CN108504074A - Methylene blue is used as the purposes of polymerization inhibitor under anaerobic or hypoxia condition - Google Patents
Methylene blue is used as the purposes of polymerization inhibitor under anaerobic or hypoxia condition Download PDFInfo
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- CN108504074A CN108504074A CN201710106800.5A CN201710106800A CN108504074A CN 108504074 A CN108504074 A CN 108504074A CN 201710106800 A CN201710106800 A CN 201710106800A CN 108504074 A CN108504074 A CN 108504074A
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- methylene blue
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/45—Heterocyclic compounds having sulfur in the ring
- C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/02—Applications for biomedical use
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Abstract
The invention belongs to polymerization inhibitor fields, are related to the purposes that methylene blue is used as polymerization inhibitor under anaerobic or hypoxia condition.By methylene blue the spontaneous polymerization of the polymerizable compound can be inhibited after concentration incorporation (methyl) acrylic compounds or (methyl) esters of acrylic acid polymerizable compound of 0.001%~0.5%wt under the conditions of 5%v/v and oxygen concentration below, improve its stability in manufacture, transport and storage process, it can be used for field of medicaments, the application range of methylene blue is enriched, while having widened the suitable application area of polymerizable compound.
Description
Technical field
The invention belongs to polymerization inhibitor fields, are related to methylene blue and are used as polymerization inhibitor under anaerobic or hypoxia condition
Purposes.
Background technology
In general, conjugated system refers to singly-bound and Multiple Bonds (including two keys and three keys) alternately arranged system, and with conjugation
The group of system is then referred to as being conjugated unsaturated group or is conjugated group.Since the unsaturated bond in conjugation unsaturated group can be with
Addition reaction occurs, therefore the compound with conjugation unsaturated group can generally aggregate into high-molecular compound so that
Such compound has polymerizability.
With conjugation unsaturated group polymerizable compound be currently known be used to prepare biodegradable material
Quality raw materials.One kind is disclosed in 01/92584 A1 of WO, and matrix material is formed by conjugation unsaturated group by nucleophilic addition
The method of material, the host material can discharge drug activity compound in connection in a controlled manner.WO 00/44808
One kind is disclosed in A1, and polymeric biomaterial method is formed by conjugation unsaturated group by nucleophilic addition, it is obtained
Aquogel type material may be used as glue or sealant, or be used for organizational project and wound healing.
It is anti-since so-called polymerization " out of control " may occur in the manufacture, transport and storage process of polymerizable compound
It answers, the weight of monomer is not only made to incur loss, can also incur even more serious safety problem.Especially in field of medicaments, nothing
By being that raw material or product all must satisfy certain purity requirement, and " out of control " polymerisation can then influence nucleophilic addition
Stoichiometry, and monomer can be caused prematurely to polymerize.
In past many decades, domestic and international scientific research personnel has been carried out for inhibiting polymerizable compound (such as (first
Base) acrylic compounds and (methyl) esters of acrylic acid etc.) polymerization research, and produced many effective Inhibition of polymerization
Agent, to prevent free radical polymerization.For example, as strong polymerization inhibitor, hydroquinone monomethyl ether (MEHQ) is with 200ppm
Concentration the polymerization of acrylic acid can be inhibited (referring to S.Schulze, H.Vogel, Aspects of when being present in acrylic acid
the safe storage of acrylic monomers:kinetics of the oxygen consumption[J],
Chem.Eng.Technol.,1998,21(10):829-836).But this polymerization inhibitor can only be sent out in the presence of oxygen
The effect of waving.For the pharmaceutical composition comprising polymerizable compound and oxygen sensitivity component, hydroquinone monomethyl ether is just not
It is adapted for use as polymerization inhibitor again, reason is that oxygen can influence the steady in a long-term of oxygen sensitivity component in the pharmaceutical composition
Property (such as polyethylene glycol can form peroxide in the presence of oxygen).
Another industrial common polymerization inhibitor is phenthazine (PTZ).Compared with hydroquinone monomethyl ether, phenthazine
Also have higher polymerization inhibiting activity (referring to Leon B.Levy, Inhibition of acrylic under anaerobic
acid polymerization by phenothiazine and p-methoxyphenol.II.Catalytic
inhibition by phenothiazine[J],J.Polymer Science:Part A:Polymer Chemistry,
1992,30(4):569-576).However, since the compound is famous with characteristics such as desinsection, antibacterial and expelling parasites, and entering
It will produce many adverse reactions (such as influence, neuromuscular problem and photosensitization to blood constituent after animal body and human body
Deng) (referring to Mitchell.S.C., The Toxicity of Phenothiazine [J], Drug metabolism and
Drug interactions,1994,11:204-235), it therefore when needing to add polymerization inhibitor in medical composition, answers
When using phenothiazinyl polymerization inhibitor with caution.
Methylene blue (also known as methylene blue, alkaline acid blue, methylene blue etc., abbreviation MB) is a kind of phenthazine salt, chemical name
For bis- (dimethylamino) phenthazine -5- chlorides of 3,7-, chemical formula C16H18ClN3S, molecular weight 319.86, fusing point are
215 DEG C, flash-point is 14 DEG C, density 1g/mL, and water-soluble and ethyl alcohol does not dissolve in ethers.Methylene blue is relatively steady in air
Fixed, aqueous solution is toxic in alkalinity.Methylene blue is widely used in chemical indicator, dyestuff, biological stain etc.,
It is medically often used as pigment, and there is biocompatibility.But it there is no so far both at home and abroad and methylene blue (especially exist
Under anaerobic or hypoxia condition) it is used as the report of polymerization inhibitor.
Invention content
In order to widen the application range of methylene blue, its effect in terms of inhibiting polymerizable compound polymerization is specified, originally
Invention is intended to provide the purposes that methylene blue is used as polymerization inhibitor.By the way that methylene blue is had altogether with certain concentration incorporation
In the polymerizable compound of yoke unsaturated group, it can prevent polymerizable compound from occurring in manufacture, transport or storage process
" out of control " polymerisation.
Specifically, the present invention adopts the following technical scheme that：
Methylene blue is used as the purposes of polymerization inhibitor under anaerobic or hypoxia condition.
In such use, the oxygen concentration of the hypoxia condition is less than 5%v/v, preferably smaller than 2%v/v, more preferably less than
0.5%v/v.The present invention is not it has surprisingly been found that anaerobic or hypoxia condition interfere with the work of the methylene blue as polymerization inhibitor
Property.Since methylene blue has the ability for serving as polymerization inhibitor under anaerobic or hypoxia condition, can be applied in argon
The pharmaceutical composition stored in the gases such as gas, nitrogen avoids damage of the oxygen for pharmaceutical composition stability, overcomes aerobic
The intrinsic defect of type polymerization inhibitor.
In such use, the methylene blue is used as the poly- of the polymerizable compound with conjugation unsaturated group
Close inhibitor.
Preferably, with methylene blue:Polymerizable compound=0.001~0.5 with conjugation unsaturated group:100
The methylene blue is incorporated into the polymerizable compound with conjugation unsaturated group, is inhibited with realizing by weight ratio
The effect of polymerizable compound polymerization；It is furthermore preferred that with methylene blue:Polymerizable compound with conjugation unsaturated group=
0.002~0.1:100 weight ratio is mixed.
Inventors have surprisingly found that under anaerobic or hypoxia condition, with methylene blue:With conjugation unsaturated group
Polymerizable compound=0.01:100 weight ratio mixed into polymerizable compound the polymerization-inhibiting effects ratio of methylene blue with
Methylene blue:Polymerizable compound=0.1 with conjugation unsaturated group:100 weight ratio (mix by 10 times of methylene blues
Enter amount) into polymerizable compound, incorporation phenthazine also wants ideal.
Preferably, (excellent comprising 2~10 in the molecular structure with the polymerizable compound for being conjugated unsaturated group
Select 4~8) there is the side chain of conjugation unsaturated group and the parent nucleus of 1 connection side chain.
In the above-mentioned polymerizable compound with conjugation unsaturated group, the conjugation unsaturated group is selected from 2- carboxyls
Vinyl, 2- carboxyl -2- methyl ethylenes, 2- alkoxy carbonyl groups vinyl, 2- alkoxy carbonyl group -2- methyl ethylenes, acryloyl-oxy
Base, methacryloxy, 3- (pyridine -2- bases) acryloxy, 3- (pyridin-4-yl) acryloxy, acrylamido,
In methacrylamido, 3- (pyridine -2- bases) acrylamido, 3- (pyridin-4-yl) acrylamido any one or
It is a variety of.
It is described that there is gathering for conjugation unsaturated group when the conjugation unsaturated group is 2- alkoxy carbonyl group vinyl
Polymerisable compounds include acrylate segments, and the acrylate segments are selected from methyl acrylate, ethyl acrylate, acrylic acid fourth
Any one or more in ester, 2-EHA, acrylic acid 2- hydroxy methacrylates, acrylic acid 2- hydroxy propyl ester segments.
It is described that there is conjugation unsaturated group when the conjugation unsaturated group is 2- alkoxy carbonyl group -2- methyl ethylenes
Group polymerizable compound include methacrylate segment, the methacrylate segment be selected from methyl methacrylate,
In butyl methacrylate, 2-hydroxyethyl methacrylate, methacrylic acid 2- hydroxy propyl ester segments any one or it is more
Kind.
In the above-mentioned side chain with conjugation unsaturated group, the conjugation unsaturated group is located at the end of the side chain
End.
In the above-mentioned side chain with conjugation unsaturated group, other than the conjugation unsaturated group, the side chain
Also include connection segment, the connection segment is the alkane chain or polymer chain of linear chain or branched chain.
When the connection segment is alkyl chain, the alkyl chain is optionally by hydroxyl, amino, alkyl, carboxyl, acyl-oxygen
Any one or more substitution in base, acylamino-, carbamyl, alkoxy carbonyl group.
When the connection segment is polymer chain, the polymer chain is selected from polyglycol chain, polyvinylpyrrolidone
In ketone chain, vinyl-vinyl pyrrolidinone copolymer chain, Ju Yi Xi oxazolins chain, ethylene-Yi Xi oxazolin copolymer chains
Any one, preferred polyethylene glycol (PEG) chain, more preferable repetitive unit number is the poly- second two of any integer in 2~200
Alcohol chain.
In the above-mentioned polymerizable compound with conjugation unsaturated group, the parent nucleus is atom (such as carbon atom, nitrogen
Atom, oxygen atom etc.) or molecule fragment (such as ethylene oxide and its polymer segments, polyalcohol and its polymer segments, sugar and
Its polymer segments etc.).
Compared with prior art, there are following advantages using the present invention of above-mentioned technical proposal：
1) it under normal conditions, is rich in if be used to prepare in the molecular structure of the polymerizable compound of biodegradable material
Side chain with conjugation unsaturated group causes it steady then the polymerizable compound just there is strong spontaneous polymerization to be inclined to
It is qualitative poor, and must be stored under anaerobic or hypoxia condition, and the present invention is it has surprisingly been found that methylene blue can be in nothing
The spontaneous polymerization for inhibiting above-mentioned polymerizable compound under oxygen or hypoxia condition improves it in manufacture, transport and storage process
Stability；
2) existing anaerobic or hypoxemia type polymerization inhibitor are not used to medical usage greatly most without biocompatibility,
Methylene blue inherently with good biocompatibility is used as the polymerization inhibitor for polymerizable compound by the present invention,
So that corresponding polymerizable compound can be used in field of medicaments, the application range of methylene blue is not only enriched, but also widen
The suitable application area of polymerizable compound；
3) when using methylene blue as polymerization inhibitor in field of medicaments, the intrinsic color of methylene blue can also
Improve medical product visibility and can identification, play a positive role.
Description of the drawings
Fig. 1 is the schematic diagram of Inhibition of polymerization effect of the different polymerization inhibitors to polymerizable compound.
Fig. 2 is different polymerization inhibitors makes polymerizable compound achieve the effect that 1% conversion ratio is illustrated at different temperatures
Figure.
Fig. 3 is the linear relationship schematic diagram of MB incorporations and the effect of its Inhibition of polymerization.
Fig. 4 is polymerization-inhibiting effects signal of the methylene blue under different polymer storage temperatures and different test temperatures
Figure.
Fig. 5 is the content signal of the acrylate group in sample under different polymer storage temperatures and different test temperatures
Figure.
Specific implementation mode
The technical solution in the present invention is made below in conjunction with the drawings and specific embodiments further elucidated above.Unless another
It is described, instrument, material and reagent used in the following example etc. can be obtained by routine business means.
Embodiment 1：Methylene blue inhibits the polymerization of polymerizable compound.
(also known as six is poly- with six glycerine for polymerizable compound (eight side chain polyethylene glycol 2000 acrylate) in the present embodiment
Glycerine or polyglycereol -6, CAS:It 36675-34-0) is used as parent nucleus, using acryloxy as conjugation unsaturated group, with poly- second
- 2000 chain of glycol is as connection segment, molecular formula C18H30O5-[O-(CH2CH2O)45- CO-CH=CH2]8。
5 part of eight side chain polyethylene glycol 2000 acrylate (each 100mg) is weighed, is polymerize respectively with variety classes and dosage
Inhibitor (methylene blue (MB)：0.1mg, 0.05mg and 0.01mg；Phenthazine (PTZ)：0.1mg；Hydroquinone monomethyl ether
(MEHQ)：0.1mg) mix, it is separately sampled after mixing, it is placed in DSC disks, the heating in nitrogen atmosphere is until completely poly-
It closes.
It is analyzed, is recorded in each when different heating rates (4,7,10 and 13K/min) according to ASTM E698 methods
The DSC curve (energy discharges and temperature) of kind sample, the results are shown in Figure 1.As shown in Figure 1, with the PTZ of same incorporation and
MEHQ is compared, and MB shows more superior property in terms of stablizing sample, effectively inhibits the polymerization of polymerizable compound.
In addition, also to each sample, (0 DEG C → 60 DEG C) reach time of 1% conversion ratio and are commented at different temperatures
It surveys, the results are shown in Figure 2.As shown in Figure 2, under conditions of same incorporation, various samples reach the time of 1% conversion ratio
Shorten with the raising of temperature, MEHQ can be completed 1% conversion ratio within about 1 day, PTZ about 100 days it
Inside can also it complete, and the time that MB is required to 100 days or more at any temperature could realize 1% conversion ratio, and mix
The influence measured for result is not notable, this also illustrates that MB has ideal inhibiting effect for polymerizable compound.
Embodiment 2：The incorporation quantity research of methylene blue as polymerization inhibitor.
For pair between the usage amount and the stability of eight side chain polyethylene glycol 2000 acrylate of clear methylene blue
It should be related to, have begun to carry out pressure test.
Eight side chain polyethylene glycol 2000 acrylate of brand-new are divided into 4 parts, mix the methylene of various concentration respectively
Base indigo plant (200,500,1000 and 2000ppm).Sample under each methylene blue incorporation of concentration is respectively weighed 2 parts, every part of 3g, point
It is not added in 20mL test tubes, with argon gas-sealed liquid (so that oxygen concentration reaches 5%v/v or less), and is capped closing.It will examination
Pipe checks sample daily in 70 DEG C of preservations, until sample polymerize completely, the results are shown in Figure 3.From the figure 3, it may be seen that methylene blue
Incorporation and stability between it is in a linear relationship, it was confirmed that the stabilizing effect be strictly realized by methylene blue.
Embodiment 3：Polymerization-inhibiting effects experiment of the methylene blue under condition of different temperatures.
To pass through freezing processing and 40 DEG C of pretreated eight side chains polyethylene glycol 2000 acrylate as polymerizable chemical combination
Object mixes appropriate methylene blue respectively, is used as test sample after mixing.Under conditions of oxygen concentration is less than 5%v/v,
By monitoring the methylene blue count in eight side chain polyethylene glycol 2000 acrylate in real time, methylene blue is investigated in different polymerizations
Polymerization-inhibiting effects under object storage temperature (freezing processing and 40 DEG C of pretreatments) and different test temperatures (5,25 and 40 DEG C),
As a result as shown in Figure 4 and Figure 5.
As shown in Figure 4, under all temperature conditions, with the passage of person's time, the concentration of methylene blue is all reducing, is showing
Methylene blue is playing its stabilization function, itself is also correspondingly consumed.After six months, the concentration of methylene blue reaches one
The numerical value of approximately constant, and when relative temperature is relatively low, this numerical value is just higher, shows by selecting appropriate low storage temperature,
The effect of methylene blue can be improved.
In addition, when detecting beginning, the methylene blue concentration being substantially reduced is shown by 40 DEG C of pretreated samples.But
It is, under 40 DEG C of test temperatures, after a period of time, pretreatment and non-pretreated sample levels become similar.40
After six months under DEG C test temperature, some eight side chain polyethylene glycol 2000 acrylic samples have occurred and that partly or entirely
Polymerization, this shows that there are a lower limits, and the methylene blue stabilization effect under it no longer shows.
As shown in Figure 5, in still unpolymerized eight side chains polyethylene glycol 2000 acrylic sample, acrylate group
Content entirely observation the period in be to maintain it is constant, this also demonstrate the methylene blue being present in sample be protection acrylate
The key component that group does not react.
Claims (9)
1. methylene blue is used as the purposes of polymerization inhibitor under anaerobic or hypoxia condition.
2. purposes according to claim 1, it is characterised in that：
The oxygen concentration of the hypoxia condition is less than 5%v/v.
3. purposes according to claim 1, it is characterised in that：
The methylene blue is used as the polymerization inhibitor for the polymerizable compound with conjugation unsaturated group.
4. purposes according to claim 3, it is characterised in that：
With methylene blue:Polymerizable compound=0.001~0.5 with conjugation unsaturated group:100 weight ratio, by institute
Methylene blue is stated to be incorporated into the polymerizable compound with conjugation unsaturated group.
5. purposes according to claim 3, it is characterised in that：
It is unsaturated with conjugation comprising 2~10 in the molecular structure of the polymerizable compound with conjugation unsaturated group
The parent nucleus of the side chain of group and 1 connection side chain.
6. purposes according to claim 5, it is characterised in that：
The conjugation unsaturated group be selected from 2- carboxy vinyls, 2- carboxyl -2- methyl ethylenes, 2- alkoxy carbonyl groups vinyl,
2- alkoxy carbonyl group -2- methyl ethylenes, acryloxy, methacryloxy, 3- (pyridine -2- bases) acryloxy, 3-
(pyridin-4-yl) acryloxy, acrylamido, methacrylamido, 3- (pyridine -2- bases) acrylamido, 3- (pyrroles
Pyridine -4- bases) any one or more in acrylamido.
7. purposes according to claim 5, it is characterised in that：
The conjugation unsaturated group is located at the end of the side chain.
8. purposes according to claim 5, it is characterised in that：
Other than the conjugation unsaturated group, the side chain also includes connection segment, and the connection segment is straight chain or branch
The alkane chain or polymer chain of chain.
9. purposes according to claim 5, it is characterised in that：
The parent nucleus is atom or molecule fragment, and the atom is carbon atom, nitrogen-atoms or oxygen atom, and the molecule fragment is ring
Oxidative ethane and its polymer segments, polyalcohol and its polymer segments or sugar and its polymer segments.
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| CN201710106800.5A CN108504074A (en) | 2017-02-27 | 2017-02-27 | Methylene blue is used as the purposes of polymerization inhibitor under anaerobic or hypoxia condition |
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| CN201710106800.5A CN108504074A (en) | 2017-02-27 | 2017-02-27 | Methylene blue is used as the purposes of polymerization inhibitor under anaerobic or hypoxia condition |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070066829A1 (en) * | 2004-06-16 | 2007-03-22 | Straumann Holding Ag | Methylene blue |
| CN103429630A (en) * | 2010-09-27 | 2013-12-04 | 罗地亚管理公司 | Controlled free-radical polymerization of N-vinyl lactams in aqueous medium |
-
2017
- 2017-02-27 CN CN201710106800.5A patent/CN108504074A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070066829A1 (en) * | 2004-06-16 | 2007-03-22 | Straumann Holding Ag | Methylene blue |
| US20080090979A1 (en) * | 2004-06-16 | 2008-04-17 | Straumann Holding Ag | Methylene blue |
| US20100216916A1 (en) * | 2004-06-16 | 2010-08-26 | Straumann Holding Ag | Methylene blue |
| CN103429630A (en) * | 2010-09-27 | 2013-12-04 | 罗地亚管理公司 | Controlled free-radical polymerization of N-vinyl lactams in aqueous medium |
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Application publication date: 20180907 |