CN106519061B - A kind of preparation method of high esterification degree seaweed isopropyl propionate - Google Patents
A kind of preparation method of high esterification degree seaweed isopropyl propionate Download PDFInfo
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- CN106519061B CN106519061B CN201610871102.XA CN201610871102A CN106519061B CN 106519061 B CN106519061 B CN 106519061B CN 201610871102 A CN201610871102 A CN 201610871102A CN 106519061 B CN106519061 B CN 106519061B
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- seaweed
- alginic acid
- isopropyl
- isopropyl propionate
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- 238000005886 esterification reaction Methods 0.000 title claims abstract description 42
- 230000032050 esterification Effects 0.000 title claims abstract description 41
- 241001474374 Blennius Species 0.000 title claims abstract description 37
- IJMWOMHMDSDKGK-UHFFFAOYSA-N Isopropyl propionate Chemical compound CCC(=O)OC(C)C IJMWOMHMDSDKGK-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 235000010443 alginic acid Nutrition 0.000 claims abstract description 42
- 229920000615 alginic acid Polymers 0.000 claims abstract description 42
- 239000000783 alginic acid Substances 0.000 claims abstract description 41
- 229960001126 alginic acid Drugs 0.000 claims abstract description 41
- 150000004781 alginic acids Chemical class 0.000 claims abstract description 30
- -1 alcohols alginic acid ester Chemical class 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 239000012024 dehydrating agents Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 238000010992 reflux Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012065 filter cake Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000010979 pH adjustment Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- RLAHWVDQYNDAGG-UHFFFAOYSA-N Methanetriol Chemical compound OC(O)O RLAHWVDQYNDAGG-UHFFFAOYSA-N 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 abstract description 11
- 238000010792 warming Methods 0.000 abstract description 3
- 235000019441 ethanol Nutrition 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- HDSBZMRLPLPFLQ-UHFFFAOYSA-N Propylene glycol alginate Chemical compound OC1C(O)C(OC)OC(C(O)=O)C1OC1C(O)C(O)C(C)C(C(=O)OCC(C)O)O1 HDSBZMRLPLPFLQ-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 235000010987 pectin Nutrition 0.000 description 3
- 239000001814 pectin Substances 0.000 description 3
- 229920001277 pectin Polymers 0.000 description 3
- 239000000770 propane-1,2-diol alginate Substances 0.000 description 3
- 235000010409 propane-1,2-diol alginate Nutrition 0.000 description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- AEMOLEFTQBMNLQ-AZLKCVHYSA-N (2r,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-AZLKCVHYSA-N 0.000 description 1
- AEMOLEFTQBMNLQ-SYJWYVCOSA-N (2s,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-SYJWYVCOSA-N 0.000 description 1
- RMGHERXMTMUMMV-UHFFFAOYSA-N 2-methoxypropane Chemical compound COC(C)C RMGHERXMTMUMMV-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- RMOUBSOVHSONPZ-UHFFFAOYSA-N Isopropyl formate Chemical compound CC(C)OC=O RMOUBSOVHSONPZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000006058 Ugi-reaction Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002527 isonitriles Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0084—Guluromannuronans, e.g. alginic acid, i.e. D-mannuronic acid and D-guluronic acid units linked with alternating alpha- and beta-1,4-glycosidic bonds; Derivatives thereof, e.g. alginates
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The present invention discloses a kind of preparation method of high esterification degree seaweed isopropyl propionate, preparation method includes the following steps: in anhydrous isopropyl alcohol, alginic acid is added, start stirring, it is added and the equimolar dehydrating agent of alginic acid water content, catalyst is added, stirring is warming up to reflux, after reaching reflux temperature, start that remaining dehydrating agent is added dropwise, after being dropped evenly in 2-4 hours, continue back flow reaction 4 ~ 15 hours, reaction was completed, after being cooled to room temperature, with lye pH adjustment=6.5 ~ 7.0, filtering, isopropanol water solution of the filter cake with mass concentration higher than 60% washs, and it is dry at 40 DEG C, obtain seaweed isopropyl propionate；The esterification degree of the seaweed isopropyl propionate prepared using the preparation method of seaweed isopropyl propionate of the present invention is higher than 65%, hence it is evident that higher than the esterification degree of the linear alcohols alginic acid ester of prior art preparation.
Description
Technical field
The present invention relates to a kind of preparation methods of alginic acid ester, more particularly to a kind of high esterification degree seaweed isopropyl propionate
Preparation method.
Background technique
Alginic acid is mainly derived from brown alga plant and bacterium, and molecular formula is (C6H7O6Na)n, relative molecular weight is in 32000-
Between 200000, it is one that molecule, which is formed by beta-D-mannuronic acid and α-L- guluronic acid by (1 → 4) glycosidic bond links,
The linear polyanion water soluble carbohydrates of kind.Alginic acid is white or pale yellow powder insoluble in methanol, ethyl alcohol, DMF etc.
Organic solvent.Degradation reaction can all occur under acid, alkalinity and hot conditions, lead to the quick reduction of molecular weight.Therefore exist
Low temperature should be placed on during storage, in environment drying, divulged information, be protected from light.
The higher alginic acid derivative of commercialization degree mainly includes sodium alginate and polyetylene glycol alginate at present.As
A kind of biodegradable fully natural green high molecular material, and there is nontoxic, tasteless, gelation, stability, thickening property, cream
The features such as property changed, suspension and film forming, is widely used to the neck such as food, medicine, weaving, agricultural and wastewater treatment at present
Domain.
Though alginic acid is insoluble in the organic solvents such as alcohol, ethylene oxide and propylene oxide, to it with certain swellability,
Because intramolecular contains carboxyl, therefore in the presence of acid or basic catalyst, can same alkylol, propylene oxide or ethylene oxide etc.
Esterifying reagent directly occurs esterification and generates alginic acid ester.Propylene oxide and reacting ethylene oxide activity are higher, in Tong Hai
Alginic acid occurs not generate hydrone in esterification reaction process, is conducive to balanced reaction and carries out to positive direction, therefore esterification degree is higher,
For example, carrying out esterification using propylene oxide and alginic acid prepares propylene glycol alginate (PGA), esterification degree can reach 90% or more.
However, since esterification can generate hydrone, and hydrone and small-molecule starting material alcohol have for alkanol direct-connected for small molecule
There are compatibility or compatibility higher, it is difficult to be separated from each other, therefore even if promote esterification to positive direction using excessive alcohol
It carries out, esterification is also difficult to obtain high esterification degree alginic acid ester, and esterification degree is usually less than 20%.Such as Broderick
(Broderick E, Lyons H, Pembroke T, the et al. The characterization of a such as Eilish
novel, covalently modified, amphiphilic alginate derivative, which retains
gelling and non-toxic properties[J]. Journal of colloid and interface
Science, 2006,298 (1): 154-161.) sulphur acid as catalyst is used, it is anti-using alginic acid and excessive butanol direct esterification
Seaweed acid butyl ester should be prepared, when esterification reaches balance, esterification degree is lower than 20%；For long chain alkanol, due to seaweed
The compatibility of acid is poor, and reactivity is lower, therefore even if being easy to the hydrone separation that same esterification generates, esterification journey
Degree is relatively low.Preparation for alginic acid long-chain alcohol ester generallys use Ugi reaction (Ugi I. The α-at present
Addition of Immonium Ions and Anions to Isonitriles Accompanied by Secondary
Reactions[J]. Angewandte Chemie International Edition in English, 1962, 1(1):
It 8-21) prepares, but the esterification degree of alginic acid ester prepared by this method is also usually less than 20%.Just at present it has been reported that
It directlys adopt alginic acid and linear alcohols carries out esterification to prepare alginic acid ester, esterification degree is usually less than 50%.
Three isopropyl ester of orthoformic acid also known as three isopropoxy methane, are a kind of colourless liquids, inflammable, can be dissolved in methanol, second
The important organic synthesis intermediate of one kind of the organic solvents such as alcohol, isopropanol.Three isopropyl ester of orthoformic acid is met water and is decomposed, and generates different
Propyl alcohol and isopropyl formate, therefore dehydrating agent use can be used as in the preparation process of seaweed isopropyl propionate.
It is an object of the invention to provide a kind of preparation methods of high esterification degree seaweed isopropyl propionate, are easy to get for raw material, can
Biodegradable fully natural green macromolecule polysaccharide alginic acid opens up new space.
Compared with existing linear alcohols alginic acid ester technology of preparing, the esterification degree of seaweed isopropyl propionate prepared by the present invention can
Reach 65% or more.
Summary of the invention
A kind of preparation method of high esterification degree seaweed isopropyl propionate, it is characterised in that implement as follows: anhydrous different
In propyl alcohol, alginic acid is added, starts stirring, is added and stirs and rise with the equimolar dehydrating agent of alginic acid water content, addition catalyst
Temperature after reaching reflux temperature, starts that remaining dehydrating agent is added dropwise, after dropping evenly in 2-4 hours, continues to flow back to flowing back
Reaction 4 ~ 15 hours, reaction was completed, and after being cooled to room temperature, with lye pH adjustment=6.5 ~ 7.0, filtering, filter cake are higher than with mass concentration
60% isopropanol water solution washing, and it is dry at 40 DEG C, obtain seaweed isopropyl propionate；Alginic acid dosage described above with it is different
The mass ratio of propyl alcohol dosage is 1:3 ~ 6；Dehydrating agent described above is three isopropyl ester of orthoformic acid；Dropwise addition residue described above is de-
Aqua is that three isopropyl ester of remaining orthoformic acid is added dropwise, and the molar ratio of dripping quantity and alginic acid dosage is 1:0.5-1；It is described above
Catalyst be the concentrated sulfuric acid or p-methyl benzenesulfonic acid that mass concentration is 98%, dosage is the mass percent of alginic acid dosage
0.2-3%；Lye described above is sodium carbonate liquor or sodium hydroxide solution.
Using the preparation method of seaweed isopropyl propionate of the present invention, the esterification degree of prepared seaweed isopropyl propionate is higher than 65%,
It is apparently higher than the esterification degree of the linear alcohols alginic acid ester of prior art preparation.This hair is further illustrated below by specific example
It is bright.
Specific embodiment
Embodiment 1
200g anhydrous isopropyl alcohol is added in 500ml four-hole boiling flask, the alginic acid 50g that water content is 6% is added, stirring is equal
It is even, the 0.4g concentrated sulfuric acid is added at room temperature and makees catalyst, is warming up to reflux temperature, back flow reaction 6h after mixing evenly, reaction terminates,
It is cooled to room temperature, adjusts pH to 6.5 ~ 7.0, filtering, filter cake mass concentration 70% with the aqueous sodium carbonate that mass concentration is 5%
Isopropanol water solution washing, dry under the conditions of 40 DEG C, seaweed isopropyl propionate is made.It tests and produces by national standard GB25533-2010
The esterification degree of product, the esterification degree of prepared seaweed isopropyl propionate are 53.44%；Use rotational viscometer distinguish test temperature for
25 DEG C, mass concentration 3%, the alginic acid and seaweed isopropyl propionate aqueous solution apparent viscosity of pH=7 obtain the table of sodium alginate soln
Sight viscosity is 157mPa.s；The apparent viscosity of seaweed isopropyl propionate solution is 39mPa.s.
Embodiment 2
200g anhydrous isopropyl alcohol is added in 500ml four-hole boiling flask, the alginic acid 50g that water content is 6% is added, stirring is equal
It is even, the three isopropyl ester 31.67g of orthoformic acid with alginic acid water content equimolar amounts is added at room temperature, adds 0.4g concentrated sulfuric acid work
Catalyst is warming up to reflux temperature after mixing evenly, is dropped evenly again in 2 hours into three isopropyl ester 29.5g of orthoformic acid.It adds
After continue to react at reflux 6 hours, reaction terminate be cooled to room temperature, with mass concentration be 5 % aqueous sodium carbonate
PH to 6.5 ~ 7.0 is adjusted, filtering, filter cake are washed with the isopropanol water solution of mass concentration 70%, dried under the conditions of 40 DEG C, are made
Obtain seaweed isopropyl propionate.The esterification degree of seaweed isopropyl propionate is 71.45% after tested.Temperature is 25 DEG C, mass concentration 3%, pH=
7 seaweed isopropyl propionate aqueous solution apparent viscosity is 58mPa.s.
Embodiment 3
With embodiment 1,0.4g concentrated sulfuric acid catalyst is only changed to 1.40g p-methyl benzenesulfonic acid and makees catalyst.Obtain alginic acid
Isopropyl ester.The esterification degree of seaweed isopropyl propionate is 55.13% after tested.Temperature is 25 DEG C, mass concentration 3%, the seaweed of pH=7
Isopropyl propionate aqueous solution apparent viscosity is 53mPa.s.
Embodiment 4
With embodiment 1,0.4g concentrated sulfuric acid catalyst is only changed to 0.6g concentrated sulfuric acid catalyst.Obtain seaweed isopropyl propionate.
The esterification degree of seaweed isopropyl propionate is 54.25% after tested.Temperature is 25 DEG C, mass concentration 3%, the seaweed isopropyl propionate of pH=7
Aqueous solution apparent viscosity is 36mPa.s.
Embodiment 5
With embodiment 2,0.4g concentrated sulfuric acid catalyst is only changed to 1.4g p-methyl benzenesulfonic acid and makees catalyst.It is different to obtain alginic acid
Propyl ester.The esterification degree of seaweed isopropyl propionate is 72.35% after tested.Temperature is 25 DEG C, mass concentration 3%, the alginic acid of pH=7
Isopropyl aqueous solution of ester apparent viscosity is 61mPa.s.
Embodiment 6
With embodiment 2,0.4g concentrated sulfuric acid catalyst is only changed to 1.2g p-methyl benzenesulfonic acid and makees catalyst.It is different to obtain alginic acid
Propyl ester.The esterification degree of seaweed isopropyl propionate is 71.32% after tested.Temperature is 25 DEG C, mass concentration 3%, the alginic acid of pH=7
Isopropyl aqueous solution of ester apparent viscosity is 63mPa.s.
As can be seen from the above-described embodiment, it under acid catalysis, is reacted, is made with the direct refuxing esterification of isopropanol alcohol by alginic acid
The esterification degree of standby seaweed isopropyl propionate is below 56%, and under identical enzymatic synthesis condition, three isopropyl of dehydrating agent orthoformic acid is added
The esterification degree of ester, seaweed isopropyl propionate is improved significantly, and esterification degree is above 70%；Using p-methyl benzenesulfonic acid do catalyst compared with
Catalyst is made using the concentrated sulfuric acid, the esterification degree of the seaweed isopropyl propionate of preparation is high.By alginic acid isopropyl prepared in the above embodiments
The solution viscosity of ester is all larger than 38mPa.s, is higher than commodity pectin solution viscosity (low ester: 37mPa.s；High ester: 18mPa.s), then
In addition seaweed isopropyl propionate structure and the structure of propylene glycol alginate and pectin have similarity, therefore seaweed isopropyl propionate has
The pectin of fictitious hosts valuableness is hoped to use.
Certainly, the above description is not a limitation of the present invention, and the present invention is also not limited to the example above, the art
Those of ordinary skill, within the essential scope of the present invention, variation, addition or the replacement made all should belong to guarantor of the invention
Protect range.
Claims (1)
1. a kind of preparation method of high esterification degree seaweed isopropyl propionate, it is characterised in that implement as follows: in anhydrous isopropyl
In alcohol, alginic acid is added, starts stirring, is added and the equimolar dehydrating agent of alginic acid water content, addition catalyst, stirring heating
To reflux, after reaching reflux temperature, start that remaining dehydrating agent is added dropwise, after dropping evenly in 2-4 hours, it is anti-to continue reflux
It answers 4 ~ 15 hours, reaction was completed, and after being cooled to room temperature, with lye pH adjustment=6.5 ~ 7.0, filtering, filter cake are higher than with mass concentration
60% isopropanol water solution washing, and it is dry at 40 DEG C, obtain seaweed isopropyl propionate；Alginic acid dosage described above with it is different
The mass ratio of propyl alcohol dosage is 1:3 ~ 6；Dehydrating agent described above is three isopropyl ester of orthoformic acid；Dropwise addition residue described above is de-
Aqua is that three isopropyl ester of remaining orthoformic acid is added dropwise, and the molar ratio of dripping quantity and alginic acid dosage is 1:0.5-1；It is described above
Catalyst be the concentrated sulfuric acid or p-methyl benzenesulfonic acid that mass concentration is 98%, dosage is the mass percent of alginic acid dosage
0.2-3%；Lye described above is sodium carbonate liquor or sodium hydroxide solution.
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Non-Patent Citations (2)
| Title |
|---|
| The characterisation of a novel, covalently modified, amphiphilic alginate derivative, which retains gelling and non-toxic properties;Eilish Broderick等;《Journal of Colloid and Interface Science》;20060118;第298卷;第154-161页 * |
| The α-Addition of Immonium Ions and Anions to Isonitriles Accompanied by Secondary Reactions;DOZ. DR. IVAR UGI;《Angew. Chem. internat. Edit.》;19620127;第1卷(第1期);第8-21页 * |
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