CN107474239A - A kind of acrylate ended Phosphorylcholine base polyethylene glycol and preparation method thereof - Google Patents
A kind of acrylate ended Phosphorylcholine base polyethylene glycol and preparation method thereof Download PDFInfo
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- CN107474239A CN107474239A CN201710681598.9A CN201710681598A CN107474239A CN 107474239 A CN107474239 A CN 107474239A CN 201710681598 A CN201710681598 A CN 201710681598A CN 107474239 A CN107474239 A CN 107474239A
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- polyethylene glycol
- base polyethylene
- phosphorylcholine base
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- phosphorylcholine
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- CQPARQSKGUFYMN-UHFFFAOYSA-N C[N](C)(C)CC[U]C Chemical compound C[N](C)(C)CC[U]C CQPARQSKGUFYMN-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F120/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
- C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterized by the type of post-polymerisation functionalisation
- C08G2650/04—End-capping
Abstract
The invention discloses a kind of acrylate ended Phosphorylcholine base polyethylene glycol and preparation method thereof, its chemical structural formula is,Wherein, PC is
Description
Technical field
The present invention relates to technical field of biological materials is belonged to, more particularly to a kind of poly- second of acrylate ended Phosphorylcholine base
Glycol and preparation method thereof.
Background technology
Polyethylene glycol (PEG) is to be ratified by FDA for the high polymer material in organism, due to its good water solubility and
Biocompatibility is widely used in formulation art.PEG has hydrophily and pliability concurrently, is that improvement macromolecular is water miscible conventional
Material has very high hydrophily and compliance, and hydration PEG chains on the one hand can be formed with water, are formed based on stable space,
Platelet etc. is adsorbed in material surface；On the other hand, hydration PEG chains have relatively low surface energy, the water of formation in water
Miniflow can hinder the adhesion and deformation of protein.Therefore material surface modifying can be reached using PEG molecules and its derivative
To the hydrophilic effect of raising.
Phosphorylcholine (PC) is the terminal hydrophyllic group for forming the soft phosphatide of membrane structure unit, is the outer layer in extracellular tunic
Functional group, simultaneous with positive and negative xenogenesis electric charge, ability and hydrophilicity with stronger combination water, this structure and composition
The interaction of surface and physiological environment will not only adsorb and depositing proteins, will not also trigger platelet activation, cause to coagulate
The adverse reactions such as blood, there is good biocompatibility.
Phosphorylcholine base polyethylene glycol overcomes the exclusive use of PEG and PC compounds and is implanted into material in vivo, particularly long
In terms of phase implantation material, the problem of biocompatibility can not fully meet clinical requirement is still suffered from.Satisfaction is chronically implanted biological material
The requirement of material (particularly contacting blood in terms of) clinically biological environment compatibility, but it is as a kind of modified material, no
Easily with other product reaction bondeds, so as to greatly limit its application.
Patent CN102070780A discloses a kind of end that can improve blood compatibility and is connected with Phosphorylcholine group
Polyethylene glycol, its other end active group are hydroxyl, can be combined by the reaction of hydroxyl with other biomaterials, to improve life
The blood compatibility of thing material, so as to widen the application of Phosphorylcholine and polyethylene glycol, but due to being confined to hold hydroxyl
The chemical reaction that base participates in, application field are limited by larger.
The content of the invention
In order to solve the deficiencies in the prior art, an object of the present invention is to provide a kind of acrylate ended Phosphorylcholine
Base polyethylene glycol, it is double bond by end group hydroxyl modification, the introducing of active terminal double bond, it is used as a kind of modified material,
Carry out the reactions such as homopolymerization to be used alone or combined with carrying out addition, copolymerization, being crosslinked other biomaterials, so as to improve other biologies
The biocompatibility of material, particularly blood compatibility, so as to widen its application significantly.
To achieve these goals, the technical scheme is that：
A kind of acrylate ended Phosphorylcholine base polyethylene glycol, its chemical structural formula be,
Wherein, PC isN=4~50.
The second object of the present invention is to provide a kind of preparation side of aforesaid propylene acid esters end-blocking Phosphorylcholine base polyethylene glycol
Method, esterification acquisition is carried out using Phosphorylcholine base polyethylene glycol and acrylic acid, or using Phosphorylcholine base polyethylene glycol with
Acryloyl chloride carries out acyl chlorides and the nucleophilic substitution of hydroxyl obtains；
Wherein, the structural formula of Phosphorylcholine base polyethylene glycol is,
In structural formula, PC isN=4~50.
The third object of the present invention is to provide a kind of aforesaid propylene acid esters end-blocking Phosphorylcholine base polyethylene glycol and is preparing life
Application in thing macromolecular material.
The fourth object of the present invention is to provide a kind of polymer with biological function, and its raw material includes aforesaid propylene acid esters
Block Phosphorylcholine base polyethylene glycol.
Beneficial effects of the present invention are：
(1) introducing of active terminal double bond, it is made to be used as a kind of modified material, it is anti-to carry out homopolymerization etc. using active terminal double bond
It should be used alone or be combined with carrying out addition, copolymerization, being crosslinked other biomaterials, so as to improve the biofacies of other biomaterials
Capacitive, it is special for being blood compatibility, so as to widen its application significantly.
(2) preparation method of the invention is simple, be easily purified, quantitatively progress, yield are higher.
Embodiment
It is noted that described further below is all exemplary, it is intended to provides further instruction to the application.It is unless another
Indicate, all technologies used herein and scientific terminology are with usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in this manual using term "comprising" and/or " bag
Include " when, it indicates existing characteristics, step, operation, device, component and/or combinations thereof.
Heretofore described esterification is a kind of organic chemical reactionses, and master refers to that alcohol and carboxylic acid are anti-in the present invention
The reaction of ester and water should be generated.Its reaction equation is as follows：
RCOOH+R'OH→RCOOR'。
Heretofore described acyl chlorides and the reaction equation of the nucleophilic substitution of hydroxyl are as follows：
RCCl+R'OH→RCOOR'。
As background technology is introduced, the polyethylene glycol that end is connected with Phosphorylcholine group in the prior art be present
Other end active group is the deficiency that hydroxyl application field is limited, and in order to solve technical problem as above, present applicant proposes one
Kind acrylate ended Phosphorylcholine base polyethylene glycol and preparation method thereof.
A kind of exemplary embodiment of the application, there is provided a kind of acrylate ended Phosphorylcholine base polyethylene glycol, its
Chemical structural formula is,
Wherein, PC isN=4~50.
In order to obtain aforesaid propylene acid esters end-blocking Phosphorylcholine base polyethylene glycol, another typical embodiment party of the application
Formula, there is provided a kind of preparation method of aforesaid propylene acid esters end-blocking Phosphorylcholine base polyethylene glycol, using the poly- second of Phosphorylcholine base
Glycol carries out esterification acquisition with acrylic acid, or carries out acyl chlorides and hydroxyl using Phosphorylcholine base polyethylene glycol and acryloyl chloride
Nucleophilic substitution obtain；
Wherein, the structural formula of Phosphorylcholine base polyethylene glycol is,
In structural formula, PC isN=4~50.
In order to improve the yield of acrylate ended Phosphorylcholine base polyethylene glycol, the application is preferable, using phosphinylidyne courage
The nucleophilic substitution that base polyethylene glycol carries out acyl chlorides and hydroxyl with acryloyl chloride prepares acrylate ended Phosphorylcholine base
Polyethylene glycol.
It is further preferred that step is：Phosphorylcholine base polyethylene glycol is dissolved in organic solvent, be first cooled to -5 DEG C~
3 DEG C, acryloyl chloride reaction a period of time is added, then temperature is risen into normal temperature and continues stirring reaction for a period of time.
Due to acrylate ended phosphinylidyne courage can not only be produced after acryloyl chloride and the reaction of Phosphorylcholine base polyethylene glycol
Base polyethylene glycol, additionally it is possible to generate HCl, when HCl amounts are excessive, the continuation of reaction can be hindered, influence acrylate ended phosphorus
The yield of phatidylcholine base polyethylene glycol, in order to further improve the yield of acrylate ended Phosphorylcholine base polyethylene glycol, this
Apply still more preferably, Phosphorylcholine base polyethylene glycol and triethylamine being dissolved in into organic solvent.Using triethylamine as tiing up acid
Agent, the HCl and triethylamine that can make generation are combined, and so as to promote the progress of reaction, improve acrylate ended phosphinylidyne courage
The yield of base polyethylene glycol.
Still more preferably, the mol ratio of the triethylamine and acryloyl chloride is 1:1, the HCl of generation can be absorbed
Completely.
Organic solvent described herein is the organic matter that can dissolve acryloyl chloride and Phosphorylcholine base polyethylene glycol, example
Such as dichloromethane.
Still more preferably, the mol ratio of the Phosphorylcholine base polyethylene glycol and acryloyl chloride is 0.67~0.91:
1。
Still more preferably, the feed postition of acryloyl chloride is that acryloyl chloride solution is slowly added dropwise under stirring.The application
Described in acryloyl chloride solution be acryloyl chloride organic solvent solution.Acryloyl chloride, which is dissolved in organic solvent, to be prevented
Acryloyl chloride recovers, and controls the addition of acryloyl chloride.
Still more preferably, the concentration of the acryloyl chloride solution is 1g/5mL.
Still more preferably, 12h is reacted after adding acryloyl chloride.
Still more preferably, temperature is risen into normal temperature and continues 12~24h of stirring reaction.
In order to obtain more pure acrylate ended Phosphorylcholine base polyethylene glycol, the application is to reacted filtrate
Purification process is carried out, is the step of the purification process：Filtering, filtrate are settled with 6 times of volume ice ether, are filtered, and ice ether is washed
Wash, normal-temperature vacuum is dried.
The polyethylene glycol and aldehyde radical Phosphorylcholine that Phosphorylcholine base polyethylene glycol can be blocked by mono amino in the application
It is prepared by compound reaction.Detailed preparation method is referring to patent CN102070780A.
The application uses the nucleophilic displacement of fluorine for carrying out acyl chlorides and hydroxyl with acryloyl chloride using Phosphorylcholine base polyethylene glycol anti-
The process that acrylate ended Phosphorylcholine base polyethylene glycol should be prepared is as follows：
Wherein, n=4~50.
The third of the application blocks Phosphorylcholine base polyethylene glycol to exist embodiment there is provided a kind of aforesaid propylene acid esters
Prepare the application in biological macromolecule material.
The 4th kind of the application is embodiment there is provided a kind of polymer with biological function, and its raw material is including above-mentioned
Acrylate ended Phosphorylcholine base polyethylene glycol.
In order that the technical scheme of the application can clearly be understood by obtaining those skilled in the art, below with reference to tool
The embodiment of body describes the technical scheme of the application in detail.
Embodiment 1
1st, the preparation of Phosphorylcholine base polyethylene glycol
The polyethylene glycol (n=10) that 0.1mol mono aminos are blocked, is dissolved in DMF, adds
0.12mol aldehyde radical Phosphorylcholine compounds, react 12h at 50 DEG C, cool to after 8 DEG C, addition concentration is 0.02g/
ML NaBH4Methanol solution (wherein NaBH4The amount of material be 0.24mol), heat up 20 DEG C, react 12h, 6 times of volume ice second
Ether settles, and filters, and ice ether washing, normal-temperature vacuum is dried to obtain the polyethylene glycol that end is connected to Phosphorylcholine group, yield
89%.
2nd, the preparation of acrylate ended Phosphorylcholine base polyethylene glycol
0.01mol Phosphorylcholine base polyethylene glycol (n=10) and 0.012mol triethylamines are dissolved in anhydrous methylene chloride, cooling
To -5 DEG C~3 DEG C, the dichloromethane solution (1g/5mL) of 0.012mol acryloyl chlorides is slowly added dropwise under stirring, maintains the temperature
12h, then 12~24h of stirring at normal temperature, filtering, filtrate are settled with 6 times of ice ether, are filtered, and normal-temperature vacuum is dried, and obtain acrylate envelope
Hold Phosphorylcholine base polyethylene glycol, yield 80%.
1H NMR(CDCl3, TMS, 400MHz) and δ：6.41st, 5.83,6.12 (3H ,-CH=CH2)；4.27 (2H ,-COO-
CH2-)；3.4-3.8(40H,-CH2-(CH2CH2O)9-CH2-；2H,-CH2-N+)；4.47(2H,-CH 2-CH2-N+)；3.95(2H,-
NH-CH2-CH 2-PC)；3.3(9H,-N+(CH3)3)；2.96(2H,-NH-CH 2-CH2-PC)；2.76(2H,-CH 2-NH-CH2-
CH2-PC)。
Embodiment 2
1st, the preparation of Phosphorylcholine base polyethylene glycol
The polyethylene glycol (n=40) that 0.1mol mono aminos are blocked, is dissolved in DMF, adds
0.12mol aldehyde radical Phosphorylcholine compounds, react 12h at 50 DEG C, cool to after 8 DEG C, addition concentration is 0.02g/
ML NaBH4Methanol solution (wherein NaBH4The amount of material be 0.24mol), heat up 20 DEG C, react 12h, 6 times of volume ice second
Ether settles, and filters, and normal-temperature vacuum is dried to obtain the polyethylene glycol that end is connected to Phosphorylcholine group, yield 90%.
2nd, the preparation of acrylate ended Phosphorylcholine base polyethylene glycol
0.01mol Phosphorylcholine base polyethylene glycol (n=40) and 0.014mol triethylamines are dissolved in anhydrous methylene chloride, cooling
To -5 DEG C~3 DEG C, the dichloromethane solution (1g/5mL) of 0.014mol acryloyl chlorides is slowly added dropwise under stirring, maintains the temperature
12h, then stirring at normal temperature 16h, filtering, filtrate are settled with 6 times of ice ether, are filtered, and ice ether washing, normal-temperature vacuum is dried, and obtains third
Olefin(e) acid ester blocks Phosphorylcholine base polyethylene glycol, yield 84%.
1H NMR(CDCl3, TMS, 400MHz) and δ：6.42nd, 5.81,6.12 (3H ,-CH=CH2)；4.28 (2H ,-COO-
CH2-)；3.3-3.8(160H,-CH2-(CH2CH2O)39-CH2-；2H,-CH2-N+)；4.46(2H,-CH 2-CH2-N+)；3.97
(2H,-NH-CH2-CH 2-PC)；3.3(9H,-N+(CH3)3)；2.97(2H,-NH-CH 2-CH2-PC)；2.76(2H,-CH 2-NH-
CH2-CH2-PC)。
The preferred embodiment of the application is the foregoing is only, is not limited to the application, for the skill of this area
For art personnel, the application can have various modifications and variations.It is all within spirit herein and principle, made any repair
Change, equivalent substitution, improvement etc., should be included within the protection domain of the application.
Claims (10)
1. a kind of acrylate ended Phosphorylcholine base polyethylene glycol, it is characterized in that, its chemical structural formula is,
Wherein, PC isN=4~50.
2. a kind of preparation method of the acrylate ended Phosphorylcholine base polyethylene glycol described in claim 1, it is characterized in that, adopt
Esterification acquisition is carried out with Phosphorylcholine base polyethylene glycol and acrylic acid, or uses Phosphorylcholine base polyethylene glycol and acryloyl
Chlorine carries out acyl chlorides and the nucleophilic substitution of hydroxyl obtains；
Wherein, the structural formula of Phosphorylcholine base polyethylene glycol is,
In structural formula, PC isN=4~50.
3. preparation method as claimed in claim 2, it is characterized in that, carried out using Phosphorylcholine base polyethylene glycol and acryloyl chloride
The nucleophilic substitution of acyl chlorides and hydroxyl prepares acrylate ended Phosphorylcholine base polyethylene glycol.
4. preparation method as claimed in claim 3, it is characterized in that, step is：Phosphorylcholine base polyethylene glycol is dissolved in organic
In solvent, -5 DEG C~3 DEG C are first cooled to, adds acryloyl chloride reaction a period of time, then temperature is risen into normal temperature and continues stirring instead
Should a period of time.
5. preparation method as claimed in claim 4, it is characterized in that, Phosphorylcholine base polyethylene glycol and triethylamine are dissolved in organic
Solvent；Preferably, the mol ratio of the triethylamine and acryloyl chloride is 1:1.
6. preparation method as claimed in claim 4, it is characterized in that, the Phosphorylcholine base polyethylene glycol and acryloyl chloride rub
You are than being 0.67~0.91:1.
7. preparation method as claimed in claim 4, it is characterized in that, the feed postition of acryloyl chloride is to be slowly added dropwise third under stirring
Alkene solution of acid chloride；Preferably, the concentration of the acryloyl chloride solution is 1g/5mL.
8. preparation method as claimed in claim 4, it is characterized in that, purification process, the purifying are carried out to reacted filtrate
The step of processing is：Filtering, filtrate are settled with 6 times of volume ice ether, are filtered, and ice ether washing, normal-temperature vacuum is dried.
9. the acrylate ended Phosphorylcholine base polyethylene glycol described in a kind of claim 1 is in biological macromolecule material is prepared
Application.
10. a kind of polymer with biological function, it is characterized in that, raw material includes the acrylate ended described in claim 1
Phosphorylcholine base polyethylene glycol.
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| CN201710681598.9A CN107474239A (en) | 2017-08-10 | 2017-08-10 | A kind of acrylate ended Phosphorylcholine base polyethylene glycol and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108546321A (en) * | 2018-04-19 | 2018-09-18 | 济南羽时信息科技有限公司 | A kind of preparation and application of the biodegradable filling material of bone of high-biocompatibility |
| CN113150270A (en) * | 2021-03-19 | 2021-07-23 | 广东丁沃生医疗器械有限公司 | Phospholipid polymer and preparation method and application thereof |
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| CN102070780A (en) * | 2010-12-21 | 2011-05-25 | 天津大学 | Polyethyleneglycol connected with phosphorylcholine group at tail end and preparation method thereof |
| CN102093552A (en) * | 2010-11-27 | 2011-06-15 | 大连工业大学 | Preparation method of phase change monomer with double-bond end groups |
| CN103421039A (en) * | 2013-09-03 | 2013-12-04 | 重庆工商大学 | 2- methacroyloxyethyl phosphorylcholine synthesizing method |
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| CN102093552A (en) * | 2010-11-27 | 2011-06-15 | 大连工业大学 | Preparation method of phase change monomer with double-bond end groups |
| CN102070780A (en) * | 2010-12-21 | 2011-05-25 | 天津大学 | Polyethyleneglycol connected with phosphorylcholine group at tail end and preparation method thereof |
| CN103421039A (en) * | 2013-09-03 | 2013-12-04 | 重庆工商大学 | 2- methacroyloxyethyl phosphorylcholine synthesizing method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108546321A (en) * | 2018-04-19 | 2018-09-18 | 济南羽时信息科技有限公司 | A kind of preparation and application of the biodegradable filling material of bone of high-biocompatibility |
| CN108546321B (en) * | 2018-04-19 | 2020-11-03 | 济南羽时信息科技有限公司 | Preparation and application of high-biocompatibility biodegradable bone filling material |
| CN113150270A (en) * | 2021-03-19 | 2021-07-23 | 广东丁沃生医疗器械有限公司 | Phospholipid polymer and preparation method and application thereof |
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Application publication date: 20171215 |