CN100488985C - Method of synthesizing poplar cellulose derivative containing unsaturated group - Google Patents
Method of synthesizing poplar cellulose derivative containing unsaturated group Download PDFInfo
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- CN100488985C CN100488985C CNB2007100198385A CN200710019838A CN100488985C CN 100488985 C CN100488985 C CN 100488985C CN B2007100198385 A CNB2007100198385 A CN B2007100198385A CN 200710019838 A CN200710019838 A CN 200710019838A CN 100488985 C CN100488985 C CN 100488985C
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Abstract
The invention discloses a synthesizing method of wood cellulose derivant with insaturated group, which comprises the following steps: 1. adopting glacial acetic acid as activator to activate wood cellulose; 2. dissolving acetic anhydride through glacial acetic acid to add into autoclave with concentrated sulfuric acid; neutralizing concentrated sulfuric acid through sodium acetate to produce sodium sulfate when the reacting solution is transparent basically; 3. dissolving esterified wood cellulose through glacial acetic acid; adding distilled water to sediment wood acetic maleic cellulose ester; filtering; washing; drying in the vacuum; obtaining the product.
Description
Technical field
The present invention relates to a kind of preparation method of cellulose ester, relate in particular to a kind of synthetic method that contains the poplar cellulose derivative of unsaturated group.
Background technology
Mierocrystalline cellulose derives from trees, cotton, crudefiber crop, plant and other agricultural byproducts, is the inexhaustible renewable resources of occurring in nature.In history, Mierocrystalline cellulose is polymer chemistry birth and the main research object of developing period.The achievement of Mierocrystalline cellulose research is that significant contribution has been made in the foundation and the development of polymer science.
Poplar is a kind of fast growing wood, and content of cellulose is high and lignin content is low, has a wide range of applications on pulping and paper-making.There is abundant quick growth poplar wood resource in China.With the cotton wood cellulose is that raw material has important practical significance.
Derivatived cellulose is the natural macromolecular material of developing the earliest, and in cellulose esters, nitrocellulose is human first plasticity-superpolymer from the occurring in nature preparation.Successfully synthetic again afterwards celluloid plastic, the fine artificial silk of nitre and smokeless powder.Along with the appearance of cellulose acetate, some cellulose nitrate goods have been replaced gradually.Cellulose acetate is discovery in 1869, but because the temperature of reaction height easily makes Mierocrystalline cellulose decompose, used sulfuric acid up to 1879, made catalyzer with zinc chloride, sodium-acetate in 1894, esterification has at normal temperatures just successfully made the cellulosetri-acetate that Mierocrystalline cellulose decomposes has not taken place.Be dissolved in the acetone through the cellulosetri-acetate saponification, and successfully made Cellulose diacetate, and begun to make plastics, film, coating, fiber etc. in 1905 with it.Comparatively be typically cellulose acetate propionate and cellulose acetate butyrate in the cellulose mixed esters class that thereupon grows up,, be widely used in high-grade car paint and printing-ink because they have good resin compatible, photostabilization and winter hardiness.Though the Application Areas of cellulose esters is constantly open, and relate to each industrial sector, formed the industrial system of cellulosics and resin gradually.When but long and slender plain ester class is used for surface coating material, softening easily, also scratch easily.This mainly is because the group of crosslinking reaction does not take place in the plain derivative of this fibrid.
(US Patent4565857) with the hydroxyl reaction on isocyanates function monomer and the Mierocrystalline cellulose, prepares and contains isocyanate functional group's cellulose ester class, can be used for the protective layer of coating in order to overcome people such as this shortcoming Richard J.Grant.People such as Phillip M.Cook (US, Patent4839230) with containing hydroxyl reaction on unsaturated double-bond isocyanates function monomer and the Mierocrystalline cellulose, prepare can with the crosslinked derivatived cellulose of vinyl monomer.Protective cover as materials such as timber, metal, plastics, paper.People (US such as Phillip Mlchael Cook, Patent5741901) be raw material and maleic anhydride graft reaction with cellulose acetate, cellulose acetate propionate or cellulose acetate butyrate, prepare the derivatived cellulose that crosslinking reaction can take place with vinyl monomer under UV-irradiation.More than three patents all be based on the basis of cellulose ester analog derivative and carry out graft reaction, it is high that raw materials cost is wanted, and product performance also are unfavorable for regulation and control.
Summary of the invention
The purpose of this invention is to provide a kind of synthetic method that contains the poplar cellulose derivative of unsaturated group, this method technical process is simple, raw material saving, efficient height, cost is low, product stability good.Cotton wood cellulose of the present invention is the poplar bleached kraft pulp, and its α-content of cellulose is 85%.
The present invention adopts following technical scheme:
The first step, 200～2000% of employing cotton wood cellulose quality Glacial acetic acid activates cotton wood cellulose as activator earlier, and activation temperature is 25～70 ℃, and soak time is 2h～24h, and the activation back adds in the reactor;
Second the step, after acetic anhydride, concentrated sulfuric acid dissolution are in Glacial acetic acid, add reactor together, stirring reaction, temperature of reaction is 40～90 ℃, 1～3 hour reaction times, when reaction soln is transparent, with sodium-acetate to changing the vitriol oil and generating sodium sulfate.Wherein the vitriol oil is as catalyzer, and consumption is 5～15% of a cotton wood cellulose quality.The acetic anhydride consumption is 60～160% of a cotton wood cellulose quality, and the Glacial acetic acid consumption is 200～2000% of a cotton wood cellulose quality.The sodium-acetate consumption is 100～500% of a vitriol oil molar weight.
The 3rd step is with the aspen fibers by using silicon cellulose solution after the esterification of the further diluted acetic acid acid anhydride of Glacial acetic acid; Add stopper and maleic anhydride, after the stirring and dissolving, add catalyst acetic acid sodium, reacted 3～20 hours down at 40～90 ℃, wherein, the Glacial acetic acid quality of dilution usefulness accounts for 300～4000% of former cotton wood cellulose acetic ester quality, the molar weight of maleic anhydride is the molar weight 150～400% of former cotton wood cellulose, the quality of stopper is 0.5～5% of a maleic anhydride quality, and the sodium-acetate consumption is 50～100% of a cotton wood cellulose molar weight
In the 4th step, reaction finishes back adding distilled water makes poplar acetic acid toxilic acid cellulose ester precipitation, and after filtration, washing obtains poplar acetic acid toxilic acid cellulose ester after the vacuum-drying.
In the technical program,, can conveniently control the quantity of two keys in the poplar acetic acid toxilic acid cellulose ester by the consumption of control acetic anhydride and maleic anhydride.All are reflected in the same reactor and finish.Used stopper is a kind of in add-on type stopper, chain transfer type stopper or electronics stopper transition.The add-on type stopper is a kind of in benzoquinones, nitro-compound, arylamine, phenols, the sulfocompound.Phenols is a kind of in Resorcinol, the phenol.The electron transfer type stopper is a kind of in iron(ic) chloride, the cupric chloride.
The present invention obtains following technique effect:
1. because poplar is a kind of fast growing wood, the content of cellulose height, content of lignin is low, and in addition, there is abundant quick growth poplar wood resource in China, thereby to being that raw material has important practical significance with the cotton wood cellulose.The present invention selects wide material sources, cheap natural poplar bleached kraft pulp for use, preparation contains the poplar cellulose derivative of unsaturated group, the utilization that has on the one hand strengthened cotton wood cellulose, on the other hand, this preparation method has that cost is low, the advantage of environmental protection.
2. in the present invention, be raw material with the cotton wood cellulose, by the consumption of control acetic anhydride and maleic anhydride, can conveniently control the quantity of the two keys of product, thereby the control product carries out the quantity in Raolical polymerizable active centre.The synthetic poplar cellulose derivative can carry out radical polymerization because of containing unsaturated double-bond, can be used for preparing the coating of materials such as timber, metal, plastics, paper, has tangible application prospect.
3. among the present invention, acetic anhydride esterification and acid anhydride maleic anhydride esterification carry out in a reactor successively, and operation is less, and auxiliary agents such as Glacial acetic acid are recyclable, thereby cost has obtained further reduction.
4. in the present invention, used stopper, can make product in preparation process, keep stability on the one hand, made product that self-polymeric reaction not take place, also made on the other hand to be reflected under the relative condition that will be high of temperature and carry out, thereby shorten the reaction times; In addition, the use of stopper has stoped monomeric polymerization, thereby makes the quality of product be guaranteed.
5. among the present invention, the reagent of reaction usefulness serves as multiple role, has both helped reducing cost, and helps again purifying.For example: Glacial acetic acid is an activator, also is solvent; Sodium-acetate is a neutralizing agent, is again the catalyzer of maleic anhydride esterification.
Description of drawings
Fig. 1 is the cellulosic IR figure of poplar.At 3500cm
-1There is the strong absorption peak of hydroxyl at the place.
Fig. 2 is the IR figure after the esterification of poplar cellulose acetate acid anhydride.At 3500cm
-1The place has the strong absorption of hydroxyl to weaken to some extent.1755cm
-1There is the strong receipts peak of ester group at the place.
Fig. 3 is the IR figure of poplar acetic acid toxilic acid cellulose ester.At 3000～3500cm
-1There is strong absorption at the place, after this is maleic anhydride esterification, is connected on carboxyl peak on the poplar acetic acid toxilic acid cellulose ester and the hydroxyl peak that does not react completely.1750cm
-1There is the strong receipts peak of ester group at the place.At 997cm
-1There is absorption peak at the place, and this is the absorption peak of two keys.
Embodiment
1 one kinds of synthetic methods that contain the poplar cellulose derivative of unsaturated group of embodiment may further comprise the steps,
The first step, 200～2000% of employing cotton wood cellulose quality Glacial acetic acid activates cotton wood cellulose as activator earlier, and the quality of Glacial acetic acid can be chosen for 300%, 400% of cotton wood cellulose quality, 600%, 800%, 1100%, 1200%, 1400%, 1500%, 1700%, 1900%, activation temperature is 25～70 ℃, for example can be chosen for 30 ℃, 35 ℃, and 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 64 ℃, 68 ℃, soak time is 2h～24h, can be chosen for 3 hours, 4 hours, 6 hours, 8 hours, 11 hours, 14 hours, 15 hours, 18 hours, 20 hours, 22 hours, 23 hours, 24 hours.
Second step is with acetic anhydride, concentrated sulfuric acid dissolution adds reactor, stirring reaction after in Glacial acetic acid together, temperature of reaction is 40～90 ℃, for example can be chosen for: 45 ℃, and 55 ℃, 60 ℃, 70 ℃, 75 ℃, 80 ℃, 90 ℃, reacted 1～3 hour, for example can be chosen for 1.2 hours, 1.5 hours, 1.8 hours, 2 hours, 2.2 hours, 2.5 hours, 2.8 hour, when reaction soln is transparent, replaces the vitriol oil and generate sodium sulfate with sodium-acetate, wherein the vitriol oil is as catalyzer, and consumption is 5～15% of a cotton wood cellulose quality, and the vitriol oil can be 98% the vitriol oil, its quality can be chosen for 6%, 8%, 9% of cotton wood cellulose quality, 11%, 12%, 14%, 14.5%, the acetic anhydride consumption is 60～160% of a cotton wood cellulose quality, for example can be chosen for: 60%, 70%, 80%, 90%, 100%, 110%, 120%, 130%, 140%, 150%, 160%, the Glacial acetic acid consumption is 200～2000% of a cotton wood cellulose quality, and for example the quality of Glacial acetic acid can be chosen for 300%, 400% of cotton wood cellulose quality, 500%, 700%, 900%, 1000%, 1200%, 1300%, 1500%, 1600%, 1700%, 1800%, 1900%, the sodium-acetate consumption is 100～500% of a vitriol oil molar weight; For example can be chosen for 100%, 150%, 200%, 250%, 300%, 350%, 400%, 450%, 500%.
In the 3rd step, the aspen fibers by using silicon cellulose solution in reactor after the esterification of the further diluted acetic acid acid anhydride of adding Glacial acetic acid adds stopper and maleic anhydride, after the stirring and dissolving, add catalyst acetic acid sodium, reacted 3～20 hours down at 40～90 ℃, temperature of reaction can be chosen for 45 ℃, and 55 ℃, 60 ℃, 70 ℃, 75 ℃, 80 ℃, 90 ℃, for obtaining higher maleic anhydride esterification effect, preferred 60-90 ℃, reaction times can be chosen for 4 hours, and 6 hours, 8 hours, 9 hours, 10 hours, 12 hours, 14 hours, 15 hours, 16 hours, 18 hours, 19 hours.Wherein, the Glacial acetic acid quality of dilution usefulness accounts for 300～4000% of former cotton wood cellulose quality, for example can be chosen for 300%, 500%, 600%, 700%, 900%, 1200%, 1500%, 1900%, 2000%, 2400%, 3000%, 3300%, 3800%, the molar weight of maleic anhydride is the molar weight 150～400% of former cotton wood cellulose, for example can be chosen for 160%, 170%, 200%, 220%, 250%, 280%, 300%, 310%, 330%, 340%, 360,380%, the quality of stopper is 0.5～5% of a maleic anhydride quality, for example can be chosen for 0.6%, 0.8%, 0.9%, 1%, 1.5%, 2%, 2.3%, 2.8%, 3%, 3.2%, 3.4%, 3.6%, 3.9%, 4.2%, 4.4%, 4.6%, 4.8%, 4.9%.The sodium-acetate consumption is 50～100% of a cotton wood cellulose molar weight, for example can be chosen for 60%, 70%, 80%, 90%, 95%;
In the technical program,, can conveniently control the quantity of two keys in the poplar acetic acid toxilic acid cellulose ester by the consumption of control acetic anhydride and maleic anhydride.All are reflected in the same reactor and finish.Used stopper is a kind of in add-on type stopper, chain transfer type stopper or electronics stopper transition.The electron transfer type stopper is a kind of in iron(ic) chloride, the cupric chloride.The add-on type stopper is benzoquinones, nitro-compound (for example, oil of mirbane, 1,3,5-trinitrobenzenes etc.), arylamine (for example, aniline, to monomethylaniline etc.), a kind of in the phenols (for example, Resorcinol, phenol etc.), sulfocompound (for example, sulphur, dimethyl sulfide etc.).Chain transfer type stopper is 1, a kind of in 1-phenylbenzene-2-trinitrophenyl-hydrazine (DPPH), arylamine (for example, aniline, to monomethylaniline etc.), the phenols (for example, Resorcinol, phenol etc.).Electronics transition, stopper was a kind of in iron(ic) chloride, the cupric chloride.
In the 4th step, reaction finishes back adding distilled water makes poplar acetic acid toxilic acid cellulose ester precipitation, filter, and washing, vacuum-drying again obtains poplar acetic acid toxilic acid cellulose ester.Cotton wood cellulose of the present invention is a bleached kraft pulp, and its α-content of cellulose is 85%.
2 one kinds of synthetic methods that contain the poplar cellulose derivative of unsaturated group of embodiment may further comprise the steps,
The first step: get 4g cotton wood cellulose powder in the four-hole boiling flask of 250ml, under condition of water bath heating, under the situation that constantly stirs (rotating speed 500r/min), drip the activation of 36g Glacial acetic acid with dropping funnel.Activation temperature activates 2 hours at 45 ℃.
Second step: after 10g Glacial acetic acid and 2.52g acetic anhydride mixed, it was evenly mixed to add 1g concentration and be 98% the vitriol oil, about refrigerator and cooled is but to 2 ℃, is added dropwise in the Mierocrystalline cellulose after having activated in the reaction flask control feed liquid heat-up rate.Temperature of reaction is set at 60 ℃, and the reaction times is about 2 hours.When observing the reaction soln substantially transparent, add 2g sodium-acetate neutralisation of sulphuric acid.
The 3rd step: in reaction flask, add Glacial acetic acid, 4.84g maleic anhydride, the 0.05g Resorcinol of 10g, accelerate stirring velocity to 1000r/min, when maleic anhydride, Resorcinol dissolve fully.Stirring velocity is dropped to 200r/min, add the 3.55g sodium-acetate.Keeping temperature of reaction is 60 ℃, continues reaction 4 hours.
The 4th step: the product in the reaction flask is cooled to 40 ℃, add 50g distilled water, accelerate to stir (rotating speed 1000r/min) half an hour, treat the complete post precipitation of poplar acetic acid toxilic acid cellulose ester, filter, use the distilled water repetitive scrubbing, 25 ℃ of dryings of vacuum obtained product in 48 hours.
Test result: the substitution value after the acetic anhydride Esterification Stage finishes: 1.89
Made product dissolves the back film forming in acetone, use ultraviolet light polymerization.Tensile strength; 70MPa elongation: 5%.(annotate: acetyl cellulose film tensile strength: 30～40MPa elongation: 7～10%)
Experimental result shows that behind the maleic anhydride esterification, through ultraviolet light polymerization, the tensile strength of film is bigger than the tensile strength of acetyl cellulose film.
Embodiment 3
The first step: identical with embodiment 2 the first steps.
Second step: the acetic anhydride consumption is 3.78g, and other condition is identical with 2 second steps of embodiment.
The 3rd step: maleic anhydride consumption 3.62g, other condition is identical with the 3rd step of embodiment 2.
The 4th step: identical with the 4th step of embodiment 2.
Test result: the substitution value after the acetic anhydride esterification: 2.31.
Made product dissolves the back film forming in acetone, use ultraviolet light polymerization.Tensile strength: 58MPa elongation: 5.8%
Comparison with embodiment 2, in the present embodiment, substitution value after the acetic anhydride esterification has increased, cause on the cotton wood cellulose and can carry out the minimizing of esterified hydroxy groups quantity for maleic anhydride, therefore the quantity of two keys also reduce in institute's synthetic product, and the reduced number of cross-linking set is through behind the ultraviolet light polymerization, the tensile strength of film is lower than examples of implementation 2, but still bigger than the tensile strength of cellulose acetate film.
Embodiment 4
The first step: identical with embodiment 3 the first steps.
Second step: identical with 3 second steps of embodiment.
The 3rd step: temperature of reaction is 40 ℃.Other condition is identical with the 3rd step of embodiment 3.
The 4th step: identical with the 4th step of embodiment 3.
Test result: the substitution value after the acetic anhydride esterification: 2.29
Made product dissolves the back film forming in acetone, use ultraviolet light polymerization.Tensile strength: 47MPa elongation: 7% in the present embodiment, and the temperature of reaction of maleic anhydride esterification class drops to 40 ℃, compares with embodiment 3, other preparation condition is all identical, because low temperature is low, the maleic anhydride esterification rate descends to some extent, thereby cross-linking set reduces.Through ultraviolet light polymerization, the tensile strength of film is lower than embodiment 3.
Embodiment 5
The first step: identical with embodiment 3 the first steps.
Second step: identical with 3 second steps of embodiment.
The 3rd step: stopper changes iron(ic) chloride into, consumption 0.07g, and, other condition is identical with the 3rd step of embodiment 3.
The 4th step: identical with the 4th step of embodiment 3.
Test result: the substitution value after the acetic anhydride esterification: 2.32.
Made product dissolves the back film forming in acetone, use ultraviolet light polymerization.Tensile strength: 60MPa elongation: 5.5% comparing embodiment 3
The first step: identical with embodiment 3 the first steps.
Second step: identical with 3 second steps of embodiment.
The 3rd step: do not add stopper, other condition is identical with the 3rd step of embodiment 3.
The 4th step: identical with the 4th step of embodiment 3.
Test result: the substitution value after the acetic anhydride esterification: 2.30
Made product dissolves the back film forming in acetone.This product solvability is relatively poor, and the film surface irregularity is in uneven thickness.Use ultraviolet light polymerization.Tensile strength: 59MPa elongation: 3%.In comparative example, owing to do not use stopper, resultants in reaction process generation self-crosslinking reaction, therefore made product dissolves relatively poorly in acetone, shows unfairness, and is in uneven thickness.
The mensuration of the substitution value of acetic anhydride Esterification Stage (DS) is carried out with reference to ASTM D 871-96 among the present invention.Concrete grammar is as follows: 1. accurately the sample about weighing 1g is put into Erlenmeyer flask.2. in the Erlenmeyer flask sample, add the ethanol of 40ml 75% (V/V), and set up blank.3. the Erlenmeyer flask stopper is unscrewed some and heated 30 minutes in 60 ℃ of water-baths, the NaOH standardized solution that accurately pipettes 50ml 0.5mol/L then heated 15 minutes in 60 ℃ of water-baths in Erlenmeyer flask again.With Erlenmeyer flask stopper jam-pack, at room temperature (be lower than 30 ℃) and placed 72 hours then.4. with phenolphthalein as indicator, with the alkali of the hydrochloric acid overtitration of 0.5mol/L.Reach the hydrochloric acid that adds 1ml after the titration end point again, placing spends the night diffuses out alkali from the cellulose acetate crude granule, till not having pink colour around the cellulose acetate crude granule.The NaOH standard solution titration that 0.5mol/L is used in the excessive acid of trace more to terminal.After reaching terminal point, also rock with strength with stopper jam-pack Erlenmeyer flask, because acid diffuses out from the cellulose acetate crude granule pink colour is taken off, therefore, alkali will then add and constantly rock till pink colour does not disappear.DS calculates by following formula:
Acetyl content (%)=[(Nb of A-B)-(Na of C-D)] * 4.3/W
DS=(3.86 * acetyl content)/(102.4-acetyl content)
NaOH milliliter in A-adding sample is counted the NaOH milliliter number in B-blank sample
HCl milliliter in C-adding sample is counted the HCl milliliter number in D-blank sample
The concentration of the concentration Nb of Na-HCl-NaOH
The quality of W-sample (g) 4.3-factor of estimation gamma value
Claims (3)
1, a kind of synthetic method that contains the poplar cellulose derivative of unsaturated group is characterized in that may further comprise the steps,
The first step adopts the Glacial acetic acid of cotton wood cellulose quality 200～2000% as activator cotton wood cellulose to be activated earlier, and activation temperature is 25～70 ℃, and soak time is 2h～24h, and the activation back adds in the reactor;
Second step, after acetic anhydride, concentrated sulfuric acid dissolution are in Glacial acetic acid, add reactor together, stirring reaction, temperature of reaction is 40～90 ℃, reacted 1～3 hour, when reaction soln is transparent, replace the vitriol oil and generate sodium sulfate with sodium-acetate, wherein the vitriol oil is as catalyzer, consumption is 5～15% of a cotton wood cellulose quality, the acetic anhydride consumption is 60～160% of a cotton wood cellulose quality, and the Glacial acetic acid consumption is 200～2000% of a cotton wood cellulose quality, and the sodium-acetate consumption is 100～500% of a vitriol oil molar weight;
The 3rd step, aspen fibers by using silicon cellulose solution in reactor after the esterification of the further diluted acetic acid acid anhydride of adding Glacial acetic acid, add stopper and maleic anhydride, after the stirring and dissolving, add catalyst acetic acid sodium, reacted 3～20 hours down at 40～90 ℃, wherein, the Glacial acetic acid quality of dilution usefulness accounts for 300～4000% of former cotton wood cellulose quality, the amount of substance of maleic anhydride be former cotton wood cellulose amount of substance 150～400%, the quality of stopper is 0.5～5% of a maleic anhydride quality, and the sodium-acetate consumption is 50～100% of a cotton wood cellulose molar weight;
In the 4th step, reaction finishes back adding distilled water makes poplar acetic acid toxilic acid cellulose ester precipitation, and after filtration, washing obtains poplar acetic acid toxilic acid cellulose ester after the vacuum-drying,
Wherein said stopper is benzoquinones, oil of mirbane, 1, aniline, a kind of in monomethylaniline, Resorcinol, phenol, sulphur, dimethyl sulfide, iron(ic) chloride, the cupric chloride.
2, synthetic method according to claim 1 is characterized in that the consumption by control acetic anhydride and maleic anhydride, the quantity of two keys in the control poplar acetic acid toxilic acid cellulose ester.
3, synthetic method according to claim 1, being reflected in the same reactor of it is characterized in that second step and the 3rd goes on foot finished.
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| CN108892728A (en) * | 2018-06-15 | 2018-11-27 | 鲁东大学 | A method of cellulose base levelling agent is prepared using unsaturated fatty acid |
| CN114634414B (en) * | 2021-10-29 | 2023-01-03 | 山东德瑞高分子材料股份有限公司 | Efficient synthesis method of hydroxypropyl methacrylate |
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