CN109535265A - A kind of preparation method of anionic hydroxyethyl cellulose - Google Patents
A kind of preparation method of anionic hydroxyethyl cellulose Download PDFInfo
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- CN109535265A CN109535265A CN201811405329.0A CN201811405329A CN109535265A CN 109535265 A CN109535265 A CN 109535265A CN 201811405329 A CN201811405329 A CN 201811405329A CN 109535265 A CN109535265 A CN 109535265A
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- hydroxyethyl cellulose
- isopropanol
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- 229920000663 Hydroxyethyl cellulose Polymers 0.000 title claims abstract description 98
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 title claims abstract description 97
- 239000004354 Hydroxyethyl cellulose Substances 0.000 title claims abstract description 92
- 125000000129 anionic group Chemical group 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 116
- 239000000047 product Substances 0.000 claims abstract description 56
- 239000007864 aqueous solution Substances 0.000 claims abstract description 40
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000012065 filter cake Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000012046 mixed solvent Substances 0.000 claims abstract description 26
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 21
- 239000010452 phosphate Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 19
- SQPBDQRPUZEAQD-UHFFFAOYSA-N (3-chloro-2-hydroxypropyl) dihydrogen phosphate Chemical compound ClCC(O)COP(O)(O)=O SQPBDQRPUZEAQD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 34
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 16
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 abstract description 4
- -1 building Substances 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 238000001914 filtration Methods 0.000 description 6
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 239000011877 solvent mixture Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKUSWAGOKUGEDX-UHFFFAOYSA-N C(CCC)Br(CCCC)(CCCC)CCCC Chemical compound C(CCC)Br(CCCC)(CCCC)CCCC OKUSWAGOKUGEDX-UHFFFAOYSA-N 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010931 ester hydrolysis Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003845 household chemical Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/05—Derivatives containing elements other than carbon, hydrogen, oxygen, halogens or sulfur
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- 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
本申请公开了一种阴离子型羟乙基纤维素的制备方法，所述方法包括将异丙醇和水混合得到异丙醇‑水的混合溶剂；在所述异丙醇‑水的混合溶剂中加入碱的水溶液、相转移催化剂的水溶液和羟乙基纤维素，然后加温搅拌，得到第一生成物；在所述第一生成物中加入3‑氯‑2‑羟丙基磷酸酯水溶液，加温反应，得到第二生成物；在所述第二生成物冷却至室温后，调节PH值，然后加入异丙醇过滤；将滤饼放入烧杯中，然后加入异丙醇水溶液洗涤滤饼，然后将滤饼用无水异丙醇进行初步干燥后，真空加热干燥至平衡，得到羟乙基纤维素磷酸酯。本申请所述的阴离子型羟乙基纤维素的制备方法实现羟乙基纤维素阴离子化，并且操作方便，异丙醇可以通过蒸馏回收，重复使用。
The present application discloses a method for preparing anionic hydroxyethyl cellulose. The method includes mixing isopropanol and water to obtain a mixed solvent of isopropanol-water; adding the mixed solvent of isopropanol and water to the mixed solvent of isopropanol and water. The aqueous solution of alkali, the aqueous solution of phase transfer catalyst and hydroxyethyl cellulose are then heated and stirred to obtain the first product; 3-chloro-2-hydroxypropyl phosphate aqueous solution is added to the first product, and the Warm reaction to obtain the second product; after the second product is cooled to room temperature, adjust the pH value, then add isopropanol to filter; put the filter cake into a beaker, then add isopropanol aqueous solution to wash the filter cake, Then, the filter cake is preliminarily dried with anhydrous isopropanol, and then dried to equilibrium by vacuum heating to obtain hydroxyethyl cellulose phosphate. The preparation method of anionic hydroxyethyl cellulose described in the present application realizes the anionization of hydroxyethyl cellulose, and the operation is convenient, and isopropanol can be recovered by distillation and reused.
Description
Technical field
This application involves hydroxyethyl cellulose field more particularly to a kind of preparation sides of anionic hydroxyethyl cellulose
Method.
Background technique
Hydroxyethyl cellulose (HEC), it belongs to non-ionic surface active substance, is a kind of water-soluble high-molecular compound.
Since hydroxyethyl cellulose has the function of thickening, suspension, bonding, floatingization, film forming, dispersion, water conservation and provides protecting colloid, hydroxyl
Ethyl cellulose has been widely used in oil exploitation, coating, building, household chemicals, papermaking, weaving, medical and food etc.
Field.
However, there is also defects for hydroxyethyl cellulose, so that it is in certain fields using there is certain limitation.
Such as in terms of oilfield: the application of hydroxyethyl cellulose is not extensive, is because it inhibits the ability of Shale Hydration dispersion
It is relatively poor.Therefore, some modifications are carried out to hydroxyethyl cellulose, performance its effective function that can be more perfect is special
Property, the application field of hydroxyethyl cellulose can be widened in this way.
Modification for hydroxyethyl cellulose, at present mainly based on cationic, anionic hydroxyethyl cellulose
May equally there be very extensive application on shampoo, detergent and other inorganic agents, but not have yin also at present
The preparation method of ionic hydroxyethyl cellulose.
Summary of the invention
This application provides a kind of preparation methods of anionic hydroxyethyl cellulose, so as to solve the deficiencies in the prior art.
This application provides a kind of preparation methods of anionic hydroxyethyl cellulose, the described method comprises the following steps:
Isopropyl alcohol and water is mixed to get the mixed solvent of isopropanol-water by step S1；
The aqueous solution of the aqueous solution of alkali, phase transfer catalyst is added in the in the mixed solvent of the isopropanol-water in step S2
And hydroxyethyl cellulose, then heating stirring, obtains the first product；
Step S3, is added the chloro- 2- Hydroxypropyl phosphate aqueous solution of ester of 3- in first product, and heating reaction obtains
Second product；
Step S4 adjusts pH value after second product is cooled to room temperature, and isopropanol filtering is then added；
Step S5, filter cake is put into beaker, and isopropanol water solution is added and washs filter cake, then by the anhydrous isopropyl of filter cake
After alcohol carries out preliminarily dried, through vacuum and heating drying to balancing, hydroxyethyl cellulose phosphate, i.e. anionic ethoxy are obtained
Cellulose.
Selectable, the alkali is sodium hydroxide.
Selectable, the alkali is sodium carbonate.
Selectable, the phase catalyst is tetrabutylammonium bromide or cetyl trimethylammonium bromide.
Selectable, the molar ratio of the hydroxyethyl cellulose monomer and the chloro- 2- Hydroxypropyl phosphate ester of 3- is 1:2-3.
Selectable, the mass ratio of the sodium hydroxide and hydroxyethyl cellulose is 0.5-1:20.
Selectable, the molar ratio of the sodium carbonate and the chloro- 2- Hydroxypropyl phosphate ester of 3- is 1:3.
Selectable, the mass ratio of the phase catalyst and the hydroxyethyl cellulose is 0.5-1:100.
It is selectable, it is described that the chloro- 2- Hydroxypropyl phosphate ester of 3- is added in first product, heat the reaction of reaction
Temperature is 80 DEG C -85 DEG C.
From the above technical scheme, this application provides a kind of preparation method of anionic hydroxyethyl cellulose, institutes
Method is stated the following steps are included: isopropyl alcohol and water to be mixed to get to the mixed solvent of isopropanol-water；In the isopropanol-water
The aqueous solution and hydroxyethyl cellulose of the aqueous solution of alkali, phase transfer catalyst is added in the mixed solvent, and then heating stirring, obtains
First product；The chloro- 2- Hydroxypropyl phosphate aqueous solution of ester of 3- is added in first product, heating reaction obtains second
Product；After second product is cooled to room temperature, pH value is adjusted, isopropanol filtering is then added；Filter cake is put into burning
In cup, isopropanol water solution is added and washs filter cake, after filter cake is then carried out preliminarily dried with anhydrous isopropyl alcohol, through heating in vacuum
It is dry extremely to balance, obtain hydroxyethyl cellulose phosphate, i.e. anionic hydroxyethyl cellulose.Anionic described herein
The preparation method of hydroxyethyl cellulose is using Isopropanol Water Solvent Mixtures as medium, will under the action of alkali and phase transfer catalyst
First product and the chloro- 2- Hydroxypropyl phosphate ester of 3- are heated to 80 DEG C -85 DEG C.Realize that hydroxyethyl cellulose anionic is formed
Hydroxyethyl cellulose phosphate, the preparation method rapid reaction of the anionic hydroxyethyl cellulose, easy to operate, isopropanol
It can be recovered by distillation, it is reusable.
Detailed description of the invention
In order to illustrate more clearly of the technical solution of the application, letter will be made to attached drawing needed in the embodiment below
Singly introduce, it should be apparent that, for those of ordinary skills, without any creative labor,
It is also possible to obtain other drawings based on these drawings.
Fig. 1 is a kind of flow chart of the preparation method of anionic hydroxyethyl cellulose provided by the present application.
Specific embodiment
Below with reference to the attached drawing in the application, the technical scheme in the embodiment of the application is clearly and completely described,
Obviously, described embodiment is only a part of the embodiment of the application, instead of all the embodiments.Based in the application
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts,
It shall fall within the protection scope of the present invention.
Many details are explained in the following description in order to fully understand the application, but the application can be with
It is different from the other modes that describe again using other to implement, those skilled in the art can be without prejudice to the application intension
In the case of do similar popularization, therefore the application is not limited by the specific embodiments disclosed below.
Hydroxyethyl cellulose (HEC), it belongs to non-ionic surface active substance, is a kind of water-soluble high-molecular compound,
The structure of hydroxyethyl cellulose is as follows:
It is a kind of flow chart of the preparation method of anionic hydroxyethyl cellulose provided by the present application, this Shen referring to Fig. 1
A kind of preparation method of anionic hydroxyethyl cellulose please be provide, the described method comprises the following steps:
Isopropyl alcohol and water is mixed to get the mixed solvent of isopropanol-water by step S1；
The aqueous solution of the aqueous solution of alkali, phase transfer catalyst is added in the in the mixed solvent of the isopropanol-water in step S2
And hydroxyethyl cellulose, then heating stirring, obtains the first product；
Step S3, is added the chloro- 2- Hydroxypropyl phosphate aqueous solution of ester of 3- in first product, and heating reaction obtains
Second product；
Step S4 adjusts pH value after second product is cooled to room temperature, and isopropanol filtering is then added；
Step S5, filter cake is put into beaker, and isopropanol water solution is added and washs filter cake, then by the anhydrous isopropyl of filter cake
After alcohol carries out preliminarily dried, through vacuum and heating drying to balancing, hydroxyethyl cellulose phosphate, i.e. anionic ethoxy are obtained
Cellulose.
Selectable, the alkali is sodium hydroxide.
Selectable, the alkali is sodium carbonate.
Selectable, the phase catalyst is tetrabutylammonium bromide or cetyl trimethylammonium bromide.
Selectable, the molar ratio of the hydroxyethyl cellulose monomer and the chloro- 2- Hydroxypropyl phosphate ester of 3- is 1:2-3.
Selectable, the mass ratio of the sodium hydroxide and hydroxyethyl cellulose is 0.5-1:20.
Selectable, the molar ratio of the sodium carbonate and the chloro- 2- Hydroxypropyl phosphate ester of 3- is 1:3.
Selectable, the mass ratio of the phase catalyst and the hydroxyethyl cellulose is 0.5-1:100.
It is selectable, it is described that the chloro- 2- Hydroxypropyl phosphate ester of 3- is added in first product, heat the reaction of reaction
Temperature is 80 DEG C -85 DEG C.
The reaction equation for preparing hydroxyethyl cellulose phosphate is as follows:
From the above technical scheme, this application provides a kind of preparation method of anionic hydroxyethyl cellulose, institutes
Method is stated the following steps are included: isopropyl alcohol and water to be mixed to get to the mixed solvent of isopropanol-water；In the isopropanol-water
The aqueous solution and hydroxyethyl cellulose of the aqueous solution of alkali, phase transfer catalyst is added in the mixed solvent, and then heating stirring, obtains
First product；The chloro- 2- Hydroxypropyl phosphate aqueous solution of ester of 3- is added in first product, heating reaction obtains second
Product；After second product is cooled to room temperature, pH value is adjusted, isopropanol filtering is then added；Filter cake is put into burning
In cup, isopropanol water solution is added and washs filter cake, after filter cake is then carried out preliminarily dried with anhydrous isopropyl alcohol, through heating in vacuum
It is dry extremely to balance, obtain hydroxyethyl cellulose phosphate, i.e. anionic hydroxyethyl cellulose.Anionic described herein
The preparation method of hydroxyethyl cellulose is using Isopropanol Water Solvent Mixtures as medium, will under the action of alkali and phase transfer catalyst
First product and the chloro- 2- Hydroxypropyl phosphate ester of 3- are heated to 80 DEG C -85 DEG C.Realize that hydroxyethyl cellulose anionic is formed
Hydroxyethyl cellulose phosphate, the preparation method rapid reaction of the anionic hydroxyethyl cellulose, easy to operate, isopropanol
It can be recovered by distillation, it is reusable, and other auxiliary materials are low in cost.
Phosphorus content according to national standard GB12393-90 method measure, detected by phosphorus content it is provided by the invention it is a kind of yin from
The anionic degree of hydroxyethyl cellulose phosphate prepared by the preparation method of subtype hydroxyethyl cellulose.
Alkali, phase transfer catalyst and hydroxyethyl cellulose is added in the above-mentioned in the mixed solvent in the isopropanol-water, added
The alkali entered is the saturated aqueous solution containing alkali, and the phase transfer catalyst of addition is the aqueous solution containing phase transfer catalyst.
Embodiment 1
300 milliliters of isopropyl alcohol and waters are mixed to get to the mixed solvent of isopropanol-water；
It is added in the in the mixed solvent of the isopropanol-water and contains the saturated aqueous solution of 10.6 grams of sodium carbonate, contains 0.5 gram of four fourth
10 milliliters of aqueous solutions of base ammonium bromide, add 50 grams of hydroxyethyl celluloses, then stir 30-45 minutes, obtain at 45 DEG C
First product；
140 gram 50% of the chloro- 2- Hydroxypropyl phosphate aqueous solution of ester of 3- is added in first product, then at 81 DEG C
Lower reaction 3 hours, obtains the second product；
After the second product is cooled to room temperature, pH value is adjusted to 6 or so, 300 milliliters of isopropanol mistake is then added
Filter；
Filter cake is put into 500 milliliters of beaker, the isopropanol water solution for being then added 85% washs 3 times, washs every time
When stir at least 15 minutes, the filter cake finally filtered is dry with anhydrous isopropyl alcohol, after removing isopropanol, be dried under vacuum to weight,
Obtain 62.5 grams of hydroxyethyl cellulose phosphate.Wherein phosphorus content 2.064%, degree of substitution 1.17.
Embodiment 2
300 milliliters of isopropyl alcohol and waters are mixed to get to the mixed solvent of isopropanol-water；
15 milliliters of the aqueous solution of the sodium hydroxide containing 3M is added, containing 0.5 gram of four fourth in the in the mixed solvent of the isopropanol-water
10 milliliters of aqueous solutions of base ammonium bromide, add 50 grams of hydroxyethyl celluloses, then stir 30-45 minutes, obtain at 45 DEG C
First product；
140 gram 50% of the chloro- 2- Hydroxypropyl phosphate aqueous solution of ester of 3- is added in first product, then at 81 DEG C
Lower reaction 3 hours, obtains the second product；
After the second product is cooled to room temperature, pH value is adjusted to 6 or so, 300 milliliters of isopropanol mistake is then added
Filter；
Filter cake is put into 500 milliliters of beaker, the isopropanol water solution for being then added 85% washs 3 times, washs every time
When stir at least 15 minutes, the filter cake finally filtered is dry with anhydrous isopropyl alcohol, after removing isopropanol, be dried under vacuum to weight,
Obtain 58 grams of hydroxyethyl cellulose phosphate.Wherein phosphorus content 1.482%, degree of substitution 0.83.
According to the above method, different phase transfer catalysts, base amount and reaction temperature have been investigated to hydroxyethyl cellulose phosphorus
The influence of acid esters, reaction result are as shown in table 1.
| Entry | HEC(g) | Base | PTC | T(℃) | Time(h) | Pdt(g) | P (%) |
| 1 | 50 | 15mL3MNaOH | TBAB | 81 | 3 | 58.0 | 1.482 |
| 2 | 50 | 30mL3MNaOH | TBAB | 81 | 3 | 55.0 | 0 |
| 3 | 50 | 10.6g Na2CO3 | TBAB | 81 | 3 | 62.8 | 2.064 |
| 4 | 50 | 10.6g Na2CO3 | TBAB | 70 | 3 | 58.6 | 1.500 |
| 5 | 50 | 10.6g Na2CO3 | TBAB | 81 | 4 | 61.2 | 1.983 |
| 6 | 50 | 10.6g Na2CO3 | CTAB | 81 | 3 | 63.0 | 2.082 |
| 7 | 50 | 10.6g Na2CO3 | TBAI | 81 | 3 | 63.4 | 2.085 |
| 8 | 50 | 10.6g Na2CO3 | none | 81 | 3 | 59 | 1.513 |
The condition of the influence hydroxyethyl cellulose anionic of table 1
In upper table, the isopropanol being added is 300 milliliters, and the chloro- 2- Hydroxypropyl phosphate ester of 50% 3- being added is water-soluble
140 grams of liquid, TBAB is tetrabutylammonium bromide, CTAB is cetyl trimethylammonium bromide, TBAI is tetrabutylammonium iodide, PTC
Dosage be 0.5 gram, P% be product in phosphorus content.
Table 1 the results show that when the amount of sodium hydroxide is smaller, that is, quite practical 1.8 grams of sodium hydroxide can be with
Hydroxyethyl cellulose phosphate is obtained, but when the dosage of sodium hydroxide doubles, can't detect the phosphorus content in product, this can
It can be that naoh concentration increases the reason for promoting phosphate fire-resistant oil.And the alkalinity of sodium carbonate is weaker than sodium hydroxide very much, because
This still can obtain hydroxyethyl cellulose phosphate even if the dosage of sodium carbonate is much larger with relatively good result.Although 16
The result of alkyl trimethyl ammonium bromide and tetrabutylammonium iodide is better than tetrabutylammonium bromide, but differs and little, it is contemplated that valence
Lattice factor should use tetrabutylammonium bromide in industrial production.Reducing thermotonus can be slack-off, and extending the time may make
Partial phosphate ester hydrolysis.Therefore, optimum reaction condition is using saturated solution of sodium carbonate, sodium carbonate and the chloro- 2- hydroxypropyl phosphorus of 3-
The molar ratio of acid esters is 1:3, and the mass ratio of hydroxyethyl cellulose and isopropanol is 1:4.5, hydroxyethyl cellulose and tetrabutyl bromine
The mass ratio for changing ammonium is about 100:1, is reacted 3 hours at 81 DEG C.
After determining reaction condition, we have done 3 amplification tests.
Example 3
1500 milliliters of isopropyl alcohol and waters are mixed to get to the mixed solvent of isopropanol-water；
It is added in the in the mixed solvent of the isopropanol-water and contains the saturated aqueous solution of 53 grams of sodium carbonate, contains 2.5 grams of tetrabutyls
50 milliliters of aqueous solutions of ammonium bromide, add 250 grams of hydroxyethyl celluloses, then stir 30-45 minutes at 45 DEG C, obtain
One product；
700 gram 50% of the chloro- 2- Hydroxypropyl phosphate aqueous solution of ester of 3- is added in first product, then at 81 DEG C
Lower reaction 3 hours, obtains the second product；
After the second product is cooled to room temperature, pH value is adjusted to 6 or so, 1500 milliliters of isopropanol mistake is then added
Filter；
Filter cake is put into 2000 milliliters of beaker, the isopropanol water solution for being then added 85% washs 3 times, washs every time
When stir at least 15 minutes, the filter cake finally filtered is dry with anhydrous isopropyl alcohol, after removing isopropanol, be dried under vacuum to weight,
Obtain 313.0 grams of hydroxyethyl cellulose phosphate.Wherein phosphorus content 2.065%, degree of substitution 1.17.
Example 4
6000 milliliters of isopropyl alcohol and waters are mixed to get to the mixed solvent of isopropanol-water；
It is added in the in the mixed solvent of the isopropanol-water and contains the saturated aqueous solution of 212 grams of sodium carbonate, contains 10 grams of tetrabutyls
100 milliliters of aqueous solutions of ammonium bromide, add 1000 grams of hydroxyethyl celluloses, then stir 30-45 minutes, obtain at 45 DEG C
First product；
2800 gram 50% of the chloro- 2- Hydroxypropyl phosphate aqueous solution of ester of 3- is added in first product, then 81
It is reacted 3 hours at DEG C, obtains the second product；
After the second product is cooled to room temperature, pH value is adjusted to 6 or so, 6000 milliliters of isopropanol mistake is then added
Filter；
Filter cake is put into 5000 milliliters of beaker, the isopropanol water solution for being then added 85% washs 3 times, washs every time
When stir at least 15 minutes, the filter cake finally filtered is dry with anhydrous isopropyl alcohol, after removing isopropanol, be dried under vacuum to weight,
Obtain 1256.3 grams of hydroxyethyl cellulose phosphate.Wherein phosphorus content 2.064%, degree of substitution 1.17.
Example 5
In one 50 liters of YHGSF frequency conversion double layer glass reaction kettle, 18 liters of isopropyl alcohol and waters are mixed to get isopropanol-
The mixed solvent of water；
It is added in the in the mixed solvent of the isopropanol-water and contains the saturated aqueous solution of 636 grams of sodium carbonate, contains 30 grams of tetrabutyls
300 milliliters of aqueous solutions of ammonium bromide, add 3 kilograms of hydroxyethyl celluloses, then stir 30-45 minutes, obtain at 45 DEG C
First product；
8.4 kilogram 50% of the chloro- 2- Hydroxypropyl phosphate aqueous solution of ester of 3- is added in first product, then 81
It is reacted 3 hours at DEG C, obtains the second product；
After the second product is cooled to room temperature, pH value is adjusted to 6 or so, 18 liters of isopropanol filtering is then added；
Filter cake is put back in reaction kettle, then be added 85% isopropanol water solution wash 3 times, every time washing when stir to
15 minutes few, the filter cake finally filtered is dry with anhydrous isopropyl alcohol, after removing isopropanol, is dried under vacuum to weight, obtains 3.8 thousand
Gram hydroxyethyl cellulose phosphate.Wherein phosphorus content 2.066%, degree of substitution 1.18.
From the above technical scheme, this application provides a kind of preparation method of anionic hydroxyethyl cellulose, institutes
Method is stated the following steps are included: isopropyl alcohol and water to be mixed to get to the mixed solvent of isopropanol-water；In the isopropanol-water
The aqueous solution and hydroxyethyl cellulose of the aqueous solution of alkali, phase transfer catalyst is added in the mixed solvent, and then heating stirring, obtains
First product；The chloro- 2- Hydroxypropyl phosphate aqueous solution of ester of 3- is added in first product, heating reaction obtains second
Product；After second product is cooled to room temperature, pH value is adjusted, isopropanol filtering is then added；Filter cake is put into burning
In cup, isopropanol water solution is added and washs filter cake, after filter cake is then carried out preliminarily dried with anhydrous isopropyl alcohol, through heating in vacuum
It is dry extremely to balance, obtain hydroxyethyl cellulose phosphate, i.e. anionic hydroxyethyl cellulose.Anionic described herein
The preparation method of hydroxyethyl cellulose is using Isopropanol Water Solvent Mixtures as medium, will under the action of alkali and phase transfer catalyst
First product and the chloro- 2- Hydroxypropyl phosphate ester of 3- are heated to 80 DEG C -85 DEG C.Realize that hydroxyethyl cellulose anionic is formed
Hydroxyethyl cellulose phosphate, the preparation method rapid reaction of the anionic hydroxyethyl cellulose, easy to operate, isopropanol
It can be recovered by distillation, it is reusable, and other auxiliary materials are low in cost.
The above is only the specific embodiments of the application, it is noted that those skilled in the art are come
It says, under the premise of not departing from the application principle, several improvements and modifications can also be made, these improvements and modifications also should be regarded as
The protection scope of the application.
Claims (9)
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Application publication date: 20190329 |