CN110452115A - A kind of synthetic method of poly 3-hydroxy butyrate quasi-oligomer and its obtained product and purposes - Google Patents
A kind of synthetic method of poly 3-hydroxy butyrate quasi-oligomer and its obtained product and purposes Download PDFInfo
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- CN110452115A CN110452115A CN201810431506.6A CN201810431506A CN110452115A CN 110452115 A CN110452115 A CN 110452115A CN 201810431506 A CN201810431506 A CN 201810431506A CN 110452115 A CN110452115 A CN 110452115A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
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Abstract
The present invention provides a kind of synthetic methods of poly 3-hydroxy butyrate quasi-oligomer, using lactone as raw material, at aluminum alkoxide Al (OR)3The oligomer is made with reaction in the presence of pyridine.The present invention also provides a kind of poly 3-hydroxy butyrate quasi-oligomer and its preparing the purposes in anti-biotic material.The lower poly 3-hydroxy butyrate quasi-oligomer of molecular weight can be made in synthetic method provided by the invention, which has excellent and stablize lasting antibacterial activity, be highly suitable as anti-biotic material.Synthesising method reacting condition of the invention is mild, and purifying process also greatly simplifies, and is suitable for industrialized production and large-scale use.
Description
Technical field
The present invention relates to chemosynthesis technical fields, and in particular to a kind of synthesis side of poly 3-hydroxy butyrate quasi-oligomer
Method, thus obtained oligomer product and its purposes.
Background technique
Poly 3-hydroxy butyrate (PHB) is a kind of biodegradable plastic generated by microbial fermentation, as a kind of micro-
The nutrition of biology and ergastic substances, PHB have excellent biocompatibility, and catabolite also belongs to human body natural component, because
The characteristic of its nontoxic residue-free is widely used in the fields such as weaving, food packaging, drug release, tissue engineering bracket.
High molecular weight PHB mainly passes through microbial fermentation (biochemical method) and chemical synthesis obtains.Biochemical method native annulus
It protects, it is safe and non-toxic, but the production cycle is long, purification and high process cost can be greatly lowered into using chemical synthesis
This, and its bioactivity will not change.Since 3-hydroxybutyrate is by thermally labile, chemical synthesis is often with beta-butyrolactone
Monomer, alkyl or metal alkoxides complex are catalyst, and it is tens of thousands of to hundreds of thousands of to prepare molecular weight by the method for ring-opening polymerisation
PHB.
About the degree of polymerization lower than 100, even lower than 20 oligomerization PHB, also have been reported that it has prevention sclerotin and dredges in recent years
Loose isoreactivity, but for preparation method, more or PHB using high molecular weight is made by hydrolysis or enzymatic hydrolysis.
Summary of the invention
To overcome limitation existing for oligomerization PHB preparation method in the prior art, an object of the present invention is to provide one
The synthetic method of kind poly 3-hydroxy butyrate quasi-oligomer.
It is a further object of the present invention to provide a kind of poly 3-hydroxy butyrate quasi-oligomers.
A further object of the invention is to provide the purposes of the poly 3-hydroxy butyrate quasi-oligomer.
A further object of the invention is to provide a kind of bio-based materials with antibacterial action.
The present invention provides the synthetic methods of one kind poly 3-hydroxy butyrate quasi-oligomer as shown in formula (1), with formula (2)
Shown in lactone be raw material, at aluminum alkoxide Al (OR)3The oligomer is made with reaction in the presence of pyridine,
In formula (1) and formula (2), R ' indicates hydrogen or C1~C5Alkyl, R indicate C1~C5Alkyl, m indicate 0~3 it is whole
Number, n indicate 1~20 integer.
Reaction route are as follows:
In existing PHB quasi polymer synthetic technology, use the lactone compounds such as beta-butyrolactone for raw material, aluminum alkoxide
Chemical synthesis process as catalyst has the following deficiencies: that (1) reaction raw materials need to be handled by stringent anhydrous and oxygen-free, and is catalyzed
Agent needs are slowly added dropwise among reaction system, and operation requires harsh；(2) reaction process needs higher temperature and longer anti-
Between seasonable；(3) for oligomer molecules amount made from generally in 2000-5000, the end group of reaction product is alkyl and hydroxyl；(4) anti-
The aluminium salt for answering system to generate is difficult to be removed, and excess EDTA solution need to be used to wash repeatedly, purification process is cumbersome.
Present inventor have discovered that carrying out open loop in the presence of aluminum alkoxide and common pyridine using lactone compound as raw material
It polymerize changeable above situation, the lower oligomer of molecular weight can be made, exists without solvent, reaction process is without height
Temperature is reacted for a long time, and method of purification can also significantly simplify.The addition for being presumably due to pyridine can be coordinated to destroy with aluminium
The tetramer structure of aluminum alkoxide, to reduce reaction temperature, improve reaction rate, the molecular weight of resulting polymers also can
Enough control is in lower level, moreover, pyridine itself also can be used as reaction medium.
In poly 3-hydroxy butyrate quasi-oligomer made from synthetic method of the present invention, end group is respectively alkoxy and double bond,
Alkoxy derives from aluminum alkoxide, and it is obtained by hydroxyls dehydrate that double bond, which then speculates,.
In synthetic method provided by the invention, oligomer shown in formula (1) is preferably few poly 3-hydroxy butyrate, and number is equal
Molecular weight can be 1000 or less.
In synthetic method provided by the invention, the aluminum alkoxide Al (OR)3It can be used in being catalyzed β-to be existing
The all kinds of butyrolactone ring-opening polymerisation preferably can be the aluminum alkoxide of low alkyl group, and more preferable R is the alkyl of C1~C5,
Including but not limited to methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl etc..
In synthetic method provided by the invention, pyridine, which also can be replaced, can be coordinated with aluminium and have certain weakly alkaline pyridine
Analog.
In synthetic method provided by the invention, the aluminum alkoxide Al (OR)3Mole dosage ratio with pyridine can be 1 ﹕ 1
~5；It is preferred that can be 1 ﹕ 1~2.
In synthetic method provided by the invention, the aluminum alkoxide Al (OR)3With the mole dosage of lactone shown in formula (2)
It preferably can be 1 ﹕ 10~30 than that can be 1 ﹕ 10~50.
In synthetic method provided by the invention, the ring-opening polymerization of lactone can carry out at lower temperature, when reaction
Between can also be obviously shortened, can be adjusted by those skilled in the art according to response situation；It is preferred that can be that will react on 30~60 DEG C
It is lower to carry out 10~40 hours；It can more preferably be carried out 20~30 hours for that will react at 40~60 DEG C.
In synthetic method provided by the invention, reaction system generation can be removed using dilute acid soln washing after completion of the reaction
Aluminium salt.Wherein, dilute acid soln can be able to be 1~5M for solution, molar concentrations such as common dilute hydrochloric acid, dilute sulfuric acids.
Shown in poly 3-hydroxy butyrate quasi-oligomer provided by the invention such as formula (1),
The definition of each group is identical as aforementioned definitions in formula (1).
It is preferable to use the described in any item synthetic methods of preceding solution to be made for oligomer provided by the invention.
Oligomer provided by the invention is preferably widow's poly 3-hydroxy butyrate shown in formula (3),
In formula (3), n is preferably represented by 1~6 integer.
The number-average molecular weight of widow's poly 3-hydroxy butyrate provided by the invention can be 1000 or less.
It is (including oligomeric shown in formula (1) and formula (3) that the present invention also provides the poly 3-hydroxy butyrate quasi-oligomers
Object) preparing the purposes in anti-biotic material.
Present inventor have discovered that have very excellent antibacterial activity using oligomer made from synthetic method of the invention,
> 99.99% can reach for the antibacterial effect of staphylococcus aureus, pneumobacillus, Candida albicans, there is broad-spectrum antiseptic
Effect.Thus poly 3-hydroxy butyrate quasi-oligomer product of the invention is particularly suitable for preparing anti-biotic material.
Anti-biotic material of the present invention can be any form or type, as long as can be low by poly 3-hydroxy butyrate class
Polymers (including oligomer shown in formula (1) and formula (3)) applies in anti-biotic material as Antibacterial Constituents, and does not influence to live
The antibacterial activity of property ingredient.Including but not limited to antibiotic preparation, antibiotic fabric, amenities, medical material etc., it is especially suitable
For weaving, the fields such as health care.Such as combinable or modified existing polymer textiles, then for example for antibiotic preparation,
It may be used as the preparations such as drug, disinfectant, in another example being used for medical material, can be used for wound covering material, dressing, operation stitching
Line, implantation material, pharmaceutical carrier and other biological medical material.Anti-biotic material of the present invention can be used alone, can also
It is used in combination with other antibiotic preparations, anti-biotic material, can also be used to be modified or be transformed other anti-biotic materials.
The present invention also provides a kind of bio-based materials with antibacterial action, uses and gather described in above technical scheme
3-hydroxybutyrate oligoesters (including oligomer shown in formula (1) and formula (3)) is used as Antibacterial Constituents.
In bio-based materials of the present invention with antibacterial action, except using poly 3-hydroxy butyrate quasi-oligomer to make
Except active constituent, any adding ingredient outside active constituent that can also use comprising existing anti-biotic material, added material,
Auxiliary substance etc. as long as active constituent can be made to the anti-biotic material of arbitrary form or type, and does not influence active constituent
Antibacterial activity, the present invention is with no restrictions.
The lower poly- 3- of molecular weight can be made in the synthetic method of poly 3-hydroxy butyrate quasi-oligomer provided by the invention
Hydroxybutyric acid oligoesters, obtained oligomer have excellent and stablize lasting antibacterial activity, all to various bacteria, fungi
Have significant antibacterial effect, but also there are the performances such as excellent biodegradability, biocompatibility, is highly suitable as
Anti-biotic material, the especially fields such as weaving, health care anti-biotic material.
Synthesising method reacting condition of the invention is mild, and the raw material used needs not move through anhydrous and oxygen-free processing, without making
With solvent, reaction temperature be can obviously reduce, and the reaction time can also be obviously shortened, and purifying process after completion of the reaction is also significantly simple
Change, target product yield is high.In terms of comprehensive, production cost can be greatly reduced in synthetic method of the invention, improve production process
Safety is highly suitable for industrialized production and large-scale use.
Detailed description of the invention
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of widow's poly 3-hydroxy butyrate made from embodiment；
Fig. 2 is the nuclear-magnetism carbon spectrogram of widow's poly 3-hydroxy butyrate made from embodiment；
Fig. 3 is the High Performance Liquid Chromatography/Mass Spectrometry figure of widow's poly 3-hydroxy butyrate made from embodiment；
Fig. 4 is the infrared spectrogram of widow's poly 3-hydroxy butyrate made from embodiment.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, it will be further described below example of the invention
The technical solution of property embodiment.
Chemical reagent used in following embodiment is then unless otherwise instructed commercial goods, used in following embodiment
Operation or instrument are then this field common operation or instrument unless otherwise instructed.
Embodiment
Aluminum isopropoxide 0.61g (3mmol), pyridine 2.5mL and beta-butyrolactone 5.2g (60mmol) are added in the reactor,
50 DEG C of reactions under conditions of nitrogen protection.After reaction about 15 minutes, reaction solution is in glassy yellow, greening after a period of time, later
Color is gradually deepened, and reaction became sepia after 24 hours.Reaction terminates after being cooled to room temperature, and 20mL 2M is added in reaction solution
In dilute hydrochloric acid, stir a period of time after with 20mL methylene chloride extraction three times, merge organic layer, successively with dilute hydrochloric acid (20mL ×
2), 2M solution of potassium carbonate (20mL × 1) and deionized water (20mL × 2) wash organic layer.It depressurizes and steams after anhydrous sodium sulfate is dry
Distillation goes solvent to obtain yellow oil.Gained grease quickly rushes column purification with methylene chloride, after vacuum distillation removes solvent
50 DEG C are dried in vacuum overnight, and obtain light yellow oil 4.0g, yield 77%.
Appropriate above-mentioned product is taken to be dissolved in deuterated chloroform (CDCl3) in, oligomerization 3-hydroxybutyrate is obtained by nuclear magnetic resonance
The nucleus magnetic hydrogen spectrum (as shown in Figure 1) and carbon of ester compose (as shown in Figure 2).
Appropriate above-mentioned product is taken to be dissolved in 1:1 methylene chloride/methanol mixed solution, 0.45 μm of filtering with microporous membrane leads to
It crosses high performance liquid chromatography-mass spectrograph and obtains High Performance Liquid Chromatography/Mass Spectrometry (HPLC-MS) figure (such as Fig. 3 of few poly 3-hydroxy butyrate
It is shown).
Appropriate above-mentioned product is taken to obtain the infrared figure (as shown in Figure 4) of few poly 3-hydroxy butyrate by infrared spectrometer.
By nucleus magnetic hydrogen spectrum (1H NMR), nuclear-magnetism carbon spectrum (13C NMR), High Performance Liquid Chromatography/Mass Spectrometry (HPLC-MS) and
Infrared spectroscopy (IR) is characterized, and determines its structure are as follows:
The peak M+1 that corresponding polymerization degree n is 1-6 can be found by LC-MS spectrogram, therefore the n in the structural formula is 1-6.
Experimental example
Widow's poly 3-hydroxy butyrate made from embodiment is diluted to 20mg/mL with phosphate buffer (PBS), shakes method
(referring to national standard method GB-T20944.3-2008) detects its antibacterial activity, and PBS group does blank control.Gained anti-microbial property
The results are shown in Table 1.
Table 1
As seen from the results in Table 1: widow's poly 3-hydroxy butyrate is to staphylococcus aureus, lung made from synthetic method of the present invention
The various bacterias such as scorching bacillus, Candida albicans, fungi all have efficient antibacterial action, and antibacterial effect can reach > 99.99%,
But also has the effect of broad-spectrum antiseptic.
Few poly 3-hydroxy butyrate is repeated as many times above-mentioned experiment, each experimental result is shown greater than 99.99%
Antibacterial activity.It places at room temperature and half a year and then detects antibacterial activity as procedure described above, still be able to have and be greater than
99.99% antibacterial activity, it is seen that its property is stablized, and antibacterial activity is stable and lasting.
Although the preferred embodiments of the invention, those skilled in the art has been disclosed in order to illustrate the present invention
Member can be the present invention it should be appreciated that in the case where not departing from present inventive concept defined by claims and range
Various modifications, addition and replacement out.
Claims (11)
1. a kind of synthetic method of the poly 3-hydroxy butyrate quasi-oligomer as shown in formula (1), is original with lactone shown in formula (2)
Material, at aluminum alkoxide Al (OR)3The oligomer is made with reaction in the presence of pyridine,
In formula (1) and formula (2), R ' indicates hydrogen or C1~C5Alkyl, R indicate C1~C5Alkyl, m indicate 0~3 integer, n table
Show 1~20 integer.
2. synthetic method according to claim 1, which is characterized in that oligomer shown in the formula (1) is oligomerization 3- hydroxyl
Base butyrate, number-average molecular weight are 1000 or less.
3. synthetic method according to claim 1 or 2, which is characterized in that the aluminum alkoxide Al (OR)3With rubbing for pyridine
Your amount ratio is 1 ﹕ 1~5.
4. synthetic method according to claim 1-3, which is characterized in that the aluminum alkoxide Al (OR)3And formula
(2) the mole dosage ratio of lactone shown in is 1 ﹕ 10~50.
5. synthetic method according to claim 1-4, which is characterized in that react at 30~60 DEG C carry out 10~
40 hours.
6. synthetic method according to claim 5, which is characterized in that use dilute acid soln washing to remove after completion of the reaction
The aluminium salt that reaction system generates.
7. a kind of poly 3-hydroxy butyrate quasi-oligomer as shown in formula (1),
In formula (1), R ' indicates hydrogen or C1~C5Alkyl, R indicate C1~C5Alkyl, m indicate 0~3 integer, n indicate 1~20
Integer.
8. oligomer according to claim 7, which is characterized in that the oligomer is oligomerization 3- hydroxyl shown in formula (3)
Butyrate,
In formula (3), n indicates 1~6 integer.
9. poly 3-hydroxy butyrate quasi-oligomer described in claim 7 or 8 is preparing the purposes in anti-biotic material.
10. purposes according to claim 9, which is characterized in that the anti-biotic material is antibiotic preparation, antibiotic fabric, defends
One of raw articles, medical material are a variety of.
11. a kind of bio-based materials with antibacterial action, which is characterized in that including poly- 3- hydroxyl described in claim 7 or 8
Butyric acid ester oligomer is as Antibacterial Constituents.
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Cited By (3)
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| CN113200849A (en) * | 2021-04-27 | 2021-08-03 | 香港理工大学 | Separation and purification method of synthesized 3-hydroxybutyrate oligomer or oligomer and application of synthesized 3-hydroxybutyrate oligomer or oligomer in antibacterial and antiviral products |
| EP3988536A1 (en) | 2020-10-26 | 2022-04-27 | Zhejiang Enmat Biological Technology Co., Ltd. | Efficient anti-bacterial hydroxy acid ester oligomer |
| CN115821426A (en) * | 2022-12-16 | 2023-03-21 | 扬州富威尔复合材料有限公司 | Crystalline bio-based low-melting-point polyester composite fiber with antibacterial function and preparation method thereof |
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| CN115821426A (en) * | 2022-12-16 | 2023-03-21 | 扬州富威尔复合材料有限公司 | Crystalline bio-based low-melting-point polyester composite fiber with antibacterial function and preparation method thereof |
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