide reaction vessel in, obtain n-vinyl pyrrolidone, styrene and The N,N-dimethylformamide mixed solution of methyl methacrylate;
0.3 part of azodiisobutyronitrile is added in the mixed solution into step 1, and is uniformly mixed for step 2;
Step 2 is obtained mixture and carries out deoxygenation processing using bubbling argon by step 3, and the processing time is 10min, is obtained To the mixture of deoxidation;
The mixture for the deoxidation that step 3 obtains is heated to 90 DEG C with the rate of heat addition of 5 DEG C/min by step 4, and permanent Temperature is kept for 24 hours, then cooled to room temperature;
Step 5, revolving 30min are removed by the n,N-Dimethylformamide in step 4 treated product, unreacted Styrene and methyl methacrylate;
Step 6 weighs 120 parts of toluene according to mass fraction and carries out precipitation purification to by step 5 treated product, Obtain the high molecular material for explosive modification.
Obtained high molecular material is measured using infrared ray, infrared spectrum as shown in fig. 6, elemental analysis result such as Under:
Element N C H
Percentage composition (%) 3.20 73.82 8.13
As shown in fig. 6, wherein wave number 1680cm-1It is nearby the stretching vibration absworption peak of-C=O in pyrrolidone ring on NVP Wave number, 698cm-1And 758cm-1It is nearby the monosubstituted characteristic absorption peak of the benzene on styrene, wave number 1724cm-1It is nearby first The stretching vibration absworption peak of-C=O in the ester group of base methyl acrylate.In conjunction with elemental analysis as a result, may thereby determine that Contain group in high molecular material, meets the general structure of subject polymer.
Embodiment 7
The method of a kind of pair of explosive modification, specifically follows the steps below
The first step weighs aforementioned 10 parts of obtained high molecular material according to mass fraction, 90 parts of the explosive containing DNAN, And mixed, obtain the mixture of high molecular material and explosive;
Second step, the mixture that the first step is obtained are placed in container, and are heated to 110 DEG C with the rate of 5 DEG C/min, are made DNAN in mixture is in a molten state, and maintains 20min;
Third step, by second step, treated that mixture is poured out, and is cooled to room temperature in air, obtains modified fried Medicine.
Embodiment 8
The method of a kind of pair of explosive modification, specifically follows the steps below:
The first step weighs aforementioned 50 parts of obtained high molecular material according to mass fraction, 50 parts of the explosive containing DNAN, And mixed, obtain the mixture of high molecular material and explosive;
Second step, the mixture that the first step is obtained are placed in container, and are heated to 120 DEG C with the rate of 5 DEG C/min, are made DNAN in mixture is in a molten state, and maintains 25min;
Third step, by second step, treated that mixture is poured out, and is cooled to room temperature in air, obtains modified fried Medicine.
Embodiment 9
The method of a kind of pair of explosive modification, specifically follows the steps below:
The first step weighs aforementioned 0.1 part of obtained high molecular material, the explosive 99.9 containing DNAN according to mass fraction Part, and mixed, obtain the mixture of high molecular material and explosive;
Second step, the mixture that the first step is obtained are placed in container, and are heated to 130 DEG C with the rate of 5 DEG C/min, are made DNAN in mixture is in a molten state, and maintains 30min;
Third step, by second step, treated that mixture is poured out, and is cooled to room temperature in air, obtains modified fried Medicine.
Embodiment 10:
The method of a kind of pair of explosive modification, specifically follows the steps below
The first step weighs aforementioned 99.9 parts of obtained high molecular material, the explosive 0.1 containing DNAN according to mass fraction Part, and mixed, obtain the mixture of high molecular material and explosive;
Second step, the mixture that the first step is obtained are placed in container, and are heated to 125 DEG C with the rate of 5 DEG C/min, are made DNAN in mixture is in a molten state, and maintains 21min;
Third step, by second step, treated that mixture is poured out, and is cooled to room temperature in air, obtains modified fried Medicine.

Claims (10)

1. a kind of high molecular material for explosive modification, which is characterized in that the N- vinyl pyrrole including arbitrary proportion reaction The polymer of alkanone and general monomeric, the molecular structural formula of the n-vinyl pyrrolidone are as follows:It is described general The general structure of monomer are as follows:The general structure of the polymer are as follows:
2. a kind of high molecular material for explosive modification as described in claim 1, which is characterized in that the general monomeric packet Include styrene, butadiene, vinyl acetate, acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, acrylic acid fourth Ester, polyalkylene glycol acrylate ester, hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylic acid-N, TMSDMA N dimethylamine base ethyl ester, methyl-prop Olefin(e) acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methacrylic acid are poly- Glycol ester, hydroxyethyl methacrylate, hydroxy propyl methacrylate, methacrylic acid-N, TMSDMA N dimethylamine base ethyl ester, acryloyl One of amine, n-isopropyl acrylamide, maleic anhydride, maleamic acid or various of monomer.
3. a kind of preparation method of the high molecular material for explosive modification, which is characterized in that be specifically implemented according to the following steps:
Step 1, the n-vinyl pyrrolidone and general monomeric for weighing any mass fraction respectively are added equipped with certain mass point In the reaction vessel of number solvent, it is uniformly mixed and obtains mixed solution;
Step 2, the initiator of certain mass score is added into mixed solution obtained in step 1, and is uniformly mixed;
Step 2 is obtained mixed solution and carries out deoxygenation processing, obtains the mixture of deoxidation by step 3;
The mixture of step 4, the deoxidation that step 3 is obtained is heated with certain rate, and after constant temperature holding a period of time again It is cooled to room temperature;
Step 5, revolving are removed by the unreacted monomer of solvent Buddhist monk in step 4 treated product;
Step 6 weighs the impurity removal reagents of certain mass score to treated that product carries out by step 5 according to mass fraction Washing, removes remaining other impurities, obtains the high molecular material for explosive modification.
4. a kind of preparation method of the high molecular material for explosive modification as claimed in claim 3, which is characterized in that described Step 1 solvent is n,N-Dimethylformamide, the mass fraction of the solvent be the total mass fraction of mixed solution 60%~ 80%;
The general monomeric includes styrene, butadiene, vinyl acetate, acrylic acid, methyl acrylate, ethyl acrylate, third Olefin(e) acid propyl ester, butyl acrylate, polyalkylene glycol acrylate ester, hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylic acid-N, N- bis- Methylamino ethyl ester, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid Butyl ester, methacrylic acid macrogol ester, hydroxyethyl methacrylate, hydroxy propyl methacrylate, methacrylic acid-N, N- bis- One of methylamino ethyl ester, acrylamide, n-isopropyl acrylamide, maleic anhydride, maleamic acid or various of monomer.
5. a kind of preparation method of the high molecular material for explosive modification as claimed in claim 3, which is characterized in that described Initiator in step 2 is azodiisobutyronitrile, and the mass fraction of initiator is mix monomer mass fraction in step 1 0.1%~1%.
6. a kind of preparation method of the high molecular material for explosive modification as claimed in claim 3, which is characterized in that described Deoxygenation processing is carried out to the mixture that step 2 obtains using bubbling argon in step 3, the processing time is 10min.
7. a kind of preparation method of the high molecular material for explosive modification as claimed in claim 3, which is characterized in that described The rate of heat addition is 5 DEG C/min in step 4, and heating target temperature is 70 DEG C -90 DEG C, thermostatic hold-time 1h-24h.
8. a kind of preparation method of the high molecular material for explosive modification as claimed in claim 3, which is characterized in that described It is 30min-120min that the time is rotated in step 5, and impurity removal reagents include ethyl alcohol, toluene, the matter of impurity removal reagents in the step 6 Measure 0.5~1 times that score is mix monomer mass fraction in step 1.
9. the method for a kind of pair of explosive modification, which is characterized in that utilize a kind of height for explosive modification as claimed in claim 2 Molecular material specifically carries out in accordance with the following steps:
The first step weighs the high molecular material as claimed in claim 2 of arbitrary proportion respectively according to mass fraction and contains DNAN Explosive, and mixed, obtain the mixture of high molecular material and explosive;
Second step, the mixture that the first step is obtained are placed in container, and are heated to certain temperature with certain rate, make to mix DNAN in object is in a molten state, and maintains certain time;
Third step, by second step, treated that mixture is poured out, and is cooled to room temperature in air, obtains explosive modified.
10. the method for a kind of pair of explosive modification as claimed in claim 9, which is characterized in that the rate of heat addition in the second step For 5 DEG C/min, heating target temperature is 110 DEG C -130 DEG C, and DNAN is made to maintain 10min-1h in molten condition.
CN201910555480.0A 2019-06-25 2019-06-25 High molecular material for explosive modification and preparation method thereof and explosive modification method Pending CN110511311A (en)

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