CN105026467A - Films of poly alpha-1,3-glucan esters and method for their preparation - Google Patents

Films of poly alpha-1,3-glucan esters and method for their preparation Download PDF

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CN105026467A
CN105026467A CN201480010961.9A CN201480010961A CN105026467A CN 105026467 A CN105026467 A CN 105026467A CN 201480010961 A CN201480010961 A CN 201480010961A CN 105026467 A CN105026467 A CN 105026467A
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dextran
poly
ester
acid
reaction
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R.B.卡萨特
J.L.波林
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Nutrition and Biosciences USA 4 Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00

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  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
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Abstract

Poly alpha-1,3-glucan ester compounds are disclosed herein with a degree of substitution of about 0.05 to about 3.0. Also disclosed are methods of producing poly alpha-1,3-glucan ester compounds and films made therefrom.

Description

Poly-α-1,3-dextran ester film and their preparation method
Present patent application is the part continuation application of the U.S. Patent application 14/136168 that on December 20th, 2013 submits to, and requires U.S. Provisional Application 61/746,328; The rights and interests of 61/746,335 and 61/746,338; Every section of patent is all filed on December 27th, 2012, existing every section all out of date, these patents are incorporated herein by reference all in full.
Technical field
The present invention is poly-α-1,3-glucan derivative field.Particularly, the present invention relates to poly-α-1,3-dextran ester, they preparation method and by they obtained films.
Background technology
To utilizing the enzymic synthesis of microorganism or plant host or genetically engineered, with the expectation seeking new texture polysaccharide, that researchist is found is biodegradable and can from the polysaccharide prepared of the ground of the raw material economics based on renewable resources.This type of polysaccharide a kind of is poly-α-1,3-dextran (being characterised in that the dextran polymer with α-1,3-glycosidic link).Contact with from streptococcus-salivarius (Streptococcussalivarius) isolated Transglucosylase by making aqueous sucrose solution, isolate this polymkeric substance (people such as Simpson, Microbiology 141: 1451-1460,1995).By poly-α-1, the temperature of maximum 150 DEG C of film that 3-dextran obtains tolerance, and the advantage (people such as Ogawa that the polymkeric substance being better than the polysaccharide deriving from β-Isosorbide-5-Nitrae-connection is provided, Fiber Differentiation Methods 47: 353-362,1980).
United States Patent (USP) 7,000,000 preparation disclosing the polysaccharide fiber comprising hexose, wherein in polymkeric substance, the hexose of at least 50%, via α-1,3-glycosidic link, utilizes streptococcus-salivarius gtfJ enzyme to connect.This enzyme utilizes sucrose as the substrate of polyreaction, thus produces poly-α-1,3-dextran and fructose as end product people such as (, 1995) Simpson.Solvent or wrap in solvent-laden mixture dissolve exceed threshold concentration time, polymer formation liquid crystal solution disclosed in this invention.The continuously firmly cotton-like fiber and using highly being applicable to yarn fabric is spun by this solution.
The information applied about preparation and their of various poly-α-1,3-glucan derivative is little.
The people such as Yui (Int.J.Biol.Macromol.14: 87-96,1992) are open, use poly-α-1, the 3-dextran extracted from the sporophore of fungi sulphur look gorgeous pore fungi, poly-α-1, the 3-dextran triacetate of synthesis.The structure of this polymkeric substance is analyzed by X-ray crystallography.
The people such as Ogawa (Carb.Poly.3: 287-297,1983) use three kinds of different poly-α-1,3-dextran triacetates of poly-α-1,3-dextran samples preparation.A kind of sample is isolated from bacterial cell exo polysaccharides, and another two kinds of samples extract from fungus sporophore.The structure X-ray crystallography of these polymkeric substance is analyzed.
In view of the potential practicality of poly-α-1,3-dextran ester derivative in various application such as masking, expect that development of new is gathered α-1,3-dextran ester derivative and prepared the method for this analog derivative.
Summary of the invention
The present invention relates to the film comprising poly-α-1,3-dextran ester, described film have following at least one: (a) is at least about the anti tear degree of 0.1gf/mil; Or the mist degree that (b) is less than about 20%.
In another embodiment, the present invention relates to the method for poly-α-1, the 3-dextran ester film of preparation, described method comprises: (a) provides poly-α-1,3-dextran ester; B () makes described poly-α-1, the 3-dextran ester of (a) and solvent contacts to prepare the solution of poly-α-1,3-dextran ester; C solution that () will gather α-1,3-dextran ester is applied on the surface; And (d) makes described solvent evaporate to provide described poly-α-1,3-dextran ester film.
Embodiment
The all patents quoted herein and the disclosure of non-patent literature are incorporated herein by reference all in full.
As used herein, term " invention " or " invention disclosed " are not intended to restriction but are generally applied to any invention defined in claim or described herein.These terms exchange use in this article.
Term " poly-α-1,3-dextran ", " α-1,3-dextran polymer " and " dextran polymer " exchange use in this article.Poly-α-1,3-dextran is the polymkeric substance comprising the glucose monomer unit linked together by glycosidic link, is wherein α-1,3-glycosidic link at least about the glycosidic link of 50%.Poly-α-1,3-dextran is a type of polysaccharide.The structure of poly-α-1,3-dextran can illustrate as follows:
Chemical process can be utilized obtain poly-α-1, the 3-dextran that can be used in this article preparing poly-α-1,3-dextran ester cpds.Alternatively, it obtains by extracting in the various organisms such as fungi from poly-α-1, the 3-dextran of generation.Also alternatively, poly-α-1,3-dextran can use such as one or more Transglucosylases (gtf) (such as gtfJ), to be promoted production life by sucrase, such as United States Patent (USP) 7,000,000 and U.S. Patent Application Publication 2013/0244288 and 2013/0244287 described in (these patents are all incorporated herein by reference).
Term " Transglucosylase ", " gtf enzyme ", " gtf enzyme catalyst ", " gtf " and " Sucrose:glucan alpha1-6-glucosyltransferase " exchange use in this article.Herein the active catalytic reaction of sucrose substrate of gft enzyme, generates product and gathers α-1,3-dextran and fructose.Other product (by product) of gtf reaction can comprise glucose (when from glucosyl-gtf enzyme intermediary composite hydrolysis glucose), various soluble oligosaccharide (DP2-DP7) and white bacterium disaccharides (when the glucose of glucosyl-gtf enzyme intermediary composite is connected to fructose).White bacterium disaccharides is the disaccharides be made up of the glucose connected by α-1,5 key and fructose.The wild-type form of Transglucosylase comprises (with N-terminal to C-terminal direction) signal peptide, variable domain, catalytic domain and glucan binding domian territory substantially.According to CAZy (carbohydrate-organized enzyme) database people such as (, Nucleic Acids Res.37: D233-238,2009) Cantarel herein gtf be classified as and join glycosylhydrolase family 70 (GH70).
For the preparation of gathering α-1 herein, the poly-α-1 of 3-dextran ester cpds, between the glucose monomer unit of 3-dextran, per-cent for the glycosidic link of α-1,3 is at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99% or 100% (or any round values between 50% and 100%).Therefore in this type of embodiment, poly-α-1,3-dextran has the glycosidic link of the non-alpha-1,3 being less than about 50%, 40%, 30%, 20%, 10%, 5%, 4%, 3%, 2%, 1% or 0% (or any round values between 0% and 50%).
Herein for the preparation of poly-α-1, the 3-dextran of poly-α-1,3-dextran ester cpds be preferably straight chain/non-branched.In certain embodiments, poly-α-1,3-dextran does not have tapping point, or the per-cent that tapping point accounts for glycosidic link in described polymkeric substance is less than about 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2% or 1%.The example of tapping point comprises α-1,6 tapping point, is such as present in those in textured polymer.
Term " glucosides connection base " and " glycosidic link " exchange use in this article, and refer to covalent linkage type carbohydrate (sugar) molecule being connected to another group such as another carbohydrate.As used herein, term " α-1,3-glycosidic link " refers to the covalent linkage type be connected to each other by the carbon 1 on adjacent alpha-D-glucose ring and carbon 3 by alpha-D-glucose molecule.This key is as provided shown in poly-α-1,3-glucan structure.In this article, " alpha-D-glucose " is called as " glucose ".
Term " poly-α-1,3-dextran ester cpds ", " poly-α-1,3-dextran ester " and " poly-α-1,3-dextran ester derivative " exchange use in this article.Poly-α-1,3-dextran ester cpds in this article can by following representation:
With regard to the chemical formula of this structure, n can be at least 6, and each R can be hydrogen atom (H) or carboxyl groups independently.Poly-α-1,3-dextran ester cpds has the substitution value of about 0.05 to about 3.0 herein.
Poly-α-1,3-dextran ester cpds disclosed herein is the compound of synthetic.
Poly-α-1,3-dextran ester cpds is owing to comprising substructure-C herein g-O-CO-C-and be called as " ester ", wherein "-C g-" represent the carbon 2,4 or 6 of the glucose monomer unit of poly-α-1,3-dextran ester cpds, and wherein "-CO-C-" is contained in carboxyl groups.
" carboxyl groups " can be such as Acetyl Groups (-CO-CH herein 3), propionyl group (-CO-CH 2-CH 3), butyryl radicals group (-CO-CH 2-CH 2-CH 3), pentanoyl group (-CO-CH 2-CH 2-CH 2-CH 3), caproyl group (-CO-CH 2-CH 2-CH 2-CH 2-CH 3), oenanthyl group (-CO-CH 2-CH 2-CH 2-CH 2-CH 2-CH 3) or capryloyl group (-CO-CH 2-CH 2-CH 2-CH 2-CH 2-CH 2-CH 3).Carbonyl group (-CO-) in carboxyl groups connects with carbon 2,4 or 6 ester of the glucose monomer unit of poly-α-1,3-dextran ester cpds.
With regard to name, can refer to one or more organic acids corresponding with the one or more carboxyl groups in compound, name poly-α-1,3-dextran ester cpds herein.Such as, the ester cpds comprising Acetyl Groups can be called as poly-α-1,3-dextran acetic ester; the ester cpds comprising propionyl group can be called as poly-α-1; 3-dextran propionic ester, and the ester cpds comprising butyryl radicals group can be called as poly-α-1,3-dextran butyric ester.But this name is not intended to refer to that poly-α-1,3-dextran ester cpds is originally as acid herein.
" poly-α-1,3-dextran triacetate " refers to poly-α-1, the 3-dextran ester cpds of the Acetyl Groups substitution value with 2.75 or higher herein.
Term " poly-α-1,3-dextran monoesters " and " monoesters " exchange use in this article.Poly-α-1,3-dextran monoesters only comprises the carboxyl groups of a type.The example of this type of monoesters is poly-α-1,3-dextran acetic ester (comprising Acetyl Groups) and poly-α-1,3-dextran propionic ester (comprising propionyl group).
Term " poly-α-1,3-dextran mixed ester " and " mixed ester " exchange use in this article.Poly-α-1,3-dextran mixed ester comprises the carboxyl groups of two or more type.The example of this type of mixed ester is poly-α-1,3-dextran acetate propionate (comprising ethanoyl and propionyl group) and poly-α-1,3-dextran acetate butyrate (comprising ethanoyl and butyryl radicals group).
Term " reaction ", " response composite " and " esterification " exchange use in this article, and refer to that comprising poly-α-1,3-dextran, at least one acid catalyst, at least one acid anhydrides and at least one organic acid reacts.Described reaction is anhydrous substantially.Under suitable condition (such as time, temperature), carry out reacting making having the poly-α-1 from least carboxyl groups of acid anhydrides; one or more oh group esterifications of 3-dextran glucose unit; thus obtain poly-α-1,3-dextran ester cpds.
Term " substantially anhydrous " and " anhydrous " exchange use in this article.Substantially anhydrous condition is wherein there is the condition being less than about 1.5 % by weight or 2.0 % by weight water.This type of condition can characterize such as reaction or reactive component.
Herein, poly-α-1, the 3-dextran of " acid exchanges " uses acid treatment, to dewater from poly-α-1,3-dextran.The sour exchange process of poly-α-1, the 3-dextran that preparation acid exchanges can comprise one or more process, wherein dextran is positioned in acid (such as organic acid), then removes from acid.
As used herein, term " acid catalyst " refers to any acid accelerating esterification process.The example of acid catalyst is mineral acid such as sulfuric acid (H 2sO 4) and perchloric acid (HClO 4).
As used herein, term " acid anhydrides " refers to have the organic compound that two are bonded to the carboxyl groups of same oxygen atom.Usually, the acid anhydrides of this paper has formula (R-CO) 2o, wherein R is saturated normal carbon chain (at the most seven carbon atoms).The example of acid anhydrides is diacetyl oxide [(CH 3-CO) 2o], propionic anhydride [(CH 3-CH 2-CO) 2o] and butyryl oxide [(CH 3-CH 2-CH 2-CO) 2o].
Term " organic acid " and " carboxylic acid " exchange use in this article.Organic acid has formula R-COOH, and wherein R is organic group, and COOH is carboxylic group.R group is generally saturated normal carbon chain (at the most seven carbon atoms) herein.Organic acid example is acetic acid (CH 3-COOH), propionic acid (CH 3-CH 2-COOH) and butyric acid (CH 3-CH 2-CH 2-COOH).
As used herein, term " substitution value " (DoS) refers to the oh group mean number replaced in each monomeric unit of poly-α-1,3-dextran ester cpds (glucose).Owing to there are three oh groups in each monomeric unit of poly-α-1,3-dextran, therefore the DoS of poly-α-1,3-dextran ester cpds can not higher than 3 herein.
Such as can via any approach known in the art, such as dissolve, mix, vibrate or homogenizing is carried out herein " contact ".When three kinds or multiple reactive component contact with each other, this type of contact can all disposable or stage by stage (such as two kinds of components mixing, is then mixed into three components) complete.
" molecular weight " of poly-α-1,3-dextran and poly-α-1,3-dextran ester cpds can be expressed as number-average molecular weight (M herein n) or weight-average molecular weight (M w).Alternatively, molecular weight can be expressed as dalton (Dalton), gram/mol, DPw (weight average degree of polymerization) or DPn (number-average degree of polymerization).It is known in the art for calculating the various methods that these molecular weight measure, such as high pressure lipuid chromatography (HPLC) (HPLC), size exclusion chromatography, (SEC) or gel permeation chromatography (GPC).
Term " volume % ", " volume percent " exchange use in this article.In solution, the volume % of solute can use following formula to measure: [(solute volume)/(liquor capacity)] × 100%.
Term " % by weight ", " weight percent (wt%) " and " weight-weight percentages (w/w%) " exchange use in this article.% by weight refers to the material per-cent be by weight included in composition, mixture or solution.
Term " increase ", " enhancing " and " improvement " exchange use in this article.These terms can refer to quantity or the activity (or any integer between 1% and 200%) of quantity or the active height at least 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, 125%, 150%, 175% or 200% such as compared than the quantity increased or activity.
Disclosed inventive embodiment relates to the composition comprised by poly-α-1, the 3-dextran ester cpds of following representation:
With regard to the chemical formula of this structure, n can be at least 6, and each R can be H or carboxyl groups independently.In addition, poly-α-1,3-dextran ester cpds has the substitution value of about 0.05 to about 3.0.
Each R group in the chemical formula of poly-α-1,3-dextran ester cpds can be H or carboxyl groups independently.Carboxyl groups can be such as Acetyl Groups, propionyl group, butyryl radicals group, pentanoyl group, caproyl group, oenanthyl group or capryloyl group herein.Thus carboxyl groups can comprise the chain of 2 to 8 carbon; This chain does not preferably have side chain.
In certain embodiments, poly-α-1,3-dextran ester cpds disclosed herein can comprise the carboxyl groups of a type.Such as, ester bond is connected to one or more R group of glucose group in above formula and can be propionyl group; Thus the R group in this concrete example is hydrogen and propionyl group independently.And for example, ester bond is connected to one or more R group of glucose group in above formula and can be Acetyl Groups; Thus the R group in this concrete example is hydrogen and Acetyl Groups independently.Some embodiment of poly-α-1,3-dextran ester cpds does not have the Acetyl Groups DoS of 2.75 or higher herein.
Alternatively, poly-α-1,3-dextran ester cpds disclosed herein can comprise two or more dissimilar carboxyl groups.The example of this compounds comprises two kinds of different carboxyl groups; such as (i) ethanoyl and propionyl group (poly-α-1; 3-dextran acetate propionate; wherein R group is H, ethanoyl or propionyl independently); or (ii) ethanoyl and butyryl radicals group (poly-α-1; 3-dextran acetate butyrate, wherein R group is H, ethanoyl or butyryl radicals independently).
Poly-α-1,3-dextran ester cpds has the substitution value (DoS) of about 0.05 to about 3.0.Alternatively, the DoS of poly-α-1,3-dextran ester cpds disclosed herein can be about 0.2 to about 2.0.Also alternatively, described DoS can be at least about 0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9,2.0,2.1,2.2,2.3,2.4,2.5,2.6,2.7,2.8,2.9 or 3.0.It will be apparent to one skilled in the art that therefore the R group of compound can not be only hydrogen because poly-α-1,3-dextran ester cpds disclosed herein has between about 0.05 to the substitution value about between 3.0.
Can mention and gather % by weight of one or more carboxyl groups in α-1,3-dextran ester cpds herein, and not mention DoS value.Such as, poly-α-1, in 3-dextran ester cpds, % by weight of carboxyl groups can be at least about 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, or 60%.
Poly-α-1, be that the per-cent of the glycosidic link of α-1,3 is at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99% or 100% (or any integer between 50% and 100%) between the glucose monomer unit of 3-dextran ester cpds.Therefore in this type of embodiment, described compound has the glycosidic link of the non-alpha-1,3 being less than about 50%, 40%, 30%, 20%, 10%, 5%, 4%, 3%, 2%, 1% or 0% (or any round values between 0% and 50%).
The main chain of poly-α-1,3-dextran ester cpds disclosed herein be preferably straight chain/non-branched.In certain embodiments, described compound does not have tapping point, or has the tapping point that the per-cent accounting for glycosidic link in described polymkeric substance is less than about 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2% or 1%.The example of tapping point comprises α-1,6 tapping point.
In certain embodiments, the chemical formula of poly-α-1,3-dextran ester cpds can have the n value at least 6.Alternatively, n can have the value at least 10,50,100,200,300,400,500,600,700,800,900,1000,1100,1200,1300,1400,1500,1600,1700,1800,1900,2000,2100,2200,2300,2400,2500,2600,2700,2800,2900,3000,3100,3200,3300,3400,3500,3600,3700,3800,3900 or 4000 (or any integers between 10 and 4000).
The molecular weight of poly-α-1,3-dextran ester cpds disclosed herein can be measured as number-average molecular weight (M n) or weight-average molecular weight (M w).Alternatively, molecular weight can dalton or gram/mol to measure.It also can be used for relating to the DP that compound gathers α-1,3-dextran polymer component w(weight average degree of polymerization) or DP n(number-average degree of polymerization).
The M of poly-α-1,3-dextran ester cpds disclosed herein nor M wcan 1000 be at least about.Alternatively, M nor M w1000 to about 600000 can be at least about.Also alternatively, M nor M wcan be such as at least about 10000,25000,50000,75000,100000,125000,150000,175000,200000,225000,250000,275000 or 300000 (or any integers between 10000 and 300000).
In certain embodiments; poly-α-1,3-dextran ester can have the Acetyl Groups DoS of at the most about 2.00,2.05,2.10,2.15,2.20,2.25,2.30,2.35,240,2.45,2.50,2.55,2.60,2.65,2.70,2.75,2.80,2.85,2.90,2.95 or 3.00.Thus such as, the DoS of Acetyl Groups can be at the most about 2.00-2.40,2.00-2.50 or 2.00-2.65.And for example, the DoS of Acetyl Groups can be about 0.05 to about 2.60, and about 0.05 to about 2.70, about 1.2 to about 2.60, or about 1.2 to about 2.70.This α-1,3-dextran ester of birdsing of the same feather flock together can be monoesters or mixed ester.
In certain embodiments; poly-α-1,3-dextran ester can have the propionyl group % by weight of at the most about 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54% or 55%.This α-1,3-dextran ester of birdsing of the same feather flock together can be monoesters or mixed ester.With regard to mixed ester; poly-α-1; 3-dextran acetate propionate can have the Acetyl Groups % by weight of at the most about 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%, and propionyl group % by weight is as such as listed above any propionyl % by weight.
In certain embodiments, poly-α-1, 3-dextran ester can have at the most about 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, or the butyryl radicals group % by weight of 60%.In other embodiments, poly-α-1,3-dextran ester can have the butyryl radicals group DoS of at the most about 0.80,0.85,0.90,0.95,1.00,1.05,1.10,1.15 or 1.20.This α-1,3-dextran ester of birdsing of the same feather flock together can be monoesters or mixed ester.With regard to mixed ester; poly-α-1; 3-dextran acetate butyrate can have the Acetyl Groups % by weight of at the most about 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35% or 36%, and butyryl radicals group % by weight is as such as listed above any butyryl radicals % by weight.
Disclosed in the invention still further relates to the method for poly-α-1, the 3-dextran ester cpds of preparation.The method comprises: in anhydrous reaction substantially; make poly-α-1; 3-dextran contacts with at least one organic acid with at least one acid catalyst, at least one acid anhydrides; wherein by the acyl radicals esterified extremely poly-α-1 derived from acid anhydrides; 3-dextran; thus formed by poly-α-1, the 3-dextran ester cpds of following representation:
Wherein
I () n is at least 6,
(ii) each R is H or carboxyl groups independently, and
(iii) described compound has the substitution value of about 0.05 to about 3.0.
Optionally separating can go out poly-α-1,3-dextran ester obtained by this method.
In anhydrous reaction substantially, poly-α-1,3-dextran is contacted with at least one organic acid with at least one acid catalyst, at least one acid anhydrides.Substantially anhydrous reaction does not comprise water herein, or comprises the water being less than about 0.05,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,1.9 or 2.0 % by weight.By using anhydrous reactive component substantially, obtain anhydrous condition substantially.Substantially anhydrous reactive component can be used for preparation reaction, but amount only makes end reaction preparation substantially anhydrous.
Poly-α-1, the 3-glucan preparation that can be used for the enzymatic generation in esterification disclosed in this invention comprises water usually.This poly-α-1,3-dextran theobromine exchanges to remove water, thus makes dextran substantially anhydrous.In certain embodiments, poly-α-1,3-dextran before contact procedure (a), can exchange with organic acid (such as acetic acid, propionic acid or butyric acid) acid, to dewater from poly-α-1,3-dextran.Sour exchange process herein can comprise makes poly-α-1, the aqueous solution boiling of 3-dextran, remove most of water (such as filtration, decantation and/or drying) via any physical route, dextran is positioned in organic acid, then removes organic acid by filtration and/or decantation.Can be included in acid with organic acid process and stir dextran, and can carry out once, twice or more time.The organic acid amount used in each process can be such as processed poly-α-1,3-dextran amount at least about 2 to 20 times, or 2 to 10 times.
In reaction disclosed in this invention, poly-α-1,3-dextran is contacted with at least one acid catalyst.In certain embodiments, acid catalyst can be mineral acid.The example that can be contained in the inorganic acid catalyst in this text response is sulfuric acid and perchloric acid.Other example of inorganic acid catalyst comprises hydrochloric acid, phosphoric acid, nitric acid, boric acid, hydrofluoric acid, Hydrogen bromide, sulfonic acid, any mineral acid and their any combination.Acid catalyst herein can usually to concentrate (such as > 95%, 96%, 97%, 98% or 99% purity) and/or anhydrous form is commercially available substantially.Such as, 95-98% purity can be at least about for the sulfuric acid in this text response.Alternatively, acid catalyst can provide in the solution of organic acid such as acetic acid.The example of this type of solution is the acetic acid solution of perchloric acid (0.1N).In reaction, the amount of acid catalyst can be such as at least about 0.005,0.0075,0.01,0.025,0.05,0.075,0.1,0.25,0.5,0.75,1.0,1.25,1.5,1.75 or 2.0 % by weight.
In reaction disclosed in this invention, poly-α-1,3-dextran is contacted with at least one acid anhydrides.The example that can be contained in the acid anhydrides in this text response comprises diacetyl oxide, propionic anhydride, butyryl oxide, valeric anhydride, caproic anhydride, heptylic anhydride, caprylic anhydride and Tetra hydro Phthalic anhydride.These any combination can be used for (such as diacetyl oxide and propionic anhydride, diacetyl oxide and butyryl oxide, propionic anhydride and butyryl oxide) in this text response.Acid anhydrides herein can usually to concentrate (such as > 95%, 96%, 97%, 98% or 99% purity) and/or anhydrous form is commercially available substantially.Such as, 97%, 98% or 99% purity can be at least about for the diacetyl oxide in this text response, propionic anhydride and/or butyryl oxide.In reaction, the amount of acid anhydrides can be such as at least about 10,15,20,25,30,35,40,45,50,55,60,65 or 70 % by weight (or any round valuess between 10 and 70 % by weight).In certain embodiments, in reaction, the amount of diacetyl oxide can be at least about 20-45 % by weight.In other embodiments, the amount of propionic anhydride or butyryl oxide can be at least about 40-50 % by weight.
In reaction disclosed in this invention, poly-α-1,3-dextran is contacted with at least one organic acid.The organic acid example that can be contained in this text response comprises acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, sad and phthalic acid.In reaction, organic acid amount can be such as at least about 5,10,15,20,25,30,35,40,45,50,55,60,65,70,75 or 80 % by weight (or any round valuess between 5 and 80 % by weight).
Usually, according to desired esterification type, select one or more acid anhydrides used in this text response.Such as, if expect the esterification of poly-α-1,3-dextran and Acetyl Groups, propionyl group and/or butyryl radicals group, then correspondingly comprise diacetyl oxide, propionic anhydride and/or butyryl oxide respectively in the reaction.One or more selected acid anhydrides are carboxyl groups sources main in esterification reaction process disclosed in this invention.However, the carboxyl groups for esterification also can derived from one or more organic acids comprised in reaction.Such as, Acetyl Groups, propionyl group, butyryl radicals group, pentanoyl group, caproyl group, oenanthyl group and capryloyl group can respectively derived from acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid and sad.The reaction comprising concrete acid anhydrides also comprises the organic acid corresponding with described acid anhydrides usually.
In some embodiment of reacting disclosed in the present invention, acid anhydrides is one or more in diacetyl oxide, propionic anhydride or butyryl oxide; And organic acid is one or more in acetic acid, propionic acid or butyric acid.Such as, the combination of (i) diacetyl oxide and acetic acid can be used to prepare poly-α-1,3-dextran acetic ester; The combination of (ii) propionic anhydride and propionic acid can be used to prepare poly-α-1,3-dextran propionic ester; Poly-α-1, the 3-dextran butyric ester of combination preparation of (iii) butyryl oxide and butyric acid can be used; The combination of (iv) propionic anhydride, propionic acid, diacetyl oxide and optional acetic acid can be used to prepare poly-α-1,3-dextran acetate propionate; The combination of (v) propionic anhydride, propionic acid and acetic acid can be used to prepare poly-α-1,3-dextran acetate propionate; The combination of (vi) butyryl oxide, butyric acid, diacetyl oxide and optional acetic acid can be used to prepare poly-α-1,3-dextran acetate butyrate; And can use (vii) butyryl oxide, poly-α-1,3-dextran acetate butyrate is prepared in the combination of butyric acid and acetic acid.In the reaction comprising acetic acid and propionic acid or butyric acid, the amount of acetic acid can be such as about 5-10,5-20 or 5-30 % by weight.
Generate mixed ester (such as poly-α-1; 3-dextran acetate propionate, poly-α-1; 3-dextran acetate butyrate) reaction usually comprise the more acid anhydrides with the carboxyl groups of the higher DoS of expectation, and comprise the acid anhydrides of the lower DoS of less expectation and/or corresponding organic acid.Such as, for generating compared with Acetyl Groups, have poly-α-1, the 3-dextran acetate propionate of higher propionyl group DoS, packet content is higher than the propionic anhydride of diacetyl oxide and/or acetic acid in the reaction.Also by comprise acid catalyst reaction in the addition sequence of acid anhydrides, regulate the DoS in mixed ester.Such as, when preparing reaction to prepare poly-α-1,3-dextran acetate propionate, if propionic anhydride added (to comprising in the preparation of acid catalyst) before diacetyl oxide, then high propionyl group DoS can be haggled in advance.
The acid anhydrides being used for this text response is selected to may correspond in exchanging the organic acid gathering α-1,3-dextran for the preparation of acid.Such as, if reaction will comprise propionic anhydride, then sour exchange process can carry out with propionic acid.Alternatively, the acid anhydrides being used for this text response is selected can be different from the organic acid exchanging poly-α-1,3-dextran for the preparation of acid.Such as, if reaction will comprise propionic anhydride, then sour exchange process can carry out with acetic acid.
Reaction herein can comprise the component beyond poly-α-1,3-dextran, acid catalyst, acid anhydrides and organic acid.Such as, one or more organic solvents such as methylene dichloride can be comprised in reaction.In reaction, organic solvent such as methylene dichloride can comprise in the reaction (such as generating dextran triacetate) by about 30-40 % by weight.
The component of this text response can any order be added together.Such as, first poly-α-1,3-dextran, acid catalyst and organic acid can be mixed, acid anhydrides can be joined in mixture afterwards.And for example, first acid anhydrides and organic acid can be mixed, poly-α-1,3-dextran and acid catalyst can be joined in mixture afterwards.And for example, first acid catalyst and organic acid can be mixed, poly-α-1,3-dextran and acid anhydrides can be joined in mixture afterwards.In certain embodiments, α-1,3-dextran and another kind of component (such as acid catalyst or acid anhydrides) will be gathered sequentially join and comprise in the mixture of other reactive component.
During each stage of this text response of preparation, cooling can be applied.Term " cooling " and " freezing " exchange use in this article, and refer to lower temperature is down in reaction or the temperature of mixture.Cooling can be carried out via any approach known in the art, such as by ice bath or industrial cooling system.The step (a) of preparation reaction can be included in after reaction is prepared and (namely comprise all poly-α-1,3-dextran, acid catalyst, acid anhydrides and organic acid) cooled, such as to about 10,11,12,13,14,15,16,17,18,19 or 20 DEG C, or about 12-18 DEG C.Alternatively, step (a) can comprise cooling (such as to any aforementioned temperature) and comprise poly-α-1,3-dextran, acid catalyst and organic acid mixture, is then joined in the mixture of cooling by acid anhydrides.Alternatively, step (a) also can comprise cooling (such as to any aforementioned temperature) and comprise acid anhydrides and organic acid mixture, then will gather α-1,3-dextran and acid catalyst joins in the mixture of cooling.Alternatively, step (a) also can comprise cooling (such as to any aforementioned temperature) and comprise acid catalyst and organic acid mixture, then will gather α-1,3-dextran and acid anhydrides joins in the mixture of cooling.Reaction optionally after its initial formulation, can keep about 1-10 minute under any aforementioned colder temperature spot.
Then, under reaction (i) can being placed in ambient temperature conditions, directly do not apply heat, and/or (ii) adopts any approach direct heating (such as water-bath, industry or electric heater) known in the art.Ambient temperature conditions can be kept such as at the most about 30,60,120,240,360 or 480 minutes (or any round values between 30 and 480 minutes).Alternatively, ambient temperature conditions can be retained to many about 24,48 or 72 hours.As used herein, term " envrionment temperature " refers to the temperature (or any integer between 15 and 30 DEG C) between about 15-30 DEG C or 20-25 DEG C.Reaction heating can be such as about 30,35,40,45,50,55,60,65,70,75 or 80 DEG C at the most (or any round valuess between 30 and 80 DEG C), about 30-60 DEG C, or about 30-50 DEG C.If needed, this type of heating can be carried out stage by stage.Such as, first reaction can be heated to about 35 DEG C, then be heated to about 39-50 DEG C.In certain embodiments, maximum temperature of reaction (such as about 36-43 DEG C) can be applied to avoid poly-α-1,3-dextran ester molecule amount excessive degradation, such as at the poly-α-1 of generation, 3-dextran propionic ester, poly-α-1, when 3-dextran acetate propionate or poly-α-1,3-dextran acetate butyrate.The temperature be heated to after any said temperature can be kept such as about 20-30,20-40,20-60 minute or about 40,60,80,100,120 or 140 minutes at the most.When heating stage by stage, one or more first temperature spot can be kept such as about 20-40 minute.Directly do not apply the embodiment of heat wherein under reaction is placed in ambient temperature conditions, if needed, subsequently reaction can be heated to any said temperature and time period.After any said temperature process (envrionment temperature and/or heating), reaction does not comprise any solid material usually, but may be thickness.
Optionally after any said temperature process (envrionment temperature and/or heating), reaction can be cooled.Such as, reaction can be cooled to about 18,19,20,21,22,23,24 or 25 DEG C, about 20-30 DEG C, or about 20-40 DEG C.The reaction being heated to 60-80 DEG C can be cooled to about 35-45 DEG C usually.The temperature of reaction during cooling can be kept such as about 5-10 minute.
Optionally, under reaction herein can being remained on rare gas element (such as nitrogen).As used herein, term " rare gas element " refers to the gas that chemical reaction does not occur under one group of specified criteria, all as disclosed for preparing those of this text response.
Optionally after any said temperature process (envrionment temperature and/or heating) and cooling process, can will react quencher.The quencher of reaction realizes by adding acid, alkali or some salt in this reaction.Can be used for the various acid of quencher reaction, alkali and salt and include but not limited to acetic acid (such as about 50-70 % by weight), any other inorganic or organic acid (such as ~ about 50-70 % by weight), magnesium acetate (such as about 20-25 % by weight), sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium bicarbonate, sodium carbonate and their combination.In some embodiment generating poly-α-1,3-dextran acetic ester, with acetic acid (such as about 50 or 70 % by weight) or magnesium acetate (such as about 20-25 % by weight) quencher reaction.
Optionally the reaction of quencher can be heated to about 40 DEG C to 150 DEG C continues to many 48 hours.Such as, such as in the process for generating poly-α-1,3-dextran acetic ester, the reaction of quencher can be heated to about 100 DEG C and continue to many about 20-40 minute (such as 25-30 minute).Optionally; water can be joined in (quencher or non-quencher) reaction; then be heated to about 40 DEG C to 150 DEG C (such as about 100 DEG C) and continue to many about 20-40 minute (such as 25-30 minute), to be reduced the DoS of carboxyl groups by hydrolysis.In the process generating poly-α-1,3-dextran acetic ester, this type of heating/water treatment steps can be used for reducing DoS.
The reagent of poly-α-1,3-dextran ester cpds non-solvent can be used poly-α-1,3-dextran ester cpds precipitation obtained for this text response.Such as, enough deionized waters and/or methyl alcohol can be joined in reaction soln to make poly-α-1,3-dextran ester cpds precipitate.Precipitation herein also can comprise makes reaction soln and non-solvent mixing via any approach known in the art, such as uses pneumatic blender.
Can optionally through poly-α-1, the 3-dextran ester cpds be settled out to be washed twice with water or more time, then washing in supercarbonate (such as sodium bicarbonate) solution (such as about 5 % by weight), neutralizes described compound.Then used water by ester cpds washing once, twice or more time, until reach neutral pH.Alternatively, poly-α-1, the 3-dextran ester cpds that used water and alkali (alkaline hydrated oxide such as diluted is sodium hydroxide, calcium hydroxide or potassium hydroxide such as) washing precipitation go out, to reach neutral pH, optionally washes with water subsequently.As used herein, term " neutral pH " refer to neither significantly for acid also significantly for alkalescence pH (such as about 6-8 or about 6.0,6.2,6.4,6.6,6.8,7.0,7.2,7.4,7.6, the pH of 7.8 or 8.0).
Poly-α-1,3-dextran ester obtained in separable disclosed reaction.Above-mentioned precipitation process can be a step in sepn process.Can before or after neutralization procedure and/or washing step, use funnel, whizzer, pressure filter or any other method that liquid can be removed from solid known in the art or equipment, the product be settled out is separated.Any method known in the art can be adopted, such as vacuum-drying, air-dry (such as about 16-35 DEG C) or lyophilize, dry isolated poly-α-1,3-dextran ester products.
Poly-α-1,3-dextran ester products can be used to repeat any above-mentioned esterification, with further modification as raw material.The method can be suitable for the DoS improving carboxyl groups, and/or is joined in ester products by one or more different carboxyl groups.
Various biochemical analysis known in the art can be adopted, such as NMR spectrum and size exclusion chromatography (SEC), confirm the structure of poly-α-1,3-dextran ester products, molecular weight and DoS.
For the preparation of gathering α-1 herein, the poly-α-1 of 3-dextran ester cpds, between the glucose monomer unit of 3-dextran, per-cent for the glycosidic link of α-1,3 is at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99% or 100% (or any round values between 50% and 100%).Therefore in this type of embodiment, poly-α-1,3-dextran has the glycosidic link of the non-alpha-1,3 being less than about 50%, 40%, 30%, 20%, 10%, 5%, 4%, 3%, 2%, 1% or 0% (or any round values between 0% and 50%).
Poly-α-1,3-dextran for the preparation of poly-α-1,3-dextran ester cpds be herein preferably straight chain/non-branched.In certain embodiments, poly-α-1,3-dextran does not have tapping point, or have the per-cent that accounts for glycosidic link in described polymkeric substance be less than about 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2% or 1% tapping point.The example of tapping point comprises α-1,6 tapping point.
For the preparation of the M of poly-α-1, the 3-dextran of poly-α-1,3-dextran ester cpds herein nor M w500 to about 300000 can be at least about.Also alternatively, M nor M wcan be such as at least about 10000,25000,50000,75000,100000,125000,150000,175000,200000,225000,250000,275000 or 300000 (or any integers between 10000 and 300000).
Disclosed herein is and use poly-α-1,3-dextran triacetate preparation to have the method for poly-α-1, the 3-dextran acetic ester of the DoS of 0.05 to 2.70.The triacetate used in the method can obtain according to such as any aforesaid method.The method comprises: make poly-α-1,3-dextran triacetate contact to form preparation with acetic acid with water, and apply about 3-10kg/cm to described preparation 2vapour pressure, the highest about 260 DEG C so that its temperature is risen to.The method obtains poly-α-1, the 3-dextran acetic ester with the DoS of 0.05 to 2.70.This type of of DoS reduces by the part hydrolysis of the Acetyl Groups of poly-α-1,3-dextran triacetate and causes.Optionally separating can go out poly-α-1,3-dextran acetic ester obtained by this method.
Poly-α-1,3-dextran triacetate in for the method before, optionally washed and/or be there is neutral pH.By being first dissolved in acetic acid by dextran triacetate, then water is joined this solution, poly-α-1,3-dextran triacetate is contacted with water with acetic acid.In certain embodiments, in preparation, the amount of acetic acid can be about 75 % by weight, 80 % by weight, 85 % by weight or 90 % by weight, and in preparation, the amount of water can be at the most about 1 % by weight, 2 % by weight, 3 % by weight, 4 % by weight, 5 % by weight, 6 % by weight, 7 % by weight, 8 % by weight, 9 % by weight or 10 % by weight.
Then the preparation comprising poly-α-1,3-dextran triacetate, acetic acid and water is made to stand about 3-10kg/cm 2vapour pressure, the highest about 260 DEG C so that its temperature is risen to.This step can optionally be implemented in pressurized vessel such as Parr reactor, autoclave or other pressurized vessel any known in the art.Such as about 4,5 or 6kg/cm can be adopted 2vapour pressure formulation temperature is risen to about 140-160 DEG C (such as 150 DEG C).This high temperature is kept about 30,40,50,60 or 70 minutes, applied pressure can be risen to about 7,8 or 9kg/cm further afterwards 2.After reaching this high pressure, temperature can be cooled to envrionment temperature.
Any one in above-disclosed precipitation, washing and separating step can be adopted, by have 0.05 to 2.70 DoS poly-α-1,3-dextran acetic ester from pressure-processed/preparation of heat-processed be separated.
Poly-α-1, the 3-dextran ester adopting above-mentioned various method to be formed can be used for preparing various types of film.Poly-α-1, the 3-dextran ester obtained according to disclosed method dissolves in one or more solvents, to provide the solution of poly-α-1,3-dextran ester.As used herein, term " solution of poly-α-1,3-dextran ester " refers to poly-α-1, the 3-dextran ester be dissolved in one or more solvents.The solvent that can be used for this object includes but not limited to METHYLENE CHLORIDE (methylene dichloride), methyl alcohol, chloroform, tetrachloroethane, formic acid, acetic acid, oil of mirbane, bromofom, pyridine, dioxane, ethanol, acetone, alcohol, aromatic substance (such as mono chloro benzene, Benzene and Toluene), ester (such as ethyl acetate and propyl acetate), ether (such as tetrahydrofuran (THF), methylcyclohexane and ethylene glycol monomethyl ether or their combination.In one embodiment, poly-α-1,3-dextran acetic ester is dissolved in acetone to prepare the solution of poly-α-1,3-dextran acetic ester.Then this solution can be applied to surface, and make solvent evaporate to form the film with desired thickness.Be suitable for this surface of using can be but be not limited to glass, , plastics or various types of substrate.The method being prepared film by above-mentioned solution is well known in the art, includes but not limited to solution-cast, spin coating, thermospray and Typical spray.In one embodiment, the solution-cast of α-1,3-dextran ester will be gathered on a glass.
By method well known in the art, the anti tear degree of poly-α-1,3-dextran ester film, tensile strength and temperature stability can be measured.As used herein, term " anti tear degree " is defined as film and can stands measuring of the degree of tearing effect.As used herein, term " tensile strength " refers to that material is not torn and the maximum tension that can stand.The suitable anti tear degree of poly-α-1,3-dextran ester film disclosed herein can be at least 0.1gf/mil.The tensile strength being applicable to the film of disclosed invention can be at least 4kgf/mm 2.In one embodiment, the anti tear degree of poly-α-1,3-dextran diacetate esters film is 2-2.4gf/mil, and tensile strength is 3.97-4.8kgf/mm 2.In another embodiment, anti tear degree is 1.4-3.1gf/mil, and tensile strength is 4.98-6.44kgf/mm 2.
By method well known in the art, mist degree and the transmissivity of poly-α-1,3-dextran ester film can be measured.As used herein, term " mist degree " refers to the per-cent of the light departing from more than 2.5 degree, incident light direction.Low haze valus corresponds to better transparency.As used herein, term " transmissivity " refers to the mark by the incident light of film under specified wavelength.Suitable film for α-1,3-dextran acetate membrane poly-in present patent application can have the mist degree of 20% and the transmissivity of at least 80% at the most.In one embodiment, mist degree is 6.2%, and transmissivity is 94.6%.
By the Weak solvent except methylene dichloride such as methyl alcohol and hexanaphthene, ethanol and propyl carbinol or a large amount of methyl alcohol or ethanol being joined in poly-α-1,3-dextran ester solution, with accelerated rates of cure, and increase the speed of masking.Shrinking percentage by control surface temperature and film limits planar orientation degree and degree of crystallinity.
example
Disclosure invention will be set forth in the following example further.Should be appreciated that, these examples although the description of some preferred aspect of the present invention, but only provide in an exemplary manner.From discussion above and these examples, those skilled in the art can determine fundamental characteristics of the present invention, and when not departing from its essence and scope, can carry out variations and modifications to adapt to different purposes and condition to the present invention.
abbreviation:
" mL " is milliliter; " g " is gram; " D1 water " is deionized water; " μ L " is microlitre; " DEG C " is degree Celsius; " mg " is milligram; " TFA " is trifluoroacetic acid; " Hz " is hertz; " MHz " is megahertz; " ppm " is part each 1,000,000 parts; " HFIP " is hexafluoro-2-propyl alcohol; " TFA-d " is deuterated trifluoroacetic acid, and " kgf " is kilogram force.
material
Sulfuric acid, acetic acid and sodium bicarbonate derive from EMD Chemicals (Billerica, MA).Diacetyl oxide derives from Acros Organics (Pittsburgh, PA).The acetic acid solution of butyric acid, butyryl oxide, propionic anhydride and 0.1N perchloric acid derives from Sigma Aldrich (St.Louis, MO).Propionic acid derives from JTBaker (Center Valley, PA).Magnesium acetate derives from Alfa Aesar (Ward Hill, MA).Except as otherwise noted, all acid used herein and acid anhydrides are all anhydrous or substantially anhydrous.
poly-α-1,3-dextran
Preparation use gtfJ zymin as described in U.S. Patent Application Publication 2013/0244288, prepare poly-α-1,3-dextran, its full text be incorporated herein by reference.
for measuring the substitution value of poly-α-1,3-dextran acetic ester derivative 1 h nucleus magnetic resonance (NMR) method
Adopt 1h NMR measures the substitution value (DoS) in poly-α-1,3-dextran acetic ester derivative.Analytical balance weighs about 20mg derivative sample in bottle.Bottle is taken off from balance, and the TFA-d of 0.7mL is joined bottle.Magnetic stirring bar is joined bottle, and stirs the mixture, until solid sample dissolves.Then by deuterated for 0.3mL benzene (C 6d 6) join bottle, than TFA-d, the better NMR provided is locked field signal to provide.Glass volumetric pipette is used to be transferred in 5-mm NMR pipe by a part (0.8mL) solution.Use and be equipped with the Agilent VNMRS 400MHz NMR spectrograph that 5mm changes quadrupole probe automatically, gather quantitatively 1h NMR spectrum.With the spectral frequency of 399.945MHz, use 6410.3Hz spectral window, 1.278 seconds acquisition times, and postpone and 124 pulses between 10 pulse per second (PPS)s, gather spectrum.The exponential multiplication of 0.78Hz is used to carry out transformation time numeric field data.
By two of gained spectrum domain integral: 3.1ppm to 6.0ppm, obtain the integration of seven poly-α-1,3-dextran protons, and 1.4ppm to 2.7ppm, obtain the integration of three acetyl protons.By by 1/3rd of acetyl protons integral area divided by 1/7th of poly-α-1,3-dextran Proton integration area, calculate degree of acetylation.
for measuring poly-α-1,3-dextran propanoate ester derivatives substitution value 1 h NMR method
Adopt 1h NMR measures the DoS in poly-α-1,3-dextran propanoate ester derivatives.Analytical balance weighs about 20mg derivative sample in bottle.Bottle is taken off from balance, and the TFA-d of 0.7mL is joined bottle.Magnetic stirring bar is joined in bottle, and stirs the mixture, until solid sample dissolves.Then by deuterated for 0.3mL benzene (C 6d 6) join bottle, than TFA-d, the better NMR provided is locked field signal to provide.Glass volumetric pipette is used a part (0.8mL) for solution to be transferred in 5-mm NMR pipe.Use and be equipped with the Agilent VNMRS 400MHz NMR spectrograph that 5mm changes quadrupole probe automatically, gather quantitatively 1h NMR spectrum.With the spectral frequency of 399.945MHz, use 6410.3Hz spectral window, 1.278 seconds acquisition times, and postpone and 32 pulses between 10 pulse per second (PPS)s, gather spectrum.Use 1.0Hz index linear to widen, transform time domain data, and benzene solvent peak is set to 7.15ppm.
Just poly-α-1,3-dextran propionic ester sample, by three of gained spectrum domain integral: 3.3ppm to 6.0ppm, obtains the integration of seven poly-α-1,3-dextran protons; 1.9ppm to 2.7ppm, obtains the integration of the methylene group of propionyl group and the methyl group of Acetyl Groups; With 0.8ppm to 1.3ppm, obtain the integration of the methyl group of propionyl group.
By the integrated value of the methyl group by propionyl group divided by three, calculate the DoS of propionyl group.Then be multiplied by 0.666 by the integrated value of the methylene group by propionyl group, calculate the integrated value of the methylene group of propionyl group.Then the domain integral of this value from the methyl group of the methylene group of propionyl group and Acetyl Groups is deducted, obtain the integrated value of the methyl group of Acetyl Groups.
for measuring poly-α-1,3-dextran mixed ester derivative substitution value 1 h NMR method
Adopt 1h NMR measures the DoS in poly-α-1,3-dextran mixed ester derivative.Analytical balance weighs about 20mg derivative sample in bottle.Bottle is taken off from balance, and the TFA-d of 0.7mL is joined bottle.Magnetic stirring bar is joined in bottle, and stirs the mixture, until solid sample dissolves.Then by deuterated for 0.3mL benzene (C 6d 6) join in bottle, lock field signal to provide the better NMR provided than TFA-d.Glass volumetric pipette is used a part (0.8mL) for solution to be transferred in 5-mm NMR pipe.Use and be equipped with the Agilent VNMRS 400MHz NMR spectrograph that 5mm changes quadrupole probe automatically, gather quantitatively 1h NMR spectrum.With the spectral frequency of 399.945MHz, use 6410.3Hz spectral window, 1.278 seconds acquisition times, and postpone and 32 pulses between 10 pulse per second (PPS)s, gather spectrum.Use 1.0Hz index linear to widen, transform time domain data, and benzene solvent peak is set to 7.15ppm.
Just poly-α-1,3-dextran acetate propionate sample, by three of gained spectrum domain integral: 3.3ppm to 6.0ppm, obtains the integration of seven poly-α-1,3-dextran protons; 1.9ppm to 2.7ppm, obtains the integration of the methylene group of propionyl group and the methyl group of Acetyl Groups; With 0.8ppm to 1.3ppm, obtain the integration of the methyl group of propionyl group.
By the integrated value of the methyl group by propionyl group divided by three, calculate the DoS of propionyl group in dextran.Then be multiplied by 0.666 by the integrated value of the methylene group by propionyl group, calculate the integrated value of the methylene group of propionyl group.Then this value is deducted from the domain integral of the methyl group of the methylene group of propionyl group and Acetyl Groups, obtain the integrated value of the methyl group of Acetyl Groups.Finally, by Acetyl Groups integrated value divided by three, obtain degree of acetylation.
Just poly-α-1,3-dextran acetate butyrate sample, by three of gained spectrum domain integral: 3.3ppm to 6.0ppm, obtains the integration of seven poly-α-1,3-dextran protons; 1.9ppm to 2.6ppm, acquisition and the carbonyl of butyryl radicals group are the integration of the methylene group of α position and the methyl group of Acetyl Groups; With 0.6ppm to 1.0ppm, obtain the integration of the methyl group of butyryl radicals group.
By the integrated value of the methyl group by butyryl radicals group divided by three, calculate the DoS of butyryl radicals group in dextran.Then be multiplied by 0.666 by the integrated value of the methylene group by butyryl radicals group, calculate the integrated value of the methylene group of butyryl radicals group.Then this value is deducted from the domain integral of the methyl group of the methylene group of butyryl radicals group and Acetyl Groups, obtain the integrated value of the methyl group of Acetyl Groups.Finally, by Acetyl Groups integrated value divided by three, obtain degree of acetylation.
the mensuration of the polymerization degree
The polymerization degree (DP) is measured via size exclusion chromatography, (SEC).To gather α-1,3-dextran ester is dissolved in HFIP (2mg/mL), vibrates 4 hours at 45 DEG C.The chromatographic separation system used is for deriving from the Alliance of Waters company (Milford, MA) tM2695 separation modules, with three On-line measurement devices: the differential refractometer 2410 deriving from Waters, derive from the multi-angle light-scattering photometer Heleos of Wyatt Technologies (Santa Barbara, CA) tM8+, and the differential capillary viscosimeter ViscoStar deriving from WyattTechnologies tM.The pillar that SEC uses is two Shodex (Showa Denko America, New York) GPC HFIP-806M tMstyrene-divinylbenzene post and a Shodex GPC HFIP-804M tMstyrene-divinylbenzene post.Move and heat up in a steamer HFIP for having answering of 0.01M sodium trifluoroacetate.Chromatographic separation condition used is at column compartment and detector compartment 50 DEG C, in sample chamber and 40 DEG C, injection compartment, and flow velocity 0.5mL/min, and volume injected 100 μ L.Software package for data reduction is the Astra 6 editions (three-in-one detection method and post correct) deriving from Wyatt.
example 1
the preparation of poly-α-1, the 3-dextran that acid exchanges
This example describes poly-α-1, the 3-dextran that preparation acid exchanges, and it can be used for the ester derivative preparing poly-α-1,3-dextran.
Poly-α-1, the 3-dextran that following preparation acid exchanges: 10g is gathered α-1,3-dextran and put in the 250mL glass beaker with 150mL Dl water.This mixture is seethed with excitement one hour on hot plate, reclaims poly-α-1,3-dextran by vacuum filtration afterwards.Then the sour exchange step under making poly-α-1,3-dextran experience twice room temperature, itself and 100mL glacial acetic acid stirred, then vacuum filtration, thus poly-α-1, the 3-dextran providing that acid exchanges.
Also can according to method above, but use propionic acid or butyric acid to substitute acetic acid, prepare other form of poly-α-1, the 3-dextran that acid exchanges.
Poly-α-1, the 3-dextran that the acid obtained by these technology exchanges is used in some example following, to prepare various poly-α-1,3-dextran ester derivative.From poly-α-1,3-dextran, remove water because acid exchanges process, poly-α-1,3-dextran acid exchanged is introduced with the esterification of acid anhydrides, do not introduce can with the water of anhydride reaction.
example 2
the preparation of poly-α-1,3-dextran acetic ester
This example describes preparation dextran ester derivative and gathers α-1,3-dextran acetic ester.
In the 500mL round-bottomed flask being equipped with magnetic stirring bar, thermopair and condenser, poly-α-1, the 3-dextran (10g) that the acid using acetic acid to obtain in example 1 exchanges is joined the mixture comprising 180mL acetic acid and 1.84g sulfuric acid.This mixture is stirred 1 minute at ambient temperature, afterwards diacetyl oxide (50mL) is joined in mixture.Make reaction carry out 30 minutes at ambient temperature, then heat 20 minutes in the water-bath of 35 DEG C, be then heated to 50 DEG C and keep 30 minutes.Gained response preparation does not comprise any solid.Then reaction is taken out from water-bath, and make it cool 15 minutes to reach 42 DEG C.Then with 25mL 70% acetic acid quencher reaction, and 40 minutes are stirred.Use pneumatic blender and DI water, α-1,3-dextran acetic ester precipitation will be gathered.In 30 minutes with water by solids wash twice, then with 5% sodium bicarbonate washing once.Then poly-α-1,3-dextran acetic ester solid is finally washed with water, until reach neutral pH (twice washing).Via collected by vacuum filtration solid, dry under vacuo, and characterize via NMR and SEC.The method obtains has the DoS of the 2.3 and M of 29170 npoly-α-1,3-dextran acetic ester.
Thus, prepare and isolate ester derivative and gather α-1,3-dextran acetic ester.
example 3
other preparation of poly-α-1,3-dextran acetic ester
This example describes and uses various reaction conditions to prepare dextran ester derivative and gather α-1,3-dextran acetic ester.
As example 1 uses acetic acid to obtain poly-α-1, the 3-dextran of acid exchange.In the 500mL round-bottomed flask being equipped with magnetic stirring bar and thermopair, the mixture of preparation 180mL acetic acid and the 0.08g vitriol oil; This mixture is cooled to 18 DEG C.Poly-α-1, the 3-dextran (10g) that acid exchanges slowly is joined in the mixture of cooling, and stirs 1 minute.Then diacetyl oxide (50mL) is joined in mixture.Making reaction carry out 10 minutes when not heating, then heating 20 minutes in the water-bath of 35 DEG C.Use ice bath, in 7 minutes, the gained reaction without any solid is cooled to 22 DEG C.Then with 25mL 70% acetic acid quencher reaction, and 40 minutes are stirred.As described in example 2, poly-α-1,3-dextran acetic ester is made to precipitate, wash and analyze.The method obtains has the DoS of the 2.41 and M of 73960 npoly-α-1,3-dextran acetic ester.
Use the reagent of different concns, different ester products can be formed.Following table 1 illustrates the method used with method is similar above, but different poly-α-1, the 3-dextran acetic ester adopting some amendment as shown in Table and synthesize.Result in table 1 shows, by changing the molecular weight of poly-α-1, the 3-dextran raw material used in reaction conditions and reaction, can change the DoS of Acetyl Groups and the molecular weight of product in ester products.
table 1
poly-α-1, the 3-dextran acetic ester obtained by poly-α-1,3-dextran
Temperature after a reacting by heating.
Thus, prepare and isolate various forms of ester derivative and gather α-1,3-dextran acetic ester.
example 4
the other preparation of poly-α-1,3-dextran acetic ester
This example describes the method for the preparation of poly-α-1,3-dextran acetic ester with hydrolysing step.
Poly-α-1, the 3-dextran (28g) that the acid using acetic acid to obtain in example 1 exchanges is joined in the mixture comprising 93.4mL acetic acid and the 2.24g vitriol oil, and mixes.This mixture is joined in the reaction vessel of the 1L jacketed being equipped with overhead type stirrer and thermopair, and uses recirculation bath to be cooled to 12 DEG C.Then reaction mixture is stirred 1 minute, add diacetyl oxide (89mL) afterwards.Use the recirculation bath being set to 42 DEG C, by reaction heating 40 minutes.With 15.25g (24%) magnesium acetate and excessive water, by this elementary reaction quencher without any solid, so that sulfuric acid content is down to 2%.Then in 25 minutes, reaction is heated to 100 DEG C, stirs 2 hours at such a temperature afterwards.By adding 5% excessive 24% magnesium acetate (6.1g), will react completely quencher.As example 2, poly-α-1,3-dextran acetic ester is made to precipitate, wash and analyze.The method obtains poly-α-1, the 3-dextran acetic ester with the DoS of 2.58.
Thus, use the method comprising hydrolysing step, carry out obtained ester derivative and gather α-1,3-dextran acetic ester.
example 5
via poly-α-1, the 3-dextran acetic ester of poly-α-1,3-dextran triacetate hydrolysis preparation
Describe via poly-α-1, the 3-dextran acetic ester of poly-α-1,3-dextran triacetate hydrolysis preparation this EXAMPLEPART.
First poly-α-1, the 3-dextran triacetate of following preparation.
Acetic acid (384mL), diacetyl oxide (990mL) and methylene dichloride (890mL) are mixed.Said preparation is joined the 4L glass reaction container being equipped with overhead type stirrer and thermopair, and be cooled to 12 DEG C.Poly-α-1, the 3-dextran (130g) that the acid using acetic acid to obtain in example 1 exchanges slowly is joined in the mixture of cooling, and stirs 1 minute.Then acetic acid (180mL) solution of perchloric acid (0.1N) is added.Reaction is made to carry out 3 hours 35 minutes at ambient temperature.Then the reaction without any solid being joined comprises in the pneumatic blender of methyl alcohol, to precipitate poly-α-1,3-dextran triacetate.Poly-α-1, the 3-dextran triacetate solids with methanol formed thus is washed 30 minutes, then uses deionization (DI) water washing twice, and wash once with 5% sodium bicarbonate.Then poly-α-1,3-dextran triacetate solid is finally washed with water, until reach neutral pH (twice washing), and via collected by vacuum filtration, dry under vacuo, and characterize via NMR and SEC.Obtained poly-α-1,3-dextran triacetate has the DoS of the 3.0 and M of 132300 n.
Prepare the hydrolysis of obtained poly-α-1,3-dextran triacetate above: be first dissolved in the acetic acid of 80mL.Then DI water (4mL) is joined in said preparation, and use magnetic stirring bar to stir, until fully mix.Then preparation is transferred in Parr reactor (Parr InstrumentCompany, Moline, IL); By 5kg/cm 2the steam of pressure blows in reactor, temperature is risen to 150 DEG C in 12 minutes.Preparation is kept 50 minutes at this temperature.Then by pressure from 5kg/cm 2rise to 8.37kg/cm 2, afterwards reaction vessel is cooled to envrionment temperature.The preparation color reclaimed from reactor is for yellow.But after adding DI water, poly-α-1, the 3-dextran acetic ester solid precipitation of white out.As example 2, isolated by vacuum filtration is used to go out this poly-α-1,3-dextran acetic ester, and washing and analysis.The method obtains has the DoS of the 2.4 and M of 44200 npoly-α-1,3-dextran acetic ester.
Thus, poly-α-1, the 3-dextran acetic ester of DoS had lower than 2.75 is obtained by poly-α-1,3-dextran triacetate.
example 6
the preparation of poly-α-1,3-dextran propionic ester
This example describes preparation dextran ester derivative and gathers α-1,3-dextran propionic ester.
Poly-α-1, the 3-dextran (M that preparation acid exchanges as described in example 1 nbe 119130), unlike the use of propionic acid instead of acetic acid.In 250mL round-bottomed flask, mix propionic acid (8mL) and sulfuric acid (0.03g), and be cooled to 18 DEG C.Poly-α-1, the 3-dextran (2g) that acid exchanges slowly is joined in the mixture of cooling, and stirs 1 minute.Then in said preparation, add propionic anhydride (10mL), add 0.6mL glacial acetic acid afterwards.Making reaction carry out 5 minutes when not heating, then heating 1 hour 45 minutes in the water-bath of 42 DEG C.Top temperature is made to be no more than 43 DEG C, to avoid molecular weight excessive degradation.Use ice bath, in 5 minutes, the gained response preparation without any solid is cooled to 20 DEG C.Then with 4mL 50% acetic acid aqueous solution quencher reaction, and 45 minutes are stirred.Use pneumatic blender and DI water, α-1,3-dextran propionic ester precipitation will be gathered.In 30 minutes with water by solids wash twice, then with 5% sodium bicarbonate washing.Then poly-α-1,3-dextran propionic ester solid is washed with water, until reach neutral pH (twice washing).Via collected by vacuum filtration solid, dry under vacuo, and characterize via NMR and SEC.Solid turns out to be poly-α-1,3-dextran propionic ester, has the propionyl group (0 % by weight Acetyl Groups) of 44.1 % by weight and the M of 59510 n.
Thus, prepare and isolate ester derivative and gather α-1,3-dextran propionic ester.
example 7
the preparation of poly-α-1,3-dextran acetate butyrate
This example describes preparation dextran mixed ester derivative and gathers α-1,3-dextran acetate butyrate.
In the 500mL round-bottomed flask being equipped with magnetic stirring bar, thermopair and condenser, poly-α-1, the 3-dextran (10g) that the acid using acetic acid to obtain in example 1 exchanges is joined the mixture comprising 21mL glacial acetic acid, 20mL butyric acid and 0.09g sulfuric acid.Use ice bath that mixture is cooled to 18 DEG C, and stir 1 minute, then butyryl oxide (39mL) is joined flask.Making reaction carry out 10 minutes when not heating, then heating 80 minutes in the water-bath of 35 DEG C, be then heated to 39 DEG C and continue 30 minutes, the top temperature wherein reached is 39 DEG C, to avoid molecular weight of product excessive descent.Use ice bath, in 10 minutes, the gained viscous solution without any solid is cooled to 20 DEG C.Then with 20mL 50% acetic acid aqueous solution quencher reaction, and 40 minutes are stirred.Use pneumatic blender and DI water, solid is gathered α-1,3-dextran acetate butyrate precipitation.In 30 minutes with water by solids wash twice, then with 5% sodium bicarbonate washing.Then the thus obtained solid of DI water washing is finally used, until reach neutral pH (twice washing).Via collected by vacuum filtration solid, dry under vacuo, and characterize via NMR and SEC.The method obtains the butyryl radicals DoS with 1.0, the ethanoyl DoS of 1.3, and the number-average molecular weight (M of 66340 n) poly-α-1,3-dextran acetate butyrate mixed ester.
Use the reagent of different concns, different mixed ester product can be formed.Following table 2 illustrates the method used with method is similar above, but different poly-α-1, the 3-dextran acetate butyrate adopting some amendment as shown in Table and synthesize.Result in table 2 shows, by changing the molecular weight of poly-α-1, the 3-dextran raw material used in reaction conditions and reaction, can change the amount of ethanoyl and butyryl radicals group and the molecular weight of product in mixed ester product.
Thus, prepare and isolate various forms of mixed ester derivative and gather α-1,3-dextran acetate butyrate.
example 8
the preparation of poly-α-1,3-dextran acetate propionate
This example describes preparation dextran mixed ester derivative and gathers α-1,3-dextran acetate propionate.
Use acetic acid as described in Example 1, poly-α-1, the 3-dextran that obtained acid exchanges.In 500mL round-bottomed flask, prepare the mixture of 35mL propionic acid and 0.09g sulfuric acid, and be cooled to 18 DEG C.Poly-α-1,3-dextran solid (10g) that acid exchanges slowly is joined in the mixture of cooling, and stirs 1 minute.Then add propionic anhydride (50mL), add 5mL glacial acetic acid afterwards.Making reaction carry out 10 minutes when not heating, then heating 1 hour in the water-bath of 30 DEG C, be then heated to 34 DEG C and continue 10 minutes.Top temperature is made to be no more than 36 DEG C, to avoid molecular weight of product excessive descent.In ice bath, in 5 minutes, the thus obtained solution without any solid is cooled to 20 DEG C.Then with 20mL 50% acetic acid aqueous solution quencher reaction, and 40 minutes are stirred.Use pneumatic blender and DI water, poly-α-1, the 3-dextran acetate propionate of precipitation from solution.In 30 minutes, with water, solid is gathered α-1,3-dextran acetate propionate product and wash twice, then with 5% sodium bicarbonate washing.Then solid is washed with water, until reach neutral pH (twice washing).Via collected by vacuum filtration solid, dry under vacuo, and characterize via NMR and SEC.The solid formed turns out to be poly-α-1,3-dextran acetate propionate, and it comprises 17.6 % by weight ethanoyl and 32.9 % by weight propionyl group, and has the M of 64030 n.
Use the reagent of different concns, different mixed ester product can be formed.Following table 3 illustrates the method used with method is similar above, but different poly-α-1, the 3-dextran acetate propionate adopting some amendment as shown in Table and synthesize.Result in table 3 shows, by changing the molecular weight of poly-α-1, the 3-dextran raw material used in reaction conditions and reaction, can change the amount of ethanoyl and propionyl group and the molecular weight of product in mixed ester product.
Thus, prepare and isolate various forms of mixed ester derivative and gather α-1,3-dextran acetate propionate.
example 9
sulfuric acid is used to gather α-1,3-dextran triacetate as catalyst preparing
This example describes and uses sulfuric acid as the catalyzer in reaction, poly-α-1, the 3-dextran triacetate of preparation.
Use poly-α-1, the 3-dextran that acetic acid preparation acid exchanges as described in Example 1.In the 500mL round-bottomed flask being equipped with magnetic stirring bar and thermopair, preparation 180mL acetic acid and 1.84g are as the mixture of the vitriol oil of catalyzer.Poly-α-1, the 3-dextran (10g) that acid exchanges slowly is added in mixture, and stirs 1 minute under a nitrogen.Use ice bath, this mixture is cooled to about 18 DEG C.Diacetyl oxide (50mL) is joined reaction, then in 45 minutes, is heated to 80 DEG C, and make it react 30 minutes at such a temperature.Use ice bath, in 5 minutes, the reaction without any solid is cooled to 40 DEG C.Then with 25mL 70% acetic acid quencher reaction, and 30 minutes are stirred.Use pneumatic blender (Waring, Torrington, CT) and DI water, α-1,3-dextran triacetate precipitation will be gathered.In 30 minutes, with water, solid is gathered α-1,3-dextran triacetate product and wash twice, then with 5% sodium bicarbonate washing.Then solid is washed with water, until reach neutral pH (twice washing).Via collected by vacuum filtration solid, dry under vacuo, and characterize via NMR and SEC.The method obtains 7.8g and has the DoS of the 3.1 and M of 5130 npoly-α-1,3-dextran triacetate.DoS reading more than 3.0 may reflect typical integration fluctuation in NMR measuring process.
Following table 4 illustrates the method used with method is similar above, but poly-α-1, the 3-dextran triacetate of the different molecular weight adopting some amendment as shown in Table and synthesize.Result in table 4 shows, by changing the molecular weight of poly-α-1, the 3-dextran raw material used in reaction conditions and reaction, can change the molecular weight of product.
table 4
use sulfuric acid catalyst, poly-α-1, the 3-dextran triacetate obtained by poly-α-1,3-dextran
Top temperature after a reacting by heating.
Thus, at use sulfuric acid as in the reaction of catalyzer, obtain and isolate various forms of poly-α-1,3-dextran triacetate.
example 10
perchloric acid is used to gather α-1,3-dextran triacetate as catalyst preparing
This example describes and uses perchloric acid to gather α-1,3-dextran triacetate as the catalyst preparing in reaction.
Use poly-α-1, the 3-dextran that acetic acid preparation acid exchanges as described in Example 1.In the 4L glass reaction container being equipped with overhead type stirrer and thermopair, the mixture of preparation 384mL acetic acid, 990mL diacetyl oxide and 890mL methylene dichloride, and be cooled to 12 DEG C.Poly-α-1, the 3-dextran (130g) that acid exchanges slowly is joined in the mixture of cooling, and stirs 1 minute.Then acetic acid (180mL) solution of perchloric acid (0.1N) is joined in mixture.Reaction is made to carry out 3 hours 35 minutes at ambient temperature.Reacting to join by not having the gained of solid comprises in the pneumatic blender of methyl alcohol, precipitates to make poly-α-1,3-dextran triacetate.α-1,3-dextran triacetate solids with methanol will be gathered and wash 30 minutes, then use DI water washing twice, and wash once with 5% sodium bicarbonate.Then poly-α-1,3-dextran triacetate is washed with water, until reach neutral pH (twice washing).Via collected by vacuum filtration solid, dry under vacuo, and characterize via NMR and SEC.The method obtains 221.5g and has the DoS of the 3.2 and M of 132300 npoly-α-1,3-dextran triacetate.DoS reading more than 3.0 may reflect typical integration fluctuation in NMR measuring process.
Following table 5 illustrates the method used with method is similar above, but poly-α-1, the 3-dextran triacetate of the different molecular weight adopting some amendment as shown in Table and synthesize.Result in table 5 shows, by changing the molecular weight of poly-α-1, the 3-dextran raw material used in reaction conditions and reaction, can change the molecular weight of product.
table 5
use perchloric acid catalysis agent, poly-α-1, the 3-dextran triacetate obtained by poly-α-1,3-dextran
Top temperature after a reacting by heating.
Thus, at use perchloric acid as in the reaction of catalyzer, prepare and isolate various forms of poly-α-1,3-dextran triacetate.
example 11
use poly-α-1,3-dextran acetic ester masking
Poly-α-1,3-dextran acetic ester obtained in example 2 is dissolved in acetone, to prepare solution with 10 % by weight mixtures.Then use film casting machine by solution-cast on clean sheet glass, and it is dry that solvent is evaporated to, to provide film.Film is taken off from glass, and cleans with DI water.Table 6 illustrates that the obtained two kinds of differences of different poly-α-1, the 3-dextran acetic ester sample of use two kinds gather the characteristic of α-1,3-dextran acetate membrane.
table 6
poly-α-1,3-dextran acetate membrane
example 12
the optical analysis of poly-α-1,3-dextran acetate membrane
The sample of poly-α-1,3-dextran acetate membrane obtained in example 11 is carried out the analysis of color and mist degree.The spectrum gathered meets ASTM E1164-09a.Spectral bandwidth (SBW)=1,1nm interval, wavelength region=830-360nm.Table 7 illustrates the result of this research.
table 7
the optical metrology of poly-α-1,3-dextran acetate membrane
Poly-α-1,3-dextran acetic ester DoS Poly-α-1,3-dextran acetic ester M n Mist degree Transmittance
2.6 78160 6.32％ 5.36％
example 13
the preparation of poly-α-1,3-dextran triacetate film
Poly-α-1, the 3-dextran triacetate of preparation as described in example 10.Being dissolved in 90g methylene dichloride by 10g being gathered α-1,3-dextran triacetate: in methyl alcohol (11.5: 1v/v), preparing the solution of poly-α-1, the 3-dextran triacetate of 10 % by weight.Then Gardner cutter (Gardner Lab Inc., Bethesda, MD) is used, by this solution-cast on clean sheet glass.Solvent is evaporated to dry.Film obtained after solvent evaporation is taken off from glass and uses DI water to clean.Table 8 summarizes and uses the tension force of obtained poly-α-1, the 3-dextran triacetate film of the method and tear data.Can find out, the M of component dextran ester ncause with the change of DoS and provide different physical propertys to obtained film.
table 8
poly-α-1,3-dextran triacetate film
example 14
the thermal analyses of poly-α-1,3-dextran triacetate film
Use MDSC and TGA, poly-α-1,3-dextran triacetate film obtained in analysis example 13.Use 5-6mg film, with the heating rate of 3 DEG C/min, the modulation amplitude of 0.48 DEG C, and modulation period second of 60, from 0 DEG C, at N 2middle use Q1000TA instrument, carries out MDSC mensuration.
Use Q500TA instrument, at N 2under from envrionment temperature to 800 DEG C, carry out TGA experiment.
The information provided in table 9 illustrates the thermostability/thermal degradation according to obtained poly-α-1, the 3-dextran triacetate film of above-disclosed method.Table 9 summarizes measures by MDSC and TGA the data gathered.Can find out, the M of component dextran ester ncause with the change of DoS and provide different physical propertys to obtained film.
table 9
mDSC and the TGA data of poly-α-1,3-dextran triacetate film
example 15
the optical analysis of poly-α-1,3-dextran triacetate film
Color and mist degree analysis are carried out to poly-α-1,3-dextran triacetate film obtained in example 13.Use be the spectral bandwidth (SBW) of 1 with the wavelength region of 1nm interval and 830-360nm, gather spectrum according to ASTM E1164-09a.The optical metrology result of poly-α-1,3-dextran triacetate film is shown in Table 10.
table 10
the optical metrology of poly-α-1,3-dextran triacetate film

Claims (7)

1. one kind comprises the film of poly-α-1,3-dextran ester, described film have following at least one:
A () is at least about the anti tear degree of 0.1gf/mil; Or
B mist degree that () is less than about 20%.
2. film according to claim 1, described poly-α-1, the 3-dextran ester wherein used is poly-α-1,3-dextran acetic ester.
3. film according to claim 1, wherein said film have following at least one:
A () about 2.0 is to the anti tear degree of about 2.4gf/mil; Or
B mist degree that () is less than about 10%.
4. film according to claim 3, described poly-α-1, the 3-dextran ester wherein used is poly-α-1,3-dextran acetic ester.
5. prepare the method for poly-α-1,3-dextran ester film for one kind, described method comprises:
A () provides poly-α-1,3-dextran ester;
B () makes poly-α-1, the 3-dextran ester of (a) and solvent contacts to prepare the solution of poly-α-1,3-dextran ester;
C solution that () will gather α-1,3-dextran ester is applied on the surface; And
D () makes described solvent evaporate to provide described poly-α-1,3-dextran ester film.
6. method according to claim 5, described poly-α-1, the 3-dextran ester wherein used is poly-α-1,3-dextran acetic ester.
7. method according to claim 5, wherein said solvent is acetone.
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