CN113956367A - Preparation method of anti-aging oxidized regenerated cellulose - Google Patents
Preparation method of anti-aging oxidized regenerated cellulose Download PDFInfo
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- CN113956367A CN113956367A CN202111294113.3A CN202111294113A CN113956367A CN 113956367 A CN113956367 A CN 113956367A CN 202111294113 A CN202111294113 A CN 202111294113A CN 113956367 A CN113956367 A CN 113956367A
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- 239000004627 regenerated cellulose Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 230000003712 anti-aging effect Effects 0.000 title description 4
- 229920002678 cellulose Polymers 0.000 claims abstract description 82
- 239000001913 cellulose Substances 0.000 claims abstract description 82
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 34
- 230000003647 oxidation Effects 0.000 claims abstract description 32
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 28
- 230000032683 aging Effects 0.000 claims abstract description 26
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims abstract description 22
- 238000006467 substitution reaction Methods 0.000 claims abstract description 21
- 238000006640 acetylation reaction Methods 0.000 claims abstract description 15
- 230000021736 acetylation Effects 0.000 claims abstract description 13
- 230000004048 modification Effects 0.000 claims abstract description 12
- 238000012986 modification Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- RVWUHFFPEOKYLB-UHFFFAOYSA-N 2,2,6,6-tetramethyl-1-oxidopiperidin-1-ium Chemical compound CC1(C)CCCC(C)(C)[NH+]1[O-] RVWUHFFPEOKYLB-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 4
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 claims description 4
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims description 4
- 229960002218 sodium chlorite Drugs 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 235000010288 sodium nitrite Nutrition 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 3
- VZGDMQKNWNREIO-UHFFFAOYSA-N carbon tetrachloride Substances ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- 239000005708 Sodium hypochlorite Substances 0.000 claims 1
- 230000003213 activating effect Effects 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 229920003043 Cellulose fiber Polymers 0.000 description 3
- 229920002201 Oxidized cellulose Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229940107304 oxidized cellulose Drugs 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000002439 hemostatic effect Effects 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- LDKDGDIWEUUXSH-UHFFFAOYSA-N Thymophthalein Chemical compound C1=C(O)C(C(C)C)=CC(C2(C3=CC=CC=C3C(=O)O2)C=2C(=CC(O)=C(C(C)C)C=2)C)=C1C LDKDGDIWEUUXSH-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000012925 biological evaluation Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008380 degradant Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 239000005337 ground glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- YLLIGHVCTUPGEH-UHFFFAOYSA-M potassium;ethanol;hydroxide Chemical compound [OH-].[K+].CCO YLLIGHVCTUPGEH-UHFFFAOYSA-M 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000004102 tricarboxylic acid cycle Effects 0.000 description 1
Classifications
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- 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
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
- C08B15/04—Carboxycellulose, e.g. prepared by oxidation with nitrogen dioxide
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/001—Use of materials characterised by their function or physical properties
- A61L24/0042—Materials resorbable by the body
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
- A61L24/08—Polysaccharides
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/04—Materials for stopping bleeding
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Materials Engineering (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Surgery (AREA)
- Engineering & Computer Science (AREA)
- Epidemiology (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention relates to a preparation method of aging-resistant oxidized regenerated cellulose, which is characterized in that selective oxidation is carried out on the basis of acetylation modification of primary hydroxyl at C6 position of cellulose with partial substitution degree, and the oxidized group is hydroxyl (-OH) which is not acetylated at C6 position of the cellulose. On the basis of acetylation modification of primary hydroxyl at the C6 position of cellulose with partial substitution degree, the selective oxidation can effectively intervene and regulate the oxidation degree of the primary hydroxyl at the C6 position of the cellulose. Since the acetyl group affects the crystallinity of cellulose, intermolecular and intramolecular forces are weakened and the oxidation yield of the oxidizing agent is increased.
Description
Technical Field
The invention discloses a preparation method of anti-aging oxidized regenerated cellulose.
Background
Cellulose is one of the older natural fibers utilized by humans, and oxidation of cellulose is a more critical process in chemical modification of cellulose, which is often used to impart specific properties to various types of cellulose fibers. The oxidation treatment of cellulose fibers with an oxidizing agent can improve the added value thereof and is an important factor for determining the physicochemical properties of the cellulose fiber material.
Cellulose is one of the polysaccharides, which is a colorless, odorless fibrous structure substance. The cellulose molecule is a linear polymer formed by connecting D-glucose through beta-1, 4-glycosidic bonds, and the relative molecular mass is 1600000-2400000. In the structural unit of the cellulose, 2, 3 and 6 positions respectively contain a hydroxyl, the C6 position is a primary hydroxyl, and the C2 position and the C3 position are secondary hydroxyls.
Since cellulose is a polyhydroxy structure, it is very sensitive to various oxidizing agents. The oxidation process of cellulose is complex, and the physicochemical properties of the final product mainly depend on the reaction conditions, such as oxidizing agent, acidity and alkalinity of the reaction system, and the like.
The difficulty of the cellulose reaction is mainly the difficulty of the reactants contacting with hydroxyl on a glucopyranose unit of a cellulose molecular chain, and the reactivity of primary hydroxyl is higher than that of secondary hydroxyl in the acetylation reaction; in the etherification reaction, the secondary hydroxyl group has higher reactivity than the primary hydroxyl group.
The oxidized cellulose fiber containing carboxyl is widely applied to medical materials, such as hemostatic gauze, absorbable surgical suture and the like, and mainly relates to medical devices and products thereof, wherein the safety evaluation of the medical devices comprises physical performance and biological evaluation. Physical properties include strength, hardness, fatigue resistance, and the like; chemical properties include corrosion resistance, solute limits and degradants. The technical requirements for these properties are to meet clinical use requirements and ensure safe use, and to set the expiration date of the product according to specific parameters of the medical equipment safety evaluation.
The oxidation of cellulose is affected by the crystallinity of cellulose, and many reactants can only reach the surface of crystalline regions of cellulose and loose amorphous regions, which are difficult to control.
The existing direct oxidation of cellulose has some disadvantages, such as: NO2And N2O4The oxidation process of the system to the cellulose is carried out under heterogeneous conditions, the reaction time is long, and the serious degradation of the cellulose is easily caused; a phosphoric acid solution system of sodium nitrate and sodium nitrite can oxidize a small amount of secondary hydroxyl in the process of oxidizing cellulose, and the selectivity is not strong; the hypochlorite system is used for oxidizing cellulose under an alkaline condition, and strong alkali has a strong degradation effect on the cellulose; sodium chlorate, sodium chlorite and sodium bromate systems have strong selectivity on primary hydroxyl groups, but the molecular chains of cellulose can be broken by an oxidation process.
Disclosure of Invention
The invention aims to provide a preparation method of anti-aging oxidized regenerated cellulose.
The object of the invention is to provide the following: a process for preparing the regenerated ageing-resistant oxidized cellulose features that the primary hydroxyl at C6 position of cellulose with partial substitution degree is acetylated and selectively oxidized, the oxidized radical is-OH which is not acetylated at C6 position of cellulose, the acetyl substitution degree at C6 position of cellulose is 0.01-1, and the partially acetylated cellulose oxidizing system contains NO2And N2O4(ii) a Phosphoric acid solution of sodium nitrate and sodium nitrite; hypochlorite; sodium chlorate, sodium chlorite, sodium bromate; 2,2,6, 6-tetramethylpiperidine oxide.
The cellulose at acetyl C6 position has an acetyl substitution degree of 0.01-1.
The selective oxidation is carried out on the basis of acetylation modification of primary hydroxyl at C6 position of cellulose with partial substitution degree, and the carboxyl content of the oxidation product is 5-14%.
The partially acetylated cellulose oxidation system comprises NO2And N2O4(ii) a Phosphoric acid solution of sodium nitrate and sodium nitrite; hypochlorite; sodium chlorate, sodium chlorite, sodium bromate; 2,2,6, 6-tetramethylpiperidine oxide.
The primary hydroxyl at the C6 site of the cellulose can generate acetylation reaction under certain conditions, and the stability of the cellulose is enhanced after acetylation modification. On the basis of acetylation modification of primary hydroxyl at C6 position of cellulose with partial substitution degree, selective oxidation is carried out, and the product has greatly improved heat resistance and corrosion resistance due to the existence of acetyl, thus having wider application.
On the basis of acetylation modification of primary hydroxyl at the C6 position of cellulose with partial substitution degree, the selective oxidation can effectively intervene and regulate the oxidation degree of the primary hydroxyl at the C6 position of the cellulose. Since the acetyl group affects the crystallinity of cellulose, intermolecular and intramolecular forces are weakened and the oxidation yield of the oxidizing agent is increased.
The reaction formula is as follows:
in addition, when the cellulose oxide is used as an absorbable hemostatic material for human bodies, the cellulose oxide containing acetyl is hydrolyzed and deacetylated to participate in tricarboxylic acid cycle of human bodies, so that the cellulose oxide is easy to absorb.
The method mainly utilizes esterification reaction (acetylation) to ensure that partial cellulose primary hydroxyl groups are esterified and oxidized in advance, and the esterified primary hydroxyl groups do not have reaction activity any more, so that the effect of adjusting the oxidation rate is achieved, and the method is more suitable for industrial production.
Detailed Description
Example 1
An aging-resistant oxidized regenerated cellulose is selectively oxidized on the basis of acetylation modification of primary hydroxyl at the C6 position of cellulose with partial substitution degree, the oxidized group is-OH which is not acetylated at the C6 position of the cellulose, the substitution degree of acetyl at the C6 position of the cellulose is 0.01-1, and the method comprises the following steps:
firstly, adding 50 kg of cellulose, 320 kg of glacial acetic acid, 0.3 kg of concentrated sulfuric acid and 190 kg of acetic anhydride into a reaction kettle, stirring and stirring at 150 revolutions per minute, heating to 50 ℃ for reaction, and reacting for 1.5-2 hours to obtain part of acetyl substituted cellulose;
and (3) testing the acetyl content: taking about 2.0g of cellulose with partial acetyl substitution, placing the cellulose in a conical flask, adding 100ml of acetone and 10ml of water, sealing the plug, stirring the mixture by using a magnetic stirrer until the cellulose is completely dissolved, precisely adding 30ml of sodium hydroxide titration solution with the concentration of 1.0mol/L, continuously stirring the mixture for 30 minutes, heating the mixture for 100ml of water, flushing the inner wall of the conical flask, continuously stirring the mixture for 2 minutes, cooling the mixture, adding 2-3 drops of phenolphthalein indicator solution, titrating the mixture to an end point by using sulfuric acid titration solution with the concentration of 0.5mol/L, and correcting the titration result by using a blank test.
Calculating the dosage of the sulfuric acid titration solution: ml 43.05mg
Second step of reacting NO2Adding the mixture into CCl4 solution to prepare mixed solution containing 20% NO2, 6.5 kg in total, adding 0.4 kg of cellulose partially substituted by acetyl, adjusting the temperature to 25-30 ℃, and reacting for 24 hours, wherein the reaction formula is as follows:
the product of formula 2, an aging resistant oxidized regenerated cellulose, is obtained.
Example 2
An aging-resistant oxidized regenerated cellulose is prepared by the following steps: the selective oxidation is carried out on the basis of acetylation modification of primary hydroxyl at C6 position of cellulose with partial substitution degree, the oxidized group is-OH which is not acetylated at C6 position of the cellulose, the substitution degree of acetyl at C6 position of the cellulose is 0.01-1, the oxidation system of the partially acetylated cellulose is 2,2,6, 6-tetramethyl piperidine oxide, and the reaction formula is as follows:
oxidizing the partially acetylated cellulose with 2,2,6, 6-tetramethylpiperidine oxide according to the reaction formula:
a first step, the same as in example 1;
secondly, activation: dissolving 16kg of lithium chloride LiCl in 20 kg of DMAc, adding 0.1 kg of partially acetyl-substituted cellulose, heating to 90-100 ℃, and stirring at the speed of 300 revolutions per minute for 70 minutes to obtain the cellulose treated by DMAc/LiCl.
Oxidation: the treated cellulose was placed in 25 kg purification, 0.27 kg TEMPO and 0.4 kg NaBr were added and the pH was adjusted to 10. + -. 0.5 with NaOH solution. Adding 0.11 kg of NaClO solution with the mass fraction of 8% to carry out TEMPO oxidation reaction. Oxidized cellulose is obtained.
And (3) detection:
1. and (3) measuring the content of carboxylic acid:
6 parts of the oxidation products of example 1 and example 2 were sampled and dried in an oven at 80 ℃ for 2 hours. 0.2g of a sample obtained after drying the sample is weighed in each portion, placed into a 300mL ground glass triangular flask, added with a rotor and 30mL of pyridine at the same time, placed on a magnetic stirrer and slowly stirred for 5 hours until the pyridine is completely dissolved, and a pyridine solution is obtained. Adding 6-7 drops of 1% thymolphthalein indicator into the pyridine solution, and dropping 0.02mol/L potassium hydroxide-ethanol standard titration solution by using a micro-burette until the solution is blue. Standing for more than 10min after the blue color is formed, wherein the end point is that the color does not disappear
And accelerated aging test:
AAT: accelerating aging time; RT: aging time in real time; q10: an aging coefficient of 10 ℃ is increased or decreased; accelerated aging temperature; t isRT: temperature under normal storage conditions.
Wherein the ambient temperature under normal storage conditions is selected from 22 deg.C, i.e. TRT==22℃
The aging temperature is 60 ℃, namely TAA=60℃
According to the general principle, Q10The use of 2 indicates that a 10 deg.C increase or decrease in temperature results in a doubling or halving of the chemical reaction rate.
According to the formula, the product which proves that the validity period can reach 1 year needs to be subjected to an aging test at 60 ℃ for 27 days.
20 parts of oxidation products of the embodiment 1 and the embodiment 2 are selected and placed in an aging box, the temperature of the aging box is 60 +/-2 ℃, and the humidity is 55 +/-10%. The time of insertion was recorded.
Secondly, every 27 days, taking out samples according to the quantity in the following table, and detecting the product quality according to the required content.
③ detection method
Appearance.
And (3) contamination bacteria: testing according to the test method specified in pharmacopoeia 2015 edition
Claims (7)
1. The preparation method of the aging-resistant oxidized regenerated cellulose is characterized in that selective oxidation is carried out on the basis of acetylation modification of primary hydroxyl at C6 position of cellulose with partial substitution degree, the oxidized group is-OH which is not acetylated at C6 position of the cellulose, and the substitution degree of acetyl at C6 position of the cellulose is 0.01-3.3, wherein the oxidation system of the partially acetylated cellulose contains NO2And N2O4(ii) a Phosphoric acid solution of sodium nitrate and sodium nitrite; hypochlorite; sodium chlorate, sodium chlorite, sodium bromate; 2,2,6, 6-tetramethylpiperidine oxide.
2. The method for preparing the aging-resistant oxidized regenerated cellulose according to claim 1, characterized in that the reaction formula is:
3. the method for preparing the aging-resistant oxidized regenerated cellulose according to claim 1 or 2, wherein the degree of substitution of acetyl group of the cellulose at acetyl C6 is 0.01-1.
4. The method for preparing the aging-resistant oxidized regenerated cellulose according to claim 1 or 2, characterized in that the selective oxidation is carried out on the basis of acetylation modification of the primary hydroxyl group at C6 position of cellulose with partial substitution degree, and the carboxyl content of the oxidation product is 5-14%.
The method for preparing the aging-resistant oxidized regenerated cellulose according to claim 1 or 2, characterized in that NO is2And N2O4Oxidizing a partially acetylated cellulose, the reaction formula being:
5. the method for preparing the aging-resistant oxidized regenerated cellulose as claimed in claim 4, wherein the aging-resistant oxidized regenerated cellulose obtained in the following step is prepared according to the following formula 2, the selective oxidation is carried out on the basis of acetylation modification of the primary hydroxyl group at the C6 position of the cellulose with partial substitution degree, the oxidized group is-OH which is not acetylated at the C6 position of the cellulose, and the acetyl substitution degree at the C6 position of the cellulose is 0.01-1, and the method comprises the following steps:
firstly, adding 50 kg of cellulose, 320 kg of glacial acetic acid, 0.3 kg of concentrated sulfuric acid and 190 kg of acetic anhydride into a reaction kettle, stirring and stirring at 150 revolutions per minute, heating to 50 ℃ for reaction, and reacting for 1.5-2 hours to obtain part of acetyl substituted cellulose;
second step of reacting NO2Is added to CCl4In solution, formulated to contain 20% NO2Taking the mixed solution as an oxidation system, adding 0.4 kg of the cellulose which is partially substituted by acetyl and obtained in the step one as the total amount of 6.5 kg, adjusting the temperature to 25-30 ℃, and reacting for 24 hours to obtain the aging-resistant oxidized regenerated cellulose obtained in the formula 2.
6. The method for preparing the aging-resistant oxidized regenerated cellulose according to claim 1 or 2, wherein 2,2,6, 6-tetramethylpiperidine oxide oxidizes partially acetylated cellulose, and the reaction formula is as follows:
7. the method for preparing an aging-resistant oxidized regenerated cellulose according to claim 6, wherein the aging-resistant oxidized regenerated cellulose obtained in the following formula 3 is prepared by performing selective oxidation on the basis of acetylation modification of a primary hydroxyl group at the C6 position of cellulose with a partial substitution degree, the oxidized group is-OH which is not acetylated at the C6 position of the cellulose, the substitution degree of an acetyl group at the C6 position of the cellulose is 0.01 to 1, and the oxidized system of the partially acetylated cellulose is 2,2,6, 6-tetramethylpiperidine oxide, and the method comprises the following steps:
firstly, adding 50 kg of cellulose, 320 kg of glacial acetic acid, 0.3 kg of concentrated sulfuric acid and 190 kg of acetic anhydride into a reaction kettle, stirring and stirring at 150 revolutions per minute, heating to 50 ℃ for reaction, and reacting for 1.5-2 hours to obtain part of acetyl substituted cellulose;
in the second step, the first step is that,
activating: dissolving 16kg of lithium chloride LiCl in 20 kg of N, N-dimethylacetamide DMAC, adding 0.1 kg of cellulose partially substituted by acetyl, heating to 90-100 ℃, and stirring at the speed of 300 revolutions per minute for 70 minutes to obtain the cellulose treated by the DMAC/LiCl;
oxidation: placing the cellulose treated by DMAC/LiCl into 25 kg of purification, adding 0.27 kg of 2,2,6, 6-tetramethylpiperidine N-oxide TEMPO and 0.4 kg of sodium bromide NaBr, and adjusting the pH value to 10 +/-0.5 by using a NaOH solution; and adding 0.11 kg of sodium hypochlorite NaClO solution with the mass fraction of 8% to perform TEMPO oxidation reaction to obtain the product aging-resistant oxidized regenerated cellulose shown in the formula 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202111294113.3A CN113956367A (en) | 2021-11-03 | 2021-11-03 | Preparation method of anti-aging oxidized regenerated cellulose |
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