CN109575149A - Quaternary alkylphosphonium salt cationic starch and preparation method thereof - Google Patents
Quaternary alkylphosphonium salt cationic starch and preparation method thereof Download PDFInfo
- Publication number
- CN109575149A CN109575149A CN201811582919.0A CN201811582919A CN109575149A CN 109575149 A CN109575149 A CN 109575149A CN 201811582919 A CN201811582919 A CN 201811582919A CN 109575149 A CN109575149 A CN 109575149A
- Authority
- CN
- China
- Prior art keywords
- salt cationic
- alkylphosphonium salt
- cationic starch
- starch
- quaternary alkylphosphonium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/02—Esters
- C08B31/04—Esters of organic acids, e.g. alkenyl-succinated starch
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention discloses a kind of quaternary alkylphosphonium salt cationic starches and preparation method thereof.The quaternary alkylphosphonium salt cationic starch is to be made from starch, esterification occurs using one or more hydroxyls on halogen acyl halide and starch molecular chain, halogen acyl halide is keyed on starch molecular chain, starch-halogen acyl halide graft of esterification modification is generated, then reacts and is prepared with starch-halogen acyl halide graft progress quaternary phosphonium using trialkyl phosphine again.Quaternary alkylphosphonium salt cationic starch thermal stability prepared by the present invention is more preferable, and adsorption capacity is stronger, and the pH scope of application is wider, has broad application prospects；Moreover, preparation method is easy, abundant raw material can prepare a plurality of types of quaternary alkylphosphonium salt cationic starches, enrich the type of cationic starch.
Description
Technical field
The present invention relates to a kind of modified starch materials, more particularly to a kind of quaternary alkylphosphonium salt cationic starch and its preparation side
Method.
Background technique
Starch is a kind of degradable, reproducible Green Polymer Material.But due to the structure of native starch and presentation
Physicochemical characteristics determines its limitation as materials'use.People develop according to the structure and physicochemical property of starch
The denaturation technique of starch, develops a variety of converted starches such as cationic starch, product be widely used in food, weaving, mining,
In the industries such as decontamination, papermaking, casting.
Cationic starch is that cationic base is introduced on ative starch strand by the method for etherificate, esterification, graft copolymerization
Group makes starch have a kind of starch derivatives of positive charge.Cationic starch because its to band negative charge substance it is affinity,
And become a kind of starch derivatives for having essential industry purposes, such as quaternary ammonium salt cationic starch, it is widely used to papermaking, mining
The fields such as industry, oil field, adhesive, cosmetics and sewage treatment.
Quaternary alkylphosphonium salt is similar to quaternary ammonium salt, is a kind of relatively common compound with cation.Phosphorus atoms radius is compared with nitrogen
Atomic radius is big, and corresponding ionic radius is also big, and polarization increases, and electropositive increases, it is easier to negatively charged substance
Generate electrostatic adsorption.Moreover, the decomposition temperature of quaternary alkylphosphonium salt is high, pH adaptability is good, and more preferably, purposes is than season for anti-microbial property
Ammonium salt is extensive.Such as quaternary phosphine salt groups are introduced on starch polymer and prepare quaternary alkylphosphonium salt cationic starch, should be that one kind has
The modified starch material of novel performance.Will have broad application prospects in industries such as chemical industry, electronics, weaving, fuel, agriculturals.
Application No. is the patents of invention of CN201210043878.4 to disclose a kind of preparation method of quaternary phosphine salt type cationic starch, certainly
By carrying out graft copolymerization under base polymerization initiator or effects of ionizing radiation, quaternary alkylphosphonium salt Cationic functional groups are keyed to starch and are divided greatly
On son, quaternary phosphine salt type cationic starch is prepared.The preparation method technics comparing of the quaternary phosphine salt type cationic starch is complicated, preparation
It is relatively simple to obtain quaternary alkylphosphonium salt cationic starch type.Therefore, it is necessary to study new quaternary alkylphosphonium salt cationic starch preparation sides
Method enriches the type of quaternary alkylphosphonium salt cationic starch.
Summary of the invention
For the deficiencies in the prior art, the purpose of the present invention be intended to provide a kind of quaternary alkylphosphonium salt cationic starch and its
Preparation method.The quaternary alkylphosphonium salt cationic starch is that halogen acyl halide is keyed on starch polymer first, then again with trialkyl
Phosphine carries out quaternary phosphonium reaction, and quaternary alkylphosphonium salt cationic starch is prepared.The preparation method is simple, abundant raw material, can prepare a variety of
Type quaternary alkylphosphonium salt cationic starch, enriches the type of cationic starch.
To realize goal of the invention, the technical solution adopted by the present invention are as follows:
A kind of quaternary alkylphosphonium salt cationic starch, the quaternary alkylphosphonium salt cationic starch refer at least one-OH in starch molecule
The product that esterification first occurs with halogen acyl halide, reacts and is formed with trialkyl phosphine generation quaternary phosphonium again.- OH is somebody's turn to do successively through ester
The group with the structure as shown in formula (I) is converted into after changing the reaction of He quaternary phosphonium:
In formula I ,-R1Indicate that carbon atom number is 1~10 alkylidene；X-Indicate Cl-Or Br-；-R2、-R3、-R4Indicate
The aliphatic group that aryl radical or carbon atom number are 1~10.
According to above-mentioned quaternary alkylphosphonium salt cationic starch, it is preferable that-the R1Indicate that carbon atom number is 1~5 alkylidene.
According to above-mentioned quaternary alkylphosphonium salt cationic starch, it is preferable that-the R2、-R3、-R4Indicate phenyl or carbon atom number
For 1~8 aliphatic group.It is further preferred that-the R2、-R3、-R4For phenyl, methyl, ethyl, propyl, butyl, hexyl, pungent
Any one in base.
A kind of preparation method of quaternary alkylphosphonium salt cationic starch, comprising the following steps:
(1) starch and dispersing agent are added in reaction flask, stirring is warming up to 60~90 DEG C, is then added into reaction flask
Halogen acyl halide, maintenance temperature of reaction system are 60~90 DEG C of 2~8h of reaction；The dispersing agent is n,N-Dimethylformamide；Institute
The molar ratio for stating hydroxyl in halogen acyl halide and starch molecule is (0.1~1): 1；
(2) trialkyl phosphine solution is added into reaction mixture obtained by step (1), is warming up to 100~135 DEG C, constant temperature is anti-
Answer 8~30h；The molar ratio of the trialkyl phosphine and halogen acyl halide is 1:(0.5~1.0)；
(3) reaction mixture obtained by step (2) being cooled to room temperature, precipitating is isolated sediment and is washed, and it is dry, it obtains
Dao quaternary alkylphosphonium salt cationic starch.
According to the preparation method of above-mentioned quaternary alkylphosphonium salt cationic starch, it is preferable that in step (1), the starch and dispersion
The ratio of additional amount is 1g starch: 2~6mL dispersing agent between agent；It is further preferred that additional amount between the starch and dispersing agent
Ratio be 1g starch: 2~4mL dispersing agent.
According to the preparation method of above-mentioned quaternary alkylphosphonium salt cationic starch, it is preferable that in step (1), the starch is cereal
At least one of starch, potato starch, bean starch.
According to the preparation method of above-mentioned quaternary alkylphosphonium salt cationic starch, it is preferable that the knot of halogen acyl halide described in step (1)
Shown in structure formula such as formula (II):
In formula (II) ,-R1Indicate that carbon atom number is 1~10 alkylidene；X indicates chlorine atom (Cl) or bromine atom
(Br), Y indicates chlorine atom (Cl) or bromine atom (Br).
According to the preparation method of above-mentioned quaternary alkylphosphonium salt cationic starch, it is preferable that-the R1Indicate carbon atom number be 1~
5 alkylidene.
According to the preparation method of above-mentioned quaternary alkylphosphonium salt cationic starch, it is preferable that the halogen acyl halide is chloracetyl chloride, bromine
Acetyl bromide, 3- chlorpromazine chloride, 4- chlorobutanoylchloride, 4- bromobutanoylchloride, any one in 6- chlorine caproyl chloride.
According to the preparation method of above-mentioned quaternary alkylphosphonium salt cationic starch, it is preferable that halogen acyl halide described in step (1) adds
Enter mode to be added dropwise, time for adding is 3~7min.
According to the preparation method of above-mentioned quaternary alkylphosphonium salt cationic starch, it is preferable that the knot of trialkyl phosphine described in step (2)
Shown in structure formula such as formula (III):
In formula (III) ,-R2、-R3、-R4Indicate that aryl radical or carbon atom number are 1~10 aliphatic group.
According to the preparation method of above-mentioned quaternary alkylphosphonium salt cationic starch, it is preferable that-the R2、-R3、-R4Indicate phenyl
Or the aliphatic group that carbon atom number is 1~8.
According to the preparation method of above-mentioned quaternary alkylphosphonium salt cationic starch, it is preferable that trialkyl phosphine described in step (2) is three
Phenylphosphine, trimethyl-phosphine, triethyl phosphine, tripropyl phosphine, tributylphosphine, three hexyl phosphines, any one in tri octyl phosphine.
According to the preparation method of above-mentioned quaternary alkylphosphonium salt cationic starch, it is preferable that trialkyl phosphine described in step (2) adds
Enter mode to be added dropwise, time for adding is 2~5min.
According to the preparation method of above-mentioned quaternary alkylphosphonium salt cationic starch, it is preferable that trialkyl phosphine solution described in step (2)
The preparation method comprises the following steps: trialkyl phosphine is dissolved with solvent, be configured to the solution that trialkyl phosphine mass fraction is 20%~50%；More
Add preferably, the solvent is dimethylbenzene, toluene, any one in trimethylbenzene.
According to the preparation method of above-mentioned quaternary alkylphosphonium salt cationic starch, it is preferable that the specific behaviour of precipitating described in step (3)
As: reaction mixture is poured slowly into precipitating agent, 20min is stirred, is filtered after standing 1h；It is further preferred that the precipitating
The volume ratio of agent and reaction mixture is 5:1, and the precipitating agent is methanol, ethyl alcohol, isopropanol, any one in n-butanol.
It is a kind of to utilize quaternary alkylphosphonium salt cationic starch products made from above-mentioned preparation method.
Compared with prior art, what the present invention obtained has the beneficial effect that
(1) the present invention provides a kind of preparation method of new quaternary alkylphosphonium salt cationic starch, which uses a step
Method process flow: by starch dispersion in n,N-Dimethylformamide, forming the homogeneous dispersion of non-solution at a certain temperature,
Esterification is carried out with halogen acyl halide, halogen acyl halide is keyed on starch polymer by esterification；Esterification terminates
Afterwards, without separation, trialkyl phosphine solution can be added directly in this dispersion and carry out quaternary phosphonium reaction, quaternary phosphonium is after reaction
Quaternary alkylphosphonium salt cationic starch can be prepared by carrying out precipitating separating treatment.It is mixed that preparation method of the invention significantly reduces reaction
The industrial chemicals such as solvent, precipitating agent used in object separating treatment are closed, process flow is simplified, improve efficiency, save energy consumption, and
And reaction time of esterification is extended, be conducive to the yield for improving quaternary alkylphosphonium salt cationic starch.
(2) starch does not dissolve in general organic solvent, though starch can be dissolved in dimethyl sulfoxide and solution, diformazan is made
Fierce exothermal decomposition reactions can occur for base sulfoxide and acyl chloride monomer；Though starch heats can be gelatinized in water, after gelatinization
Reaction system viscosity is high, is unfavorable for the mixing that comes into full contact with of reaction mass, and halogen acyl halide meets water facile hydrolysis.Therefore, it is necessary to
Find the dispersing agent of a kind of suitable starch and halogen acyl halide progress esterification.By experimental study and exploration, the present invention is selected
Dispersing agent of the n,N-Dimethylformamide as reaction system, by starch dispersion in n,N-Dimethylformamide, starch with
N,N-Dimethylformamide can form the homogeneous dispersion of non-solution at 60~90 DEG C, not only starch can be made evenly dispersed, but also
It can be avoided reaction system and high viscosity be presented, be easy to the mixing dispersion of reaction mass, be conducive to starch and halogen acyl halide carries out ester
Change reaction, be also beneficial to the progress of subsequent quaternary phosphonium reaction, improves esterification He the reaction efficiency of quaternary phosphonium reaction.
(3)-the OH on starch molecular chain and halogen acyl halide occur that by-product HCl, HCl can be generated during esterification
Accumulation be able to suppress the progress of esterification, be unfavorable for sufficiently reacting for starch and halogen acyl halide, lead to esterification efficiency
Low, reaction is incomplete.The application selects dispersing agent of the n,N-Dimethylformamide as starch, and n,N-Dimethylformamide is not only
Starch can be made evenly dispersed, be conducive to esterification, it is often more important that n,N-Dimethylformamide can be generated with esterification
HCl forms complex compound, reduces the concentration of HCl in reaction system, inhibits the side effect of HCl, promote the progress of esterification, improves
The efficiency of starch esterification.
(4) trialkyl phosphine and dispersing agent n,N dimethylformamide are immiscible, and reaction system directly is added in trialkyl phosphine
In, it is unfavorable for the progress of quaternary phosphonium reaction.The present invention is made into molten using toluene, dimethylbenzene or trimethylbenzene as solvent dissolution trialkyl phosphine
After liquid, toluene, dimethylbenzene or trimethylbenzene can dissolve each other to form mixed solution with n,N dimethylformamide, both realize three alkane of dissolution
The purpose of base phosphine, and to the dispersibility that Starch graft copolymer coal-water has had, be conducive to the progress of quaternary phosphonium reaction.
(5) for the present invention using esterification two kinds of reaction mechanisms of He quaternary phosphonium, esterification reaction temperature is that 60~90 DEG C of , quaternary phosphoniums are anti-
Answer temperature be 100~135 DEG C, higher reaction temperature be conducive to improve esterification He quaternary phosphonium reaction speed, improve esterification and
The reaction efficiency of quaternary phosphonium is particularly conducive to the preparation of high degree of substitution quaternary alkylphosphonium salt cationic starch.
(6) preparation method of quaternary alkylphosphonium salt cationic starch of the present invention is easy, easy to industrialized production, and raw material is rich
Richness can prepare a plurality of types of quaternary alkylphosphonium salt cationic starches, enrich the type of cationic starch.
For quaternary alkylphosphonium salt cationic starch prepared by the present invention compared with quaternary ammonium salt cationic starch, thermal stability is more preferable, absorption
Ability is stronger, and the pH scope of application is wider, and antibacterial effect more preferably, has broad application prospects.
Detailed description of the invention
Fig. 1 is the infrared spectrum that the embodiment of the present invention 1 prepares quaternary alkylphosphonium salt cationic maize starch；
Fig. 2 is the infrared spectrum that the embodiment of the present invention 2 prepares quaternary alkylphosphonium salt cation cassava starch.
Specific embodiment
Below by way of specific embodiment, invention is further described in detail, but does not limit the scope of the invention.
Embodiment 1:
A kind of quaternary alkylphosphonium salt cationic starch, the quaternary alkylphosphonium salt cationic starch refer at least one-OH in starch molecule
The product that esterification first occurs with 4- chlorobutanoylchloride, reacts and is formed with tributylphosphine generation quaternary phosphonium again is somebody's turn to do-OH and successively passes through
The group with the structure as shown in formula (IV) is converted into after esterification He quaternary phosphonium reaction:
Specific step is as follows for above-mentioned quaternary alkylphosphonium salt cationic starch preparation method:
48.6g cornstarch (molal quantity of hydroxyl is 0.9mol in starch molecule) is added in 250mL four-hole boiling flask,
100mLN is added, dinethylformamide stirs and is warming up to 80 DEG C, and 15.8g 4- chlorobutanoylchloride is added dropwise into four-hole boiling flask
(0.113mol), 5min drop finish, the isothermal reaction 4h at 80 DEG C；Then it is 39.2% that mass fraction is added dropwise into reaction system again
Tributylphosphine solution, 5min drop finish, and are warming up to 130 DEG C, isothermal reaction 10h, mole of the tributylphosphine and 4- chlorobutanoylchloride
Than for 1:0.818；Reaction mixture is cooled to room temperature after the reaction was completed, is at room temperature slowly added into reaction mixture
Stirring while adding in 800mL ethyl alcohol, 5min is added, and continues stirring 20 minutes, is filtered after standing 1h, is obtained sediment, will precipitate
Object twice, in 60 DEG C of dryings to constant weight, obtains quaternary alkylphosphonium salt cationic starch with ethanol washing.Wherein, the tributylphosphine solution
It is that 27.7g tributylphosphine (0.137mol) is dissolved in the solution being configured in 50mL dimethylbenzene.
The infrared spectrum of quaternary alkylphosphonium salt cationic starch manufactured in the present embodiment is as shown in Figure 1, wherein 3429cm-1For hydroxyl
Absorption vibration peak, 2921cm-1For the stretching vibration absworption peak of methylene, 1731cm-1For carbonyl absorption vibration peak, 1261cm-1
For on quaternary phosphine salt groups with P bonding-the symmetric curvature vibration peak of c h bond, show that quaternary phosphine salt groups are grafted on big point of starch
On son.
Embodiment 2:
A kind of quaternary alkylphosphonium salt cationic starch, the quaternary alkylphosphonium salt cationic starch refer at least one-OH in starch molecule
The product that esterification first occurs with 4- chlorobutanoylchloride, reacts and is formed with tributylphosphine generation quaternary phosphonium again is somebody's turn to do-OH and successively passes through
The group with the structure as shown in formula (V) is converted into after esterification He quaternary phosphonium reaction:
Specific step is as follows for above-mentioned quaternary alkylphosphonium salt cationic starch preparation method:
48.6g tapioca (molal quantity of hydroxyl is 0.9mol in starch molecule) is added in 500mL four-hole boiling flask,
100mLN is added, dinethylformamide stirs and is warming up to 80 DEG C, and 14.3g 4- chlorobutanoylchloride is added dropwise into four-hole boiling flask
(0.102mol), 7min drop finish, the isothermal reaction 4h at 80 DEG C；Then it is 21.4% that mass fraction is added dropwise into reaction system again
Tributylphosphine solution, 3min drop finish, and are heated to 130 DEG C, isothermal reaction 12h, the tributylphosphine and 4- chlorobutanoylchloride
Molar ratio is 1:0.879；Reaction mixture is cooled to room temperature after the reaction was completed, at room temperature, reaction mixture is slowly added to
Into 1000mL ethyl alcohol, 5min is added, and continues stirring 20 minutes, is filtered after standing 1h, and twice with ethanol washing, dry at 60 DEG C
It is dry to constant weight, obtain quaternary alkylphosphonium salt cationic starch.Wherein, the tributylphosphine solution is by 23.5g tributylphosphine
(0.116mol) is dissolved in the solution being configured in 100mL dimethylbenzene.
The infrared spectrum of quaternary alkylphosphonium salt cationic starch manufactured in the present embodiment is as shown in Figure 2, wherein 3425cm-1For hydroxyl
Absorption vibration peak, 2925cm-1For the stretching vibration absworption peak of methylene, 1727cm-1For carbonyl absorption vibration peak, 1262cm-1
For on quaternary phosphine salt groups with P bonding-the symmetric curvature vibration peak of c h bond, show that quaternary phosphine salt groups are grafted on big point of starch
On son.
Embodiment 3:
A kind of quaternary alkylphosphonium salt cationic starch, the quaternary alkylphosphonium salt cationic starch refer at least one-OH in starch molecule
The product that esterification first occurs with bromoacetyl bromide, reacts and is formed with triphenylphosphine generation quaternary phosphonium again is somebody's turn to do-OH successively through ester
The group with the structure as shown in formula (VI) is converted into after changing the reaction of He quaternary phosphonium:
Specific step is as follows for above-mentioned quaternary alkylphosphonium salt cationic starch preparation method:
50.0 cornstarch (molal quantity of hydroxyl is 0.93mol in starch molecule) are added in 500mL four-hole boiling flask,
150mLN is added, dinethylformamide stirs and is warming up to 90 DEG C, and 36.3g bromoacetyl bromide is added dropwise into four-hole boiling flask
(0.18mol), 6min drop finish, the isothermal reaction 2h at 90 DEG C；Then it is 47.7% that mass fraction is added dropwise into reaction system again
Triphenylphosphine solution, 4min drop finish, and are heated to 120 DEG C, isothermal reaction 30h, and the triphenylphosphine and bromoacetyl bromide rub
You are than being 1:1；Reaction mixture is cooled to room temperature after the reaction was completed, reaction mixture is slowly added into 1100mL at room temperature
In ethyl alcohol, 5min is added, and continues stirring 20 minutes, is filtered after standing 1h, and twice with ethanol washing, dry to perseverance at 60 DEG C
Weight, obtains quaternary alkylphosphonium salt cationic starch.Wherein, the triphenylphosphine solution is to be dissolved in 47.1g triphenylphosphine (0.18mol)
The solution being configured in 60mL dimethylbenzene.
Embodiment 4:
A kind of quaternary alkylphosphonium salt cationic starch, the quaternary alkylphosphonium salt cationic starch refer at least one-OH in starch molecule
The product that esterification first occurs with 6- chlorine caproyl chloride, reacts and is formed with tri octyl phosphine generation quaternary phosphonium again is somebody's turn to do-OH and successively passes through
The group with the structure as shown in formula (VII) is converted into after esterification He quaternary phosphonium reaction:
Specific step is as follows for above-mentioned quaternary alkylphosphonium salt cationic starch preparation method:
48.6g wheaten starch (molal quantity of hydroxyl is 0.9mol in starch molecule) is added in 500mL four-hole boiling flask,
100mLN is added, dinethylformamide stirs and is warming up to 90 DEG C, and 22.8g 6- chlorine caproyl chloride is added dropwise into four-hole boiling flask
(0.135mol), 5min drop finish, the isothermal reaction 6h at 90 DEG C；Then it is 50% 3 that mass fraction is added dropwise into reaction system again
Octyl phosphine solution, 5min drop finish, and are heated to 135 DEG C, isothermal reaction 16h, the tri octyl phosphine rubs with 6- chlorine caproyl chloride
You are than being 1:0.96；Reaction mixture is cooled to room temperature after the reaction was completed, is at room temperature slowly added into reaction mixture
In 900mL ethyl alcohol, 5min is added, and continues stirring 20 minutes, is filtered after standing 1h, and twice with ethanol washing, in 60 DEG C of dryings
To constant weight, quaternary alkylphosphonium salt cationic starch is obtained.Wherein, the tri octyl phosphine solution is that 51.8g tri octyl phosphine (0.14mol) is molten
The solution being configured in 60mL dimethylbenzene.
Embodiment 5:
A kind of quaternary alkylphosphonium salt cationic starch, the quaternary alkylphosphonium salt cationic starch refer at least one-OH in starch molecule
The product that esterification first occurs with 4- bromobutanoylchloride, reacts and is formed with triphenylphosphine generation quaternary phosphonium again is somebody's turn to do-OH and successively passes through
The group with the structure as shown in formula (VIII) is converted into after esterification He quaternary phosphonium reaction:
Specific step is as follows for above-mentioned quaternary alkylphosphonium salt cationic starch preparation method:
50.0g tapioca (molal quantity of hydroxyl is 0.93mol in starch molecule) is added to 500mL four-hole boiling flask
In, 100mLN is added, dinethylformamide stirs and is warming up to 80 DEG C, and 37.8g 4- bromine fourth is added dropwise into four-hole boiling flask
Acyl chlorides (0.204mol), 5min drop finish, the isothermal reaction 4h at 80 DEG C；Then mass fraction is added dropwise into reaction system again is
45.1% triphenylphosphine solution, 5min drop finish, and are heated to 120 DEG C, isothermal reaction 30h, the triphenylphosphine and 4- bromine fourth
The molar ratio of acyl chlorides is 1:0.76；Reaction mixture is cooled to room temperature after the reaction was completed, it is at room temperature that reaction mixture is slow
It is added in 1000mL ethyl alcohol, 5min is added, and continues stirring 20 minutes, is filtered after standing 1h, and twice with ethanol washing, 60
It is DEG C dry to constant weight, obtain quaternary alkylphosphonium salt cationic starch.Wherein, the triphenylphosphine solution is by 70.7g triphenylphosphine
(0.27mol) is dissolved in the solution being configured in 100mL dimethylbenzene.
Embodiment 6:
A kind of quaternary alkylphosphonium salt cationic starch, the quaternary alkylphosphonium salt cationic starch refer at least one-OH in starch molecule
The product that esterification first occurs with chloracetyl chloride, reacts and is formed with three hexyl phosphines generation quaternary phosphonium again is somebody's turn to do-OH successively through ester
The group with the structure as shown in formula (VIII) is converted into after changing the reaction of He quaternary phosphonium:
Specific step is as follows for above-mentioned quaternary alkylphosphonium salt cationic starch preparation method
48.6g cornstarch (molal quantity of hydroxyl is 0.9mol in starch molecule) is added in 500mL four-hole boiling flask,
200mL n,N-Dimethylformamide is added, stir and is warming up to 60 DEG C, 10.9g chloracetyl chloride is added dropwise into four-hole boiling flask
(0.097mol), 5min drop finish, the isothermal reaction 4h at 60 DEG C；Then it is 39.2% that mass fraction is added dropwise into reaction system again
Three hexyl phosphine solution, 5min drop finish, and are heated to 135 DEG C, isothermal reaction 16h, and the three hexyls phosphine and chloracetyl chloride rub
You are than being 1:1；Reaction mixture is cooled to room temperature after the reaction was completed, reaction mixture is slowly added into 1300mL at room temperature
In ethyl alcohol, 5min is added, and continues stirring 20 minutes, is filtered after standing 1h, and twice with ethanol washing, dry to perseverance at 60 DEG C
Weight, obtains quaternary alkylphosphonium salt cationic starch.Wherein, the three hexyls phosphine solution is to be dissolved in tri- hexyl phosphine (0.097mol) of 27.7g
The solution being configured in 50mL dimethylbenzene.
Embodiment 7:
A kind of quaternary alkylphosphonium salt cationic starch, the quaternary alkylphosphonium salt cationic starch refer at least one-OH in starch molecule
The product that esterification first occurs with chloracetyl chloride, reacts and is formed with trimethyl-phosphine generation quaternary phosphonium again is somebody's turn to do-OH successively through ester
The group with the structure as shown in formula (IX) is converted into after changing the reaction of He quaternary phosphonium:
Specific step is as follows for above-mentioned quaternary alkylphosphonium salt cationic starch preparation method:
48.6g tapioca (molal quantity of hydroxyl is 0.9mol in starch molecule) is added to 1000mL four-hole boiling flask
In, 150mL n,N-Dimethylformamide is added, stirs and is warming up to 60 DEG C, 101.7g chloracetyl is added dropwise into four-hole boiling flask
Chlorine (0.9mol), 5min drop finish, the isothermal reaction 8h at 60 DEG C；Then it is 49.8% that mass fraction is added dropwise into reaction system again
Trimethyl-phosphine solution, 5min drop finish, and are heated to 100 DEG C, isothermal reaction 20h, and the trimethyl-phosphine and chloracetyl chloride rub
You are than being 1:0.5；Reaction mixture is cooled to room temperature after the reaction was completed, reaction mixture is slowly added to 1600mL at room temperature
In n-butanol, 5min is added, and continues stirring 20 minutes, is filtered after standing 1h, and washed twice with n-butanol, is dried extremely at 60 DEG C
Constant weight obtains quaternary alkylphosphonium salt cationic starch.Wherein, the trimethyl-phosphine solution is to be dissolved in 136.8g trimethyl-phosphine (1.8mol)
The solution being configured in 160mL toluene.
Embodiment 8:
A kind of quaternary alkylphosphonium salt cationic starch, the quaternary alkylphosphonium salt cationic starch refer at least one-OH in starch molecule
The product that esterification first occurs with 6- chlorine caproyl chloride, reacts and is formed with triethyl phosphine generation quaternary phosphonium again is somebody's turn to do-OH and successively passes through
The group with the structure as shown in formula (X) is converted into after esterification He quaternary phosphonium reaction:
Specific step is as follows for the preparation method of above-mentioned quaternary alkylphosphonium salt cationic starch
48.6g cornstarch (molal quantity of hydroxyl is 0.9mol in starch molecule) is added in 500mL four-hole boiling flask,
100mL n,N-Dimethylformamide is added, stir and is warming up to 90 DEG C, 45.6g 6- chlorine hexanoyl is added dropwise into four-hole boiling flask
Chlorine (0.27mol), 5min drop finish, the isothermal reaction 6h at 90 DEG C；Then mass fraction is added dropwise into reaction system again is
47.1% triethyl phosphine solution, 5min drop finish, and are heated to 110 DEG C, isothermal reaction 20h, the triethyl phosphine and 6- chlorine oneself
The molar ratio of acyl chlorides is 1:0.692；Reaction mixture is cooled to room temperature after the reaction was completed, reaction mixture is slowly added into
In 900mL methanol, 5min is added, and continues stirring 20 minutes, is filtered after standing 1h, and washed twice with methanol, in 60 DEG C of dryings
To constant weight, quaternary alkylphosphonium salt cationic starch is obtained.Wherein, the triethyl phosphine solution is that 46.0g triethyl phosphine (0.39mol) is molten
The solution being configured in 60mL dimethylbenzene.
Embodiment 9:
A kind of quaternary alkylphosphonium salt cationic starch, the quaternary alkylphosphonium salt cationic starch refer at least one-OH in starch molecule
The product that esterification first occurs with chloracetyl chloride, reacts and is formed with tripropyl phosphine generation quaternary phosphonium again is somebody's turn to do-OH successively through ester
The group with the structure as shown in formula (XI) is converted into after changing the reaction of He quaternary phosphonium:
Specific step is as follows for the preparation method of above-mentioned quaternary alkylphosphonium salt cationic starch
48.6g wheaten starch (molal quantity of hydroxyl is 0.9mol in starch molecule) is added in 500mL four-hole boiling flask,
200mL n,N-Dimethylformamide is added, stir and is warming up to 60 DEG C, 50.85g chlorine caproyl chloride is added dropwise into four-hole boiling flask
(0.45mol), 5min drop finish, the isothermal reaction 8h at 60 DEG C；Then it is 45.5% that mass fraction is added dropwise into reaction system again
Tripropyl phosphine solution, 5min drop finish, and are heated to 135 DEG C, isothermal reaction 8h, mole of the tripropyl phosphine and chloracetyl chloride
Than for 1:1；Reaction mixture is cooled to room temperature after the reaction was completed, reaction mixture is slowly added into 1500mL isopropanol
In, 5min is added, and continues stirring 20 minutes, is filtered after standing 1h, and washed twice with isopropanol, it dries at 60 DEG C to constant weight,
Obtain quaternary alkylphosphonium salt cationic starch.Wherein, the tripropyl phosphine solution is that 72g tripropyl phosphine (0.45mol) is dissolved in 100mL tri-
The solution being configured in toluene.
The foregoing is merely illustrative of the preferred embodiments of the present invention, but is not limited only to examples detailed above, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of quaternary alkylphosphonium salt cationic starch, which is characterized in that the quaternary alkylphosphonium salt cationic starch refers in starch molecule at least
The product for having-an OH that esterification first occurs with halogen acyl halide, reacts and is formed with trialkyl phosphine generation quaternary phosphonium again, should-
OH is successively converted into the group with the structure as shown in formula (I) after esterification He quaternary phosphonium reaction:
In formula I ,-R1Indicate that carbon atom number is 1~10 alkylidene；X-Indicate Cl-Or Br-；-R2、-R3、-R4Indicate aromatic hydrocarbon
The aliphatic group that base or carbon atom number are 1~10.
2. quaternary alkylphosphonium salt cationic starch according to claim 1, which is characterized in that-the R1Indicate carbon atom number be 1~
5 alkylidene.
3. quaternary alkylphosphonium salt cationic starch according to claim 1, which is characterized in that-the R2、-R3、-R4Indicate phenyl
Or the aliphatic group that carbon atom number is 1~8.
4. a kind of preparation method of quaternary alkylphosphonium salt cationic starch, which comprises the following steps:
(1) starch and dispersing agent are added in reaction flask, stirring is warming up to 60~90 DEG C, is then added into reaction flask halogenated
Carboxylic acid halides, maintenance temperature of reaction system are 60~90 DEG C of 2~8h of reaction；The dispersing agent is n,N-Dimethylformamide；The halogen
The molar ratio of hydroxyl is (0.1~1) in halogen acyl halide and starch molecule: 1；
(2) trialkyl phosphine solution is added into reaction mixture obtained by step (1), is warming up to 100~135 DEG C, isothermal reaction 8~
30h；The molar ratio of the trialkyl phosphine and halogen acyl halide is 1:(0.5~1.0)；
(3) reaction mixture obtained by step (2) being cooled to room temperature, precipitating is isolated sediment and is washed, and it is dry, obtain season
Phosphonium salt cationic starch.
5. the preparation method of quaternary alkylphosphonium salt cationic starch according to claim 4, which is characterized in that described in step (1)
Shown in the structural formula of halogen acyl halide such as formula (II):
In formula (II) ,-R1Indicate that carbon atom number is 1~10 alkylidene；X indicates chlorine atom (Cl) or bromine atom (Br), Y table
Show chlorine atom (Cl) or bromine atom (Br).
6. the preparation method of quaternary alkylphosphonium salt cationic starch according to claim 5, which is characterized in that-the R1Indicate carbon
The alkylidene that atomicity is 1~5.
7. the preparation method of quaternary alkylphosphonium salt cationic starch according to claim 4, which is characterized in that described in step (2)
Shown in the structural formula of trialkyl phosphine such as formula (III):
In formula (III) ,-R2、-R3、-R4Indicate that aryl radical or carbon atom number are 1~10 aliphatic group.
8. the preparation method of quaternary alkylphosphonium salt cationic starch according to claim 7, which is characterized in that-the R2、-R3、-R4
Indicate that phenyl or carbon atom number are 1~8 aliphatic group.
9. the preparation method of quaternary alkylphosphonium salt cationic starch according to claim 4, which is characterized in that described in step (2)
Trialkyl phosphine solution the preparation method comprises the following steps: trialkyl phosphine is dissolved with solvent, be configured to trialkyl phosphine mass fraction be 20%~
50% solution；The solvent is any one of dimethylbenzene, toluene, trimethylbenzene.
10. a kind of utilize quaternary alkylphosphonium salt cationic starch products made from any preparation method of claim 4~9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811582919.0A CN109575149A (en) | 2018-12-24 | 2018-12-24 | Quaternary alkylphosphonium salt cationic starch and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811582919.0A CN109575149A (en) | 2018-12-24 | 2018-12-24 | Quaternary alkylphosphonium salt cationic starch and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109575149A true CN109575149A (en) | 2019-04-05 |
Family
ID=65930957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811582919.0A Pending CN109575149A (en) | 2018-12-24 | 2018-12-24 | Quaternary alkylphosphonium salt cationic starch and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109575149A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118185198A (en) * | 2024-04-02 | 2024-06-14 | 宁波宇华实业股份有限公司 | Corrosion-resistant self-cleaning PE pipeline and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739786A (en) * | 2013-12-31 | 2014-04-23 | 河南金誉包装科技股份有限公司 | High polymer quaternary phosphonium salt antibacterial material and preparation method thereof |
| CN105968217A (en) * | 2016-05-05 | 2016-09-28 | 中国科学院烟台海岸带研究所 | Acetylated starch quaternary phosphonium salt and its preparation method and use |
-
2018
- 2018-12-24 CN CN201811582919.0A patent/CN109575149A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739786A (en) * | 2013-12-31 | 2014-04-23 | 河南金誉包装科技股份有限公司 | High polymer quaternary phosphonium salt antibacterial material and preparation method thereof |
| CN105968217A (en) * | 2016-05-05 | 2016-09-28 | 中国科学院烟台海岸带研究所 | Acetylated starch quaternary phosphonium salt and its preparation method and use |
Non-Patent Citations (4)
| Title |
|---|
| JANTAS, R ET AL: "Starch functionalized by chloroacetate groups: Coupling of bioactive salicylic acid", 《STARCH-STARKE》 * |
| SARA R.LABAFZADEH ET AL: "Amination and thiolation of chloroacetyl cellulose through reactivedissolution in N,N-dimethylformamide", 《CARBOHYDRATE POLYMERS》 * |
| 杨锦宗: "《工业有机合成基础》", 31 December 1998, 中国石化出版社 * |
| 程能林: "《溶剂手册 第2版》", 30 September 1994, 化学工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118185198A (en) * | 2024-04-02 | 2024-06-14 | 宁波宇华实业股份有限公司 | Corrosion-resistant self-cleaning PE pipeline and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108779086B (en) | Method for preparing IDO inhibitor EPACADOSTAT | |
| CN104098770B (en) | A kind of synthetic method of helical structure polyaniline nano fiber | |
| CN102796222B (en) | Synthesis method of hydrophobically associated polyacrylamide | |
| WO2018207934A1 (en) | Composition for polymerization, polymer of same and method for producing polymer | |
| CN102732041A (en) | Phosphorus-containing Schiff base derivative intumescent fire retardant and preparation method thereof | |
| CN104844745B (en) | A kind of response type phosphonium flame retardant and preparation method thereof | |
| CN109575149A (en) | Quaternary alkylphosphonium salt cationic starch and preparation method thereof | |
| CN103044641B (en) | A kind of preparation method of amphiphilic block inner quaternary ammonium oil displacement agent | |
| CN104861161B (en) | A kind of method for preparing Amino End Group polyethylene glycol | |
| CN107365403A (en) | A kind of preparation method of drilling fluid heat resisting fluid loss reducing agent | |
| CN113214319B (en) | Quaternary phosphonium salt flame retardant and synthetic method and application thereof | |
| CN104744709A (en) | Dendritic polyamide type ester quaternary ammonium salt and synthetic process thereof | |
| EP2481414B1 (en) | A process for the preparation of cross-linked polyallylamines or pharmaceutically acceptable salts thereof | |
| CN101157667A (en) | Morpholine quaternary ammonium salt ion liquid and preparation method thereof | |
| CN104761673B (en) | A kind of carbomer and preparation method thereof | |
| CN101698660A (en) | Imidazole-type ionic liquid containing disubstituted phenyl, and preparation method thereof | |
| CN108659241B (en) | Star-shaped polymer with temperature responsiveness, pH responsiveness and carbon dioxide responsiveness, self-healing hydrogel and preparation method | |
| CN103890121B (en) | Dendroid starch based dextrin adhesives | |
| CN105924679A (en) | Nano-composite intumescent flame retardant and preparing method thereof | |
| CN102585097A (en) | Method for preparing amphoteric starch | |
| CN111592616A (en) | Preparation method of nanoscale hyperbranched hydrophobically associating polyacrylamide | |
| CN107216468A (en) | A kind of supramolecular hydrogel and preparation method thereof | |
| CN103483216B (en) | Polymerizable monomer, and preparation method and application thereof | |
| CN102174056B (en) | Methyltri(2,3-dichloropropoxy)silane compound and preparation method thereof | |
| CN103585925A (en) | Preparation method of double-end based amide type glycine betaine surfactant and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190405 |