CN1438248A - Method for preparing cellulose glycerine ether nitric ester - Google Patents
Method for preparing cellulose glycerine ether nitric ester Download PDFInfo
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- CN1438248A CN1438248A CN 03104638 CN03104638A CN1438248A CN 1438248 A CN1438248 A CN 1438248A CN 03104638 CN03104638 CN 03104638 CN 03104638 A CN03104638 A CN 03104638A CN 1438248 A CN1438248 A CN 1438248A
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Abstract
The invention belongs to a method of making fibrin glycerin ether nitrate by etherification and acetification, using alpha-monochloro glycidic alcohol, natural cotton and wood fibrin as raw materials and the synthesization. Under protection of inert gases, in inert organic reaction medium, make basification on the cotton and wood fibrin by NaOH water solution to get alkali fibrin, make basification and alpha-chlorine glycidic alcohol at low temperature by high-concentration alkali solution to get glycidic alcohol, in batches add epoxy-propyl alcohol to the reaction medium under protection of inert gases, make etherification reaction in proper temperature range by stirring, and then through the courses of neutralization, washing and dryness, etc, get fibrin glycidyl ether whose molar substituted degree is 0.5-1.5.
Description
Technical field
This patent belongs to the preparation of nitric acid ester of cellulose glycidyl ether and synthesizes, and it belongs to technical field of polymer chemistry, and its national patent classification number is C08.
Background technology
Soluble cotton (NC) can be widely used in single-base powder, double-base powder, triple base propellant, modification double-basis and the composite modified double-base propellant by different nitrogen content grades (11%～13.5%), is one of most important starting material of gunpowder.Because NC is the macromolecular material of semi-rigid chain, its thermoplasticity is limited, especially along with the raising of nitrogen content, more and more be difficult for plasticized dose (NG, TEGDN, DEGDN etc.) and absorb, and processing difficulties, the mechanical property of shaped charge is relatively poor.Composite double base propellant and cross-linking modified double-base propellent are the developing direction of double-base propellent, but that the former adopts usually also is No.3NC, nitrogen content in order to improve energy, has but reduced its mechanical property in a large amount of adding high energy oxidizers, additive about 12%; The latter is polymer binder or the multi-functional linking agent that adds the band active group in the composite modified double-base propellant component, in fact also is to be cost with the energy that reduces propelling agent.
It can tackiness agent be the key of development gunpowder of new generation and propelling agent that the synthetic cellulose base novel contains.Wherein an approach is that Mierocrystalline cellulose at first is transformed into polyhydroxy ethers, to improve the nitrogen content of its nitrated after product, improve the kindliness of cellulose macromolecule simultaneously, because the side chain of polyhydroxy ethers plays an intramolecularly plastification usually, further nitrated, can the synthetic thermoplastic height, energy can tackiness agent near nitrocellulosic novel containing.
Contain in the side chain in institute's synthetic ether of cellulose-OH HEC arranged, HPC, HPMC etc. do not contain two keys in the product, or compare with raw cellulose, the content of its hydroxyl all has reduction largely, can the high ether of cellulose of synthesis of hydroxy content be the problem that people are concerned about always, because it is these ether of cellulose performances are more superior, functional stronger, it is wider to carry out chemical modification, and material can be widely used in high added value chemical fields such as military project after the modification.But these ethers synthetic has bigger difficulty and complicacy, its reason is that the hydroxyl on it is active more than hydroxyl on the glucosyl residue of pristine fibre element, the etherification reaction process becomes and becomes increasingly complex, further nitrated also very difficult, select suitable nitrated system that the homogeneity and the substitution value of the nitro replacement of institute's synthetic product are all had a direct impact.
This patent belongs to a kind of preparation method of nitric acid ester of cellulose glycidyl ether and synthesizes.
Patent content
This method is to utilize the pure and mild natural cotton of α-a glycerin chlorohydrin, wood cellulose to prepare the method for nitric acid ester of cellulose glycidyl ether.Comprise that cotton, wood cellulose are under the protection of rare gas element; in the inert organic reaction medium, be the soda cellulose that the quaternization of 20%～50% the NaOH aqueous solution obtains certain alkali content through over-richness; processing obtains R-GLYCIDOL to α-glycerin chlorohydrin alcohol through 45%～60% alkali lye under-5～0 ℃ of condition, then at rare gas element N
2Protection under freshly prepd R-GLYCIDOL is added in the reaction medium in batches, carry out etherification reaction 50～150 ℃ of temperature ranges with under stirring, obtain molar substitution at 0.5～1.5 cellulose glycidyl ether through processes such as neutralization, washing and dryings again.The nitrated of cellulose glycidyl ether is to adopt HNO
3/ CH
2Cl
2=1: 0.7～1.5 nitrating agent, the nitrated reaction under 20～35min condition down at 20～35 ℃ carried out.
Preparation technology and study route are as follows:
The route of cellulose glycidyl ether (being substituted by example with one-level) is:
Adopt the process high-concentration alkali liquor processing under-5～0 ℃ of condition of α-glycerin chlorohydrin alcohol to obtain R-GLYCIDOL and carry out etherificate; at first to alkalize to Mierocrystalline cellulose; i.e. alkali activation in advance; itself and R-GLYCIDOL are reacted; preparation process is in specific time, reacts under stirring and nitrogen protection.Neutralization, boiling then, solidify, decon, carry out drying treatment again.
Synthetic cellulose glyceryl ether and its nitration reaction all belong to heterogeneous liquid-solid reaction, and the product nitric acid ester of cellulose glycidyl ether is after utilizing soda cellulose to carry out etherificate in organic medium, pass through the ester that nitration reaction obtains again, and preparation process comprises following several stages:
1) Mierocrystalline cellulose alkalization: with 20%～50%NaOH aqueous solution, the ratio of alkali/Mierocrystalline cellulose/water=1: 0.9～1.2: 1.5 alkalizes to Mierocrystalline cellulose in the inertia organic medium, is under 15 ℃～25 ℃ conditions, processing 1h.
2) preparation of etherifying agent: highly purified α-glycerin chlorohydrin alcohol is handled 1～2h through high-concentration alkali liquor under-5～0 ℃ of condition, removes the NaCl solid of generation after filtration, makes R-GLYCIDOL (or solution) through (or without) distillation again.
3) preparation of cellulose glycidyl ether: R-GLYCIDOL (or solution) was added in the Mierocrystalline cellulose organic medium mixed system that has alkalized before this, the concentration of R-GLYCIDOL in system is 7%～30% (quality), and occurrence depends on the molar substitution of wanting the synthetic cellulose glycidyl ether.Reaction divided for two (or one) stages: the fs is temperature to be risen to 50～85 ℃ react 40～60min under stirring state; Again temperature is risen to 100～150 ℃ and under stirring state, react 120～180min.
4) centrifugal and neutralization: reaction solution is got in whizzer or the pumping and filtering device, fallen unnecessary reaction solution entirely very soon.Again synthetic product is added in the acetone-water mixed solvent, adds after an amount of hydrochloric acid or acetic acid neutralizes, repeatedly wash, filter (whizzer drying) purifying with B.
5) washing is dry: be to wash in pure water or acetone-water mixed solvent.Leach and dry, obtain the powdery substance of fibrous white, have stronger wetting ability, in dry sealed vessel, preserve.
6) cellulose glycidyl ether is nitrated: the nitrated of cellulose glycidyl ether is to adopt HNO
3/ CH
2Cl
2=1: 0.7～1.5 nitrating agent, the nitrated reaction under 20～35min condition down at 20～35 ℃ carried out.
Specific embodiment
Embodiment 1: at first toluene 58g, Virahol 2.5g, water 15g, sheet alkali 8g are added in the autoclave, be warming up to 80 ℃ of stirrings, until dissolving evenly, be cooled to 5～10 ℃ or normal temperature.The purified cotton 10g that accurately takes by weighing after the pulverizing adds in the reactor, with nitrogen purge three times.Start stirring, at 25 ℃ of 60min that alkalize down.Utilize highly purified α-glycerin chlorohydrin alcohol 50g to be added in the Virahol of 300mL simultaneously, cool off this solution system to-5 ℃, then under the continuously stirring situation, in 60min, slowly add 38g concentration and be 45% alkali aqueous solution, under-5～0 ℃ of condition, keep the 30min stirring reaction then, through and filtering to remove the NaCl solid that reaction generates, obtain clear solution and all be added in the autoclave, fill nitrogen emptying twice after the sealing, be warmed up to 70 ℃ and under agitation react 60min; Temperature is risen to 120 ℃ again,, obtain cellulose glycidyl ether constantly reacting 120min under the stirring state.Further adopt HNO3/CH
2Cl
2=1: 1 nitrating agent is nitrated to it, and nitrated is to obtain the cellulose glycidyl ether nitrated ester under the reaction 30min condition down at 25 ℃.
Embodiment 2: at first toluene 98g, water 10g, sheet alkali 5g are added in the autoclave, be warming up to 80 ℃ of stirrings, until dissolving evenly, be cooled to 5～10 ℃ or normal temperature.The purified cotton 10g that accurately takes by weighing after the pulverizing adds in the reactor, with nitrogen purge three times.Start stirring, at 25 ℃ of 60min that alkalize down.Utilize highly purified α-glycerin chlorohydrin alcohol 55g to be added in the Virahol of 300mL simultaneously, cool off this solution system to-5 ℃, then under the continuously stirring situation, in 60min, slowly add 40g concentration and be 48% alkali aqueous solution, under-5～0 ℃ of condition, keep the 30min stirring reaction then, through filtering to remove the NaCl solid that reaction generates, and obtained carrying out underpressure distillation again behind the clear solution and obtain R-GLYCIDOL.R-GLYCIDOL all is added in the autoclave, fills nitrogen emptying twice after the sealing, be warmed up to 70 ℃ and under agitation react 60min; Temperature is risen to 140 ℃ again,, obtain cellulose glycidyl ether constantly reacting 100min under the stirring state.Further adopt HNO
3/ CH
2Cl
2=1: 1 nitrating agent is nitrated to it, and nitrated is to obtain the cellulose glycidyl ether nitrated ester under the reaction 30min condition down at 25 ℃.
Embodiment 1: at first toluene 80g, Virahol 2.5g, water 8g, sheet alkali 4g are added in the autoclave, be warming up to 80 ℃ of stirrings, until dissolving evenly, be cooled to 5～10 ℃ or normal temperature.The purified cotton 10g that accurately takes by weighing after the pulverizing adds in the reactor, with nitrogen purge three times.Start stirring, at 25 ℃ of 60min that alkalize down.Utilize highly purified α-glycerin chlorohydrin alcohol 50g to be added in the Virahol of 300mL simultaneously, cool off this solution system to-5 ℃, then under the continuously stirring situation, in 60min, slowly add 40g concentration and be 50% alkali aqueous solution, under-5～0 ℃ of condition, keep the 30min stirring reaction then, through filtering to remove the NaCl solid that reaction generates, and obtained carrying out underpressure distillation again behind the clear solution and obtain R-GLYCIDOL.R-GLYCIDOL all is added in the autoclave, fills nitrogen emptying twice after the sealing, be warmed up to and be raised to 120 ℃,, obtain cellulose glycidyl ether constantly reacting 180min under the stirring state.Further adopt HNO
3/ CH
2Cl
2=1: 1 nitrating agent is nitrated to it, and nitrated is to obtain the cellulose glycidyl ether nitrated ester under the reaction 30min condition down at 25 ℃.
Claims (8)
1. the method for preparing cellulose glycidyl ether after the preparation method of nitric acid ester of cellulose glycidyl ether, this method utilize the pure and mild natural cotton of α-a glycerin chlorohydrin, wood cellulose through etherificate, esterification.Comprise cotton; wood cellulose is under the protection of rare gas element; in the inertia organic medium, obtain the soda cellulose of certain alkali content through the alkalinisation treatment of the certain density NaOH aqueous solution; α-one glycerin chlorohydrin alcohol is handled through high-concentration alkali liquor at low temperatures and is obtained R-GLYCIDOL; under protection of inert gas, freshly prepd R-GLYCIDOL is added in the reaction medium that contains the soda cellulose that has alkalized in batches then; carry out etherification reaction in suitable temperature range with under stirring, again through neutralization; washing and process such as drying obtain molar substitution at 0.5～1.5 cellulose glycidyl ether.It is nitrated to utilize nitric acid and inert organic solvents mixed system as nitrating agent cellulose glycidyl ether to be carried out, and obtains the nitric acid ester of cellulose glycidyl ether of nitrogen content 12%～13.9%.
2. according to right 1 described method, it is characterized in that adopting natural cotton, wood cellulose is raw material.
3. according to right 1 described method, the medium that adopts that it is characterized in that alkalizing is the inertia organic medium---aromatic series, aliphatic hydrocarbon and various alcohols material.
3. according to right 1 described method, it is characterized in that adopting R-GLYCIDOL is etherifying agent.R-GLYCIDOL be through α-glycerin chlorohydrin alcohol under-5～0 ℃ low temperature, alkalizing in concentration is 45%～60% the NaOH aqueous solution obtains.
4. according to right 1 described method, it is characterized in that temperature risen under 50～90 ℃ the temperature of reaction and carry out etherificate 1h, at 100～150 ℃ of reaction 3h down, reaction will be carried out under nitrogen protection then.
5. according to right 1 described method, the liquid-solid ratio that it is characterized in that etherification reaction is 15～30.
6. according to right 1 described method, institute's synthetic cellulose glycidyl ether, its general formula is:
Or H, and
Or H
7. according to right 1 described method, the nitrated of cellulose glycidyl ether is to adopt HNO
3/ CH
2Cl
2=1: 0.7～1.5 nitrating agent, nitrated is to react 30min down at 20～35 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB03104638XA CN100453557C (en) | 2003-02-19 | 2003-02-19 | Method for preparing cellulose glycerine ether nitric ester |
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|---|---|---|---|
| CNB03104638XA CN100453557C (en) | 2003-02-19 | 2003-02-19 | Method for preparing cellulose glycerine ether nitric ester |
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| CN1438248A true CN1438248A (en) | 2003-08-27 |
| CN100453557C CN100453557C (en) | 2009-01-21 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422216C (en) * | 2004-04-30 | 2008-10-01 | 北京理工大学 | Azido dihydroxypropyl cellulose nitrate preparation method and synthesis |
| CN102344495A (en) * | 2011-11-10 | 2012-02-08 | 北京理工大学 | Cyanoethyl cellulose glycerin ether and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB177809A (en) * | 1921-04-02 | 1923-10-01 | Leon Lilienfeld | Manufacture of cellulose derivatives |
| US3638698A (en) * | 1966-09-30 | 1972-02-01 | Us Navy | Crosslinked carboxymethyl cellulose nitrates propellants |
| JPS4819231B1 (en) * | 1970-03-06 | 1973-06-12 | ||
| JP2856545B2 (en) * | 1990-11-28 | 1999-02-10 | 旭化成工業株式会社 | Production method of new cellulose nitrate |
| JPH10175372A (en) * | 1996-12-18 | 1998-06-30 | Fuji Photo Film Co Ltd | Abrasion recording material |
| JP4449086B2 (en) * | 1998-06-19 | 2010-04-14 | 日油株式会社 | Method for producing cellulose nitrate derivative |
-
2003
- 2003-02-19 CN CNB03104638XA patent/CN100453557C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100422216C (en) * | 2004-04-30 | 2008-10-01 | 北京理工大学 | Azido dihydroxypropyl cellulose nitrate preparation method and synthesis |
| CN102344495A (en) * | 2011-11-10 | 2012-02-08 | 北京理工大学 | Cyanoethyl cellulose glycerin ether and preparation method thereof |
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| Publication number | Publication date |
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| CN100453557C (en) | 2009-01-21 |
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Granted publication date: 20090121 Termination date: 20120219 |