CN108948337A - A kind of vinyl modified star pla-pcl and its synthetic method - Google Patents
A kind of vinyl modified star pla-pcl and its synthetic method Download PDFInfo
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- CN108948337A CN108948337A CN201810526489.4A CN201810526489A CN108948337A CN 108948337 A CN108948337 A CN 108948337A CN 201810526489 A CN201810526489 A CN 201810526489A CN 108948337 A CN108948337 A CN 108948337A
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- pcl
- pla
- vinyl modified
- star pla
- modified star
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The present invention relates to a kind of vinyl modified star pla-pcl and its synthetic methods, its synthetic method are as follows: using polyalcohol and cyclic annular caprolactone monomer as raw material, ring-opening polymerization is carried out under stannous octoate catalysis, obtain star pla-pcl high molecular material, terminal groups modification is carried out to star pla-pcl again, obtains vinyl modified star pla-pcl.Vinyl modified star pla-pcl provided by the invention can be used for the high molecular material of photocuring solid forming, fusion sediment forming increasing material manufacturing.
Description
Technical field
The invention belongs to technical field of polymer materials, it is related to a kind of vinyl modified star pla-pcl and its synthesis side
Method.
Background technique
The raw material that photocuring solid increases material manufacturing technology (SLA) uses is the liquid photosensitive resin containing unsaturated bond,
Other materials can be added wherein and form composite material.It is to adopt UV laser beam under computerizeing control with computer model
Each layering section be path point by point scanning, it is solid after so that the thin resin layer in scanned area is generated photopolymerization or photo-crosslinking
Change, after the completion of one layer of solidification, in vertical direction mobile work platform, the resin surface of prior cured is made to cover one layer of new liquid
Resin, successively scanning, solidification, finally obtains three-dimensional prototype.SLA technology is high with precision, surface quality is good, performance is stable, produces
The advantages that product mechanical strength is high.SLA technology is the most mature and most widely used 3D printing technique of current technology, the disadvantage is that molding
Product, which needs to clean, removes impurity, may cause deformation of products, and photosensitive resin price is costly, cannot generally degrade.
Pla-pcl class high molecular material is answered because having good biocompatibility and degradability in bio-medical field
With increasingly extensive.The medical instrument of pla-pcl class material has been widely used in clinic, but mainly uses conventional melt at present
Pla-pcl class material is processed into product by injection molded processing technology, on the one hand, existing common pla-pcl material structure
In there is no unsaturated double-bond or triple bonded group, cannot be processed with technologies such as photocuring solid forming increasing material manufacturings, although can
To be processed using fusion sediment forming increases material manufacturing technology, cause the more difficult dismounting of product support, precision lower, it is difficult to meet
The personalized customization requirement of fine structure medical instrument.
Therefore, the present invention develops the highly branched chain structure and vinyl that vinyl modified star pla-pcl has multi-arm star
Functional group, the pla-pcl material, can be vertical using photocuring while keeping good biocompatibility and degradability
The technologies such as body forming, fusion sediment forming increasing material manufacturing are processed, and processing performance is good, has important economic value, answers
With in extensive range.
Summary of the invention
The technical problem to be solved by the present invention is to aiming at the above shortcomings existing in the prior art, provide a kind of vinyl
Modified star pla-pcl and its synthetic method.
In order to solve the above technical problems, present invention provide the technical scheme that
A kind of vinyl modified star pla-pcl is provided, the chemical structural formula with following formula I, Formula II or formula III:
Wherein R1Selected from hydrogen atom, alkyl, aryl, or with one or more hydroxyls, amino, carboxyl, alkoxy,
The alkyl of aryl or aryloxy group；N represents the natural number of 1-100000.
Preferably, the vinyl modified star pla-pcl structural formula is as follows:
Wherein n is the natural number of 1-100000.
Preferably, the vinyl modified star pla-pcl structural formula is as follows:
Wherein n is the natural number of 1-100000.
Preferably, the vinyl modified star pla-pcl structural formula is as follows:
Wherein n is the natural number of 1-100000.
The present invention also provides the synthetic methods of above-mentioned vinyl modified star pla-pcl: with polyalcohol and cyclic annular caprolactone
Monomer is raw material, carries out ring-opening polymerization under stannous octoate catalysis, obtains star pla-pcl high molecular material, then to star
Shape pla-pcl carries out terminal groups modification, obtains vinyl modified star pla-pcl.
Preferably, the polyalcohol is one of glycerine, pentaerythrite, inositol.
Preferably, the cyclic annular caprolactone monomer is 6-caprolactone.
Preferably, the ring-opening polymerization condition are as follows: small in 50-300 DEG C of reaction 3-240 under the conditions of vacuum sealing
When.
According to the above scheme, specific the preparation method is as follows:
1) polyalcohol, cyclic annular caprolactone monomer and stannous octoate are dissolved in the stannous octoate solution that organic solvent obtains and mixed
It closes, solvent is removed under reduced pressure, lead to argon gas, then vacuum sealing carries out ring-opening polymerization, then post-processing obtains star pla-pcl
High molecular material；
2) under an inert atmosphere, by the terminal hydroxy group of star pla-pcl high molecular material obtained by step 1) and acryloyl chloride,
Propylene acylbromide, acrylic anhydride, acrylic acid or acrylate are reacted, and vinyl modified star pla-pcl is obtained.
According to the above scheme, the step 1) solvent is selected from n,N-Dimethylformamide, dimethyl sulfoxide, chloroform, dichloro
One of methane, carbon tetrachloride, tetrahydrofuran, ethyl acetate, toluene, dimethylbenzene, acetone are a variety of.The vinyl of terminal hydroxy group
The adoptable raw material of modified-reaction is one of acryloyl chloride, propylene acylbromide, acrylic anhydride, acrylic acid, acrylate or more
Kind.
Preferably, the step 1) polyalcohol and cyclic annular caprolactone monomer mole ratio are 1:1-100000.
Preferably, the molar ratio of the step 1) stannous octoate and cyclic annular caprolactone monomer is 1:100-50000.
The invention also includes the products that above-mentioned vinyl modified star pla-pcl is processed.
According to the above scheme, the processing method includes photocuring solid forming, fusion sediment forming increasing material manufacturing method.
The present invention is first using glycerine, pentaerythrite or inositol as core, using caprolactone cyclic compound as monomer,
Under stannous octoate catalysis, using ring-opening polymerization method, star-branched pla-pcl high molecular material is synthesized, then by terminal hydroxy group
Vinyl modified reaction is carried out, the star-branched pla-pcl material of vinyl modified is obtained.
The beneficial effects of the present invention are: 1, provided by the invention vinyl modified star pla-pcl because have multi-arm star
The highly branched chain structure and vinyl-functional of shape have good biocompatibility and degradability, are a kind of with good
Parent/hydrophobicity, high strength, high tenacity, the good elastic high molecular material with processing performance, can be used photocuring solid
Forming, fusion sediment forming increases material manufacturing technology or photocuring solid forming-fusion sediment shape double mode increasing material manufacturing skill
Art carries out processing and the products such as various macromolecule devices at low cost, with high accuracy, medical instrument is prepared, and is a kind of with good
The biological medical polymer material of biocompatibility, biodegradability, compared with traditional linear pla-pcl material, application
Range is wider；2, the method that preparation method of the present invention is reacted using ring-opening polymerisation, end group synthesizes molecular weight height, molecular weight point
Cloth is relatively narrow, the star-branched pla-pcl high molecular material of the higher vinyl modified of purity, high excellent of, yield high with the degree of polymerization
Point.
Specific embodiment
Technical solution in order to enable those skilled in the art to better understand the present invention makees the present invention below with reference to embodiment
It is described in further detail.
Embodiment 1
Take the nothing of 15.16g 6-caprolactone (0.105mol), the glycerine (0.1mmol) of 0.0092g, 105 μ L stannous octoates
Water beetle benzole soln (0.1mol/L) sequentially adds in the drying polymerization bottle with magneton, and solvent, then logical argon gas is then removed under reduced pressure,
4 times repeatedly, after vacuum-packed polymerization bottle is finally reacted 48h under constant temperature (120 DEG C), then use 100mL bis-
Chloromethanes lysate, then with 500mL ethyl alcohol/n-hexane (v/v=1:1) reprecipitation, three-arm star-shaped is dried in vacuo to obtain after filtering
Polycaprolactone white solid 13.35g, yield 88%.
Under the protection of nitrogen, 12g (0.1mmol) three-arm star-shaped polycaprolactone is dissolved in the water removal tetrahydrofuran of 100mL
In, under condition of ice bath, magnetic agitation is kept, 10.1g (0.1mol, 13.9mL) triethylamine is first added, then 9.1g is slowly added dropwise
The acryloyl chloride of (0.1mol, 8.2m L), there is white precipitate in discovery system during being added dropwise, and ice bath reacts 4h.It will react molten
Liquid filtering, after filtrate is concentrated, with methanol reprecipitation, vacuum drying obtains ethylene to constant weight to precipitated product at normal temperature
Base is modified three-arm star-shaped pla-pcl product 10.21g, yield 85%, and molecular formula is formula 1.Gel permeation chromatography (GPC) measurement,
Its number-average molecular weight Mn is 17.35 × 104, molecular weight distributing index 1.41.
Embodiment 2
Take 50.05g 6-caprolactone (0.347mol), the pentaerythrite (0.1mmol) of 0.0136g, 17.4 μ L stannous octoates
Anhydrous toluene solution (0.1mol/L), sequentially add in the drying polymerization bottle with magneton, be then removed under reduced pressure solvent, then logical argon
Gas 4 times repeatedly, after vacuum-packed polymerization bottle is finally reacted 72h under constant temperature (140 DEG C), then uses 200mL
Methylene chloride lysate, then with 1000mL ethyl alcohol/n-hexane (v/v=1:1) reprecipitation, four arm stars are dried in vacuo to obtain after filtering
Shape polycaprolactone white solid 40.05g, yield 80%.
Under the protection of argon gas, four arm star polycaprolactone of 10g (0.02mmol) is dissolved in the water removal tetrahydrofuran of 30mL
In, under condition of ice bath, magnetic agitation is kept, 80.8g (0.8mol, 111.2mL) triethylamine is first added, then 84g is slowly added dropwise
The methacrylic chloride of (0.8mol, 86.6mL), there is white precipitate in discovery system during being added dropwise, and ice bath reacts 8h.It will be anti-
Solution is answered to filter, after filtrate is concentrated, with methanol reprecipitation, vacuum drying obtains precipitated product to constant weight at normal temperature
Four arm star pla-pcl product 9.68g of vinyl modified, yield 78%, molecular formula are formula 2.Gel permeation chromatography (GPC) is surveyed
Fixed, number-average molecular weight Mn is 47.2 × 104, molecular weight distributing index 1.65.
Embodiment 3
Take 20.04g 6-caprolactone (0.139mol), 0.18g inositol (1mmol), 695 μ L stannous octoates without water beetle
Benzole soln (0.1mol/L) sequentially adds in the drying polymerization bottle with magneton, solvent, then logical argon gas is then removed under reduced pressure, so
4 times repeatedly, after finally reacting vacuum-packed polymerization bottle for 24 hours under constant temperature (160 DEG C), then use 150mL dichloromethane
Alkane lysate, then with 750mL ethyl alcohol/n-hexane (v/v=1:1) reprecipitation, be dried in vacuo after filtering six arm stars gather oneself
Lactone white solid 16.98g, yield 84%.
Under the protection of nitrogen, six arm star polycaprolactone of 10g (0.5mmol) is dissolved in the water removal tetrahydrofuran of 40mL
In, under condition of ice bath, magnetic agitation is kept, 1.516g (3.75mmol, 2.08mL) triethylamine is first added, then be slowly added dropwise
The acrylic anhydride of 1.89g (15mmol), there is white precipitate in discovery system during being added dropwise, and ice bath reacts 6h.By reaction solution
Filtering, after filtrate is concentrated, with methanol reprecipitation, vacuum drying obtains vinyl to constant weight to precipitated product at normal temperature
Modified six arm star pla-pcl product 8.64g, yield 84%, molecular formula are formula 3.Gel permeation chromatography (GPC) measurement, number
Average molecular weight Mn is 2.15 × 104, molecular weight distributing index 1.5.
Claims (10)
1. a kind of vinyl modified star pla-pcl, which is characterized in that its chemistry knot with following formula I, Formula II or formula III
Structure formula:
Wherein R1Selected from hydrogen atom, alkyl, aryl, or with one or more hydroxyls, amino, carboxyl, alkoxy, aryl
Or the alkyl of aryloxy group；N represents the natural number of 1-100000.
2. vinyl modified star pla-pcl according to claim 1, which is characterized in that the vinyl modified star
Pla-pcl structural formula is as follows:
Wherein n is the natural number of 1-100000.
3. vinyl modified star pla-pcl according to claim 1, which is characterized in that the vinyl modified star
Pla-pcl structural formula is as follows:
Wherein n is the natural number of 1-100000.
4. vinyl modified star pla-pcl according to claim 1, which is characterized in that the vinyl modified star
Pla-pcl structural formula is as follows:
Wherein n is the natural number of 1-100000.
5. a kind of preparation method of any vinyl modified star pla-pcl of claim 1-4, which is characterized in that step
It is rapid as follows: using polyalcohol and cyclic annular caprolactone monomer as raw material, to carry out ring-opening polymerization under stannous octoate catalysis, obtain star
Shape pla-pcl high molecular material, then terminal groups modification is carried out to star pla-pcl, obtain vinyl modified star pla-pcl.
6. the preparation method of vinyl modified star pla-pcl according to claim 5, which is characterized in that described polynary
Alcohol is one of glycerine, pentaerythrite, inositol；The ring-type caprolactone monomer is 6-caprolactone.
7. the preparation method of vinyl modified star pla-pcl according to claim 5, which is characterized in that the open loop
Polymeric reaction condition are as follows: under the conditions of vacuum sealing in 50-300 DEG C reaction 3-240 hours.
8. the preparation method of vinyl modified star pla-pcl according to claim 5, which is characterized in that specific steps
It is as follows:
1) polyalcohol, cyclic annular caprolactone monomer and stannous octoate are dissolved in the stannous octoate solution that organic solvent obtains to mix, are subtracted
Pressure removes solvent, leads to argon gas, then vacuum sealing carries out ring-opening polymerization, and then post-processing obtains star pla-pcl macromolecule
Material；
2) under an inert atmosphere, by the terminal hydroxy group and acryloyl chloride, propylene of star pla-pcl high molecular material obtained by step 1)
Acylbromide, acrylic anhydride, acrylic acid or acrylate are reacted, and vinyl modified star pla-pcl is obtained.
9. the preparation method of vinyl modified star pla-pcl according to claim 8, which is characterized in that step 1) institute
It states solvent and is selected from N,N-dimethylformamide, dimethyl sulfoxide, chloroform, methylene chloride, carbon tetrachloride, tetrahydrofuran, acetic acid
One of ethyl ester, toluene, dimethylbenzene, acetone are a variety of.It is propylene that the vinyl modified of terminal hydroxy group, which reacts adoptable raw material,
One of acyl chlorides, propylene acylbromide, acrylic anhydride, acrylic acid, acrylate are a variety of.
10. the product that vinyl modified star pla-pcl according to claim 1 to 4 is processed.
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| CN112048040A (en) * | 2020-08-27 | 2020-12-08 | 武汉工程大学 | Photocuring 3D printing vinyl star-shaped polycarbonate composite photosensitive resin and preparation method and application thereof |
| CN112062916A (en) * | 2020-08-27 | 2020-12-11 | 武汉工程大学 | Photocuring 3D printing vinyl star-shaped polycaprolactone composite photosensitive resin and preparation method and application thereof |
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| CN112898498B (en) * | 2021-02-11 | 2022-08-26 | 上海利鑫生物科技有限公司 | Recyclable foam material and preparation method thereof |
| CN113105593A (en) * | 2021-03-26 | 2021-07-13 | 四川大学 | Photocurable 3D printing-molded flexible degradable polymer composite resin and preparation method thereof |
| CN113174023A (en) * | 2021-03-26 | 2021-07-27 | 四川大学 | Photosensitive liquid fully-degradable oligomer capable of being rapidly photocured and formed and preparation method thereof |
| CN113372515A (en) * | 2021-08-13 | 2021-09-10 | 山东诺尔生物科技有限公司 | Six-claw-shaped drilling fluid coating agent and preparation method thereof |
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Application publication date: 20181207 |