CN105884913B - A kind of preparation method of trimethyl silicon substrate starch ether - Google Patents
A kind of preparation method of trimethyl silicon substrate starch ether Download PDFInfo
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Abstract
A kind of preparation method of trimethyl silicon substrate starch ether is using mantoquita as catalyst, and hexamethyldisilazane is organic silicon ether agent, the silicon substrate hydrophobic modification of starch is carried out in organic solvent, between the trimethyl silicon substrate starch ether degree of substitution of gained is 0.83~2.68.Method reaction condition provided by the invention is mild, and operating process is simple, and degree of substitution is controllable, and products obtained therefrom has good dissolubility in organic solvent, and has stronger hydrophobicity.
Description
Technical field
The present invention relates to a kind of preparation methods of trimethyl silicon substrate starch ether.
Background technology
Starch is increasingly subject to people because having many advantages, such as to derive from a wealth of sources, due to cheap, nontoxic, good biological degradability
Concern.Starch, which carries out hydrophobization modification, can destroy starch crystals area and noncrystalline domain intermolecular hydrogen bonding, it can be made from parent
It is aqueous to become hydrophobicity, it is substantially improved in THF, acetone, CHCl3In dissolubility.Common starches hydrophobized modified group
All kinds of halohydrocarbyl structures are more used, the carbon atom being connected with halogen atom is easy to that substitution reaction occurs with hydroxyl, in starch
The hydrocarbyl group connected with ehter bond is introduced on molecule.The reaction condition of starch hydroxyl and halogenated hydrocarbons is higher, reaction efficiency is relatively low；
Its hydrophobicity power is influenced by alkyl chain structure, and therefore, it is starch chemistry to establish the starches hydrophobized method of modifying for being easy to react
One of the important content of product research.Trimethylsilyl ethers is introduced in starch molecule can also improve its hydrophobicity, and product is difference
The trimethyl silicon substrate starch ether of degree of substitution.
It is mainly at present that starch and trim,ethylchlorosilane are anti-in the case where pyridine makees acid binding agent to the research of starch trimethyl silication
Answer that (Dong Xueting, Li Bo, Li Tao wait synthesis [J] the chemical research of trimethyl silicon substrate starch ethers and application, 2008,20 (8):
992-995.), but pyridine toxicity used is big.Starch reacted with hexamethyldisilazane in the case where DMSO makees solvent (Sugih A.K.,
Picchioni F.,Janssen L.P.B.M.,et al.Synthesis of poly-(epsilon)-caprolactone
grafted starch co-polymers by ring-opening polymerisation using silylated
starch precursors[J].Carbohydrate polymers,2009,77(2):267-275.), due to not adding catalysis
Agent, reaction need to carry out under 70 degrees Celsius, the time up to for 24 hours, the degree of substitution of product there was only 0.68.Starch and hexamethyl chlorine
Silane reacts (Petzold K., Einfeldt L., Gunther W., et al.Regioselective in the case where liquefied ammonia makees solvent
functionalization of starch:Synthesis and HNMR characterization of 6-O-silyl
ethers[J].Biomacromolecules,2001,2(3):965-969.), reaction condition is more harsh.And it is to urge with mantoquita
Agent catalytic starch occurs the method that etherification reaction prepares silicon etherification starch with hexamethyldisilazane and has not been reported.
Invention content
The purpose of the present invention is to provide a kind of preparation method of trimethyl silicon substrate starch ether, be using mantoquita as catalyst,
Hexamethyldisilazane (HMDS) is organic silicon ether agent, carries out the silicon substrate hydrophobic modification of starch in organic solvent.The party
The advantages of method, is, in the presence of low dosage mantoquita, the reaction time is short, reaction condition is mild, hexamethyldisilazane conversion ratio
High, product degree of substitution height.
A kind of preparation method of trimethyl silicon substrate starch ether, using starch and HMDS as raw material, is to urge with mantoquita in solvent
Agent carries out silicon etherification reaction to starch in 25~80 DEG C under ultrasound condition, obtains trimethyl silicon substrate starch ether,
Wherein, mantoquita be copper sulphate, copper nitrate, copper acetate, 1~2 kind in copper chloride, the molar ratio of mantoquita and HMDS is
1~5:100.
In above-mentioned technical proposal, the preferably described reaction temperature is 25~50 DEG C.
In above-mentioned technical proposal, preferably the molar ratio of mantoquita and HMDS is 2.1:100.
In above-mentioned technical proposal, the solvent is organic solvent, preferably n,N-Dimethylformamide, N, N- dimethyl second
Amide, N, 1~2 kind in N- dimethyl sulfoxide (DMSO)s, sulfolane, further preferably n,N-Dimethylformamide, N, N- dimethyl
Acetamide.
In above-mentioned technical proposal, the dosage of the preferably described HMDS is the amount of dehydrated glucose unit (AGU) substance in starch
1~6 times.The degree of substitution of product can be adjusted in the present invention by adjusting the dosage of HMDS.
In above-mentioned technical proposal, the preferably described solvent is 5~15 with starch and HMDS total weight ratios:1 (v/w), further
Preferably 8~12:1(v/w).
In above-mentioned technical proposal, the preferably described starch is cereal starch, potato starch, bean starch, as waxy corn forms sediment
Powder, potato starch, potato starch, wheaten starch, tapioca etc..
In above-mentioned technical proposal, the preferably described ultrasonic power is 50~600W, further preferably 50~150W.
In above-mentioned technical proposal, preferably mantoquita is copper sulphate, copper nitrate.
The trimethyl silicon substrate starch ether prepared using the above method, degree of substitution are 0.83~2.68.
Further, yet other embodiments are：
A kind of preparation method of trimethyl silicon substrate starch ether, including following processing steps：
By material rate, starch is placed in solvent, ultrasonic disperse to homogeneous system, it is warming up to 25 under ultrasound condition~
80 DEG C, HMDS is added dropwise, magnetic agitation is reacted 1~12h, sampled into gas phase analysis HMDS contents, gas chromatography every half an hour
Determine reaction end.After reaction, product is cooled to room temperature, pours out upper layer solvent, and ethyl alcohol is poured into lower layer's product
And deionized water, product is precipitated, then filters, 60~90 DEG C of vacuum drying obtain the crude product of trimethyl silicon substrate starch ether.By institute
After the crude product grinding for stating trimethyl silicon substrate starch, dissolving in acetone, obtains supernatant after centrifugation, by supernatant concentration, then
Deionized water is added thereto, product is precipitated, repetitive operation obtains the trimethyl silicane of purifying until crude product powder becomes colorless
Base starch ether.
Beneficial effects of the present invention are：Compared with the prior art, preparation method reaction condition provided by the invention is mild, instead
Short between seasonable, operating process is simple, and degree of substitution is controllable, and products obtained therefrom has good dissolubility in organic solvent, and has
Stronger hydrophobicity.
Description of the drawings
Fig. 1 is the IR spectrograms of starch and different degree of substitution product；
Fig. 2 is different degree of substitution trimethyl silicon substrate starch ether1H NMR spectras；
Fig. 3 is the trimethyl silicon substrate starch ether contact angle schematic diagram of DS=2.59.
Specific implementation mode
Following non-limiting embodiments can make those skilled in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
The measurement of trimethyl silicon substrate starch ether degree of substitution：Using1H NMR methods determine the substitution of trimethyl silicon substrate starch ether
Spend (Mormann W., Wezstein M.Trimethylsilylation of Cellulose in Ionic Liquids
[J].Macromolecular Bioscience,2009,9(4):369-375.), the calculation formula of degree of substitution (DS) is to use
The ratio of the proton signal peak area of methyl and glucose unit proton signal peak area calculates in trimethyl silicon substrate：
DS=7A/9B (1)
Wherein, A represents methyl signals peak area on trimethyl silicane, δ=0.1~0.4；B represents the signal peak of starch backbone
Area, δ=3.3~5.5.
Embodiment 1
The DMF of 100ml is added as solvent, according to n (Cu (NO in the waxy corn starch for taking 10g3)2·3H2O):n
(HMDS)=2.1:100, Cu (NO are added3)2·3H2O is as catalyst, 50W ultrasonic disperses to homogeneous system, at 50 DEG C, according to
n(HMDS):N (AGU)=3:1 is added dropwise HMDS, and magnetic agitation is sampled every half an hour into gas phase analysis HMDS contents, gas phase color
Spectrometry determines reaction end, and after reacting 7h, HMDS conversion ratios are 100%.After reaction, product is cooled to room temperature, poured out
Upper layer solvent, and ethyl alcohol and deionized water are poured into lower layer's product, product is precipitated, then filters, 90 DEG C of vacuum drying obtain three
Methylsilyl starch ether crude product.After the crude product of the trimethyl silicon substrate starch is ground, dissolving in acetone, obtains after centrifugation
To supernatant, by supernatant concentration, then a large amount of deionized waters are added thereto, product, repetitive operation, until crude product powder is precipitated
End becomes colorless, and obtains the trimethyl silicon substrate starch ether of purifying, yield 78.7%,1The DS that H NMR methods measure product is
2.36。
Comparative example 1
The DMF of 100ml is added as solvent, 50W ultrasonic disperses to homogeneous system, heating in the waxy corn starch for taking 10g
To 50 DEG C, according to n (HMDS) and n (AGU)=3:1 is added dropwise HMDS, and magnetic agitation is sampled every half an hour into gas phase analysis HMDS
Content, gas chromatography determines reaction end, and after reaction for 24 hours, HMDS conversion ratios are 100%.
With under the same terms, n (Cu (NO are added3)2·3H2O):Cu (the NO of n (HMDS)=2.1%3)2·3H2O is used as and urges
Agent (embodiment 1) is compared, and the reaction time is extended to for 24 hours by 7h, and energy consumption dramatically increases.
Embodiment 2
The DMF of 100ml is added as solvent, according to n (Cu (NO in the waxy corn starch for taking 10g3)2·3H2O):n
(HMDS)=2.1% Cu (NO are added3)2·3H2O is as catalyst, 50W ultrasonic disperses to homogeneous system, at 80 DEG C, according to n
(HMDS) with n (AGU)=3:1 is added dropwise HMDS, and magnetic agitation is sampled every half an hour into gas phase analysis HMDS contents, gas phase color
Spectrometry determines reaction end, and after reacting 2h, HMDS conversion ratios are 100%.After reaction, product is cooled to room temperature, poured out
Upper layer solvent, and a large amount of ethyl alcohol and deionized water are poured into lower layer's product, product is precipitated, then filters, 90 DEG C of vacuum drying,
Obtain trimethyl silicon substrate starch ether crude product.After the crude product of the trimethyl silicon substrate starch is ground, dissolving in acetone, centrifuges
After obtain supernatant, by supernatant concentration, then a large amount of deionized waters are added thereto, product, repetitive operation, until thick production are precipitated
Object powder becomes colorless, and obtains the trimethyl silicon substrate starch ether of purifying, yield 76.9%,1The DS that H NMR methods measure product is
2.35。
Comparative example 2
The DMF of 100ml is added as solvent, 50W ultrasonic disperses to homogeneous system, heating in the waxy corn starch for taking 10g
To 80 DEG C, according to n (HMDS) and n (AGU)=3:1 is added dropwise a certain amount of HMDS, and magnetic agitation is sampled every half an hour into gas phase
HMDS contents are analyzed, gas chromatography determines reaction end, and after reacting 8h, HMDS conversion ratios can be only achieved 100%.
With under the same terms, n (Cu (NO are added3)2·3H2O):Cu (the NO of n (HMDS)=2.1%3)2·3H2O is used as and urges
Agent (embodiment 2) is compared, and the reaction time extends to 8h by 2h, and energy consumption dramatically increases.
Embodiment 3~4
According to n (HMDS) and n (AGU)=1:1 and 2:HMDS is added dropwise in 1 ratio, and other conditions are consistent with embodiment 1, obtain
The product that degree of substitution is 0.84 and 1.63 is obtained, yield is respectively 84% and 81.5%.
Embodiment 5~8
The waxy corn starch in embodiment 1 is replaced using potato starch, potato starch, wheaten starch, tapioca,
Other conditions are consistent with embodiment 1, reacted with HMDS, obtain corresponding derivative.
Embodiment 9~11
Using DMAC N,N' dimethyl acetamide, N, N- dimethyl sulfoxide (DMSO)s, sulfolane replace the N in embodiment 1, N- dimethyl methyls
Amide, other conditions are consistent with embodiment 1, reacted with HMDS, obtain starch derivatives.
Embodiment 12~14
Cu (the NO in embodiment 1 are replaced using copper sulphate, copper acetate, copper chloride3)2·3H2O, other conditions and embodiment
1 is consistent, is reacted with HMDS, obtains starch derivatives.
Embodiment 15
Trimethyl silicon substrate starch ether dissolubility and hydrophobicity measure：
Trimethyl silicon substrate starch ether (sample of 1 degree of substitution 2.36 of embodiment, the reality of a certain amount of different degree of substitution are weighed respectively
Apply the sample of 3 degree of substitution 0.84 of example, the sample of 4 degree of substitution 1.63 of embodiment), then it is dissolved in 100g DMSO, DMF, H respectively2O, third
Ketone, THF, CHCl3In, supersaturated solution is formed, then in the lower placement 2h of heating, solution is filtered after cooling, by filtrate
It is transferred in culture dish, is placed in oven and dried to constant weight, weigh its weight m (g), be its solubility.For DS=2.36's
Its dissolubility in THF, chloroform, acetone of trimethyl silicon substrate starch ether is respectively 33.4g/100gTHF, 20.5g/100g
CHCl3, 26.2g/100g acetone.
1 starch of table and different degree of substitution trimethyl silicon substrate starch ether solubility
Note) × indicate that the trimethyl silicon substrate starch ether of the degree of substitution is insoluble in this solvent
Embodiment 16
DS=2.36 trimethyl silicon substrate starch ether products are pressed into the thin slice of surfacing with powder compressing machine, use five-spot
It is averaged to get contact angle, θ=130.88 ° after wafer surface takes 5 points of measurements.
Claims (4)
1. a kind of preparation method of trimethyl silicon substrate starch ether, it is characterised in that：In solvent, using starch and HMDS as raw material,
Using mantoquita as catalyst, silicon etherification reaction is carried out to starch in 25~80 DEG C under ultrasound condition, obtains trimethyl silicon substrate starch ether, institute
It is 0.83~2.68 to obtain trimethyl silicon substrate starch ether degree of substitution；
Wherein, mantoquita be copper sulphate, copper nitrate, copper acetate, 1~2 kind in copper chloride, the molar ratio of mantoquita and HMDS is 1~
5:100；The dosage of the HMDS is 1~6 times of the amount of dehydrated glucose unit substance in starch；The ultrasonic power be 50~
600W；The solvent is 5~15 with starch and HMDS total weight ratios:1.
2. according to the method described in claim 1, it is characterized in that：The starch is cereal starch, potato starch, beans shallow lake
Powder.
3. according to the method described in claim 1, it is characterized in that：Solvent for use is N,N-dimethylformamide, N, N- diformazans
Yl acetamide, N, 1~2 kind in N- dimethyl sulfoxide (DMSO)s, sulfolane.
4. according to the method described in claim 1, it is characterized in that：Including following processing steps：
By material rate, starch is placed in solvent, ultrasonic disperse to homogeneous system is warming up to 25~80 under ultrasound condition
DEG C, HMDS is added dropwise, magnetic agitation is reacted 1~12h, sampled into gas phase analysis HMDS contents every half an hour, gas chromatography is true
Determine reaction end；
After reaction, product is cooled to room temperature, pours out upper layer solvent, and ethyl alcohol and deionization are poured into lower layer's product
Water is precipitated product, then filters, and 60~90 DEG C of vacuum drying obtain the crude product of trimethyl silicon substrate starch ether；
After the crude product of the trimethyl silicon substrate starch is ground, dissolving in acetone, obtains supernatant, by supernatant after centrifugation
Concentration, then deionized water is added thereto, product is precipitated, repetitive operation obtains the three of purifying until crude product powder becomes colorless
Methylsilyl starch ether.
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