CN107459634A - A kind of unsaturated aliphatic polyester and its preparation method and application - Google Patents
A kind of unsaturated aliphatic polyester and its preparation method and application Download PDFInfo
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- CN107459634A CN107459634A CN201710667116.4A CN201710667116A CN107459634A CN 107459634 A CN107459634 A CN 107459634A CN 201710667116 A CN201710667116 A CN 201710667116A CN 107459634 A CN107459634 A CN 107459634A
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- aliphatic polyester
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- succinic anhydride
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- 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
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A—HUMAN NECESSITIES
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/52—Hydrogels or hydrocolloids
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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Abstract
The present invention relates to a kind of unsaturated aliphatic polyester, the polyester is the construction unit shown in chemical formula (I) and the construction unit shown in chemical formula (II) by 3:7~7:The polyester of the 3 linear random arrangement of mol ratio, its number-average molecular weight are 5000~12000, and monodispersity index is 1.21~1.80；Described unsaturated aliphatic polyester is that GMA, n-butyl glycidyl ether and succinic anhydride are carried out ring opening copolymer and obtained.Unsaturated aliphatic polyester of the present invention can be used for preparing tissue engineering bracket, and the support has preferable modulus of elasticity and swelling behavior, and cytotoxicity is low, good biocompatibility, and cellular affinity is high.
Description
Technical field
The present invention relates to organic high molecular compound, and in particular to unsaturated aliphatic polyester, the unsaturated fat adoption
Ester is applied to medical material.
Background technology
Its main chain of aliphatic polyester is formed by connecting by aliphatic structure unit by the ester bond of facile hydrolysis, and main chain is submissive,
It is easy in the presence of microorganism, is degraded by the catalysis of enzyme.Therefore, aliphatic polyester is because it has good life
Thing compatibility and biodegradability, it is a kind of important bio-medical material, is widely used in biomedicine field, such as medicine
Sustained release, operation suture thread, bone immobilizing material, tissue engineering material etc..Conventional aliphatic polyester has PGA (PGA), gathered
Lactide (PLA), glycolide-lactide copolymer (PLGA), polycaprolactone (PCL) etc..The synthesis side of aliphatic polyester at present
Method has two kinds.First is prepared using bifunctional monomer by condensation, such as is condensed and gathered with binary acid and dihydric alcohol
Conjunction obtains.Second is to use its ester compounds or lactone compound as monomer, carries out ring opening copolymer and obtains.But aliphatic poly
The defects of several larger be present in ester, and first, the hydrophily of aliphatic polyester is poor, bioactivity is low, affinity to cell and viscous
Attached power is weak.Second, the main chain of aliphatic polyester lacks reactivity site, limits the application of aliphatic polyester.
Unsaturated aliphatic polyester refers to the aliphatic polyester containing unsaturated double-bond, can be with the monomer containing unsaturated double-bond
Or prepolymer is solidified.At present, the preparation method of unsaturated aliphatic polyester mainly uses condensation methods.Condensation methods be exactly by
Undersaturated dibasic aliphatic acid or dibasic aliphatic acid anhydrides obtain with undersaturated dihydric alcohol polycondensation.Insatiable hunger prepared by this method
Contain unsaturated double-bond with aliphatic polyester main chain.Yang Qun etc. using fumaric acid, diglycol and 1,4- butanediols as
Raw material, unsaturated aliphatic polyester and copolyesters are synthesized using melt-polycondensation, it is found that the unsaturated aliphatic polyester can be with
Biodegradable (apply chemical industry, 2013, the 3rd phase of volume 42,490).But the unsaturated fat adoption that above-mentioned document is reported
Unsaturated double-bond in ester is located at main chain, and reactivity is low, carries out photocuring ability with other monomers containing unsaturated double-bond, no
It is tissue engineering bracket that can apply.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of unsaturated aliphatic polyester, the unsaturated aliphatic polyester side
Contain unsaturated double-bond on chain, there is good biocompatibility and low cytotoxicity with the photocuring hydrogel obtained by it.
Technical proposal that the invention solves the above-mentioned problems is：
A kind of unsaturated aliphatic polyester, the polyester are shown in construction unit and chemical formula (II) shown in chemical formula (I)
Construction unit press 3:7~7:The polyester of the 3 linear random arrangement of mol ratio, its number-average molecular weight (abbreviation Mn) for 5000~
12000, monodispersity index (abbreviation PDI) is 1.21~1.80,
Described unsaturated aliphatic polyester is by GMA, n-butyl glycidyl ether and fourth two
Acid anhydrides carries out ring opening copolymer and obtained.
Above-mentioned unsaturated aliphatic polyester, wherein construction unit shown in the chemical formula (I) with shown in chemical formula (II)
The mol ratio of construction unit be preferably 2:3~3:2, number-average molecular weight is 5000~10000, monodispersity index preferably 1.21
~1.60.
The specific preparation method of above-mentioned unsaturated aliphatic polyester is as follows：
Succinic anhydride is taken, adds GMA, n-butyl glycidyl ether, tert-butylhydroquinone
And catalyst, it is dissolved into appropriate mixed solution, under nitrogen protection, 90~120 DEG C of ring opening copolymers react 5~12h, remove
Solvent obtains described unsaturated aliphatic polyester；Wherein,
Described GMA and the addition sum of n-butyl glycidyl ether, which are equal to, takes fourth two
The mole of acid anhydrides, described first base propylene acid glycidyl ester ester ︰ n-butyl glycidyl ethers=︰ 3 of 3 ︰ 7~7 mol ratio；
The addition of described tert-butylhydroquinone is the 1~10% of the mole of taken succinic anhydride；
The addition of described catalyst is the 1~10% of the mole of taken succinic anhydride；
Described mixed solution is made up of the ethyl acetate and butyl acetate of isometric ratio；
Described catalyst is one kind in tetra-n-butyl ammonium bromide, zinc acetate, zinc Isoocatanoate and cobalt iso-octoate.
In the above method, the mol ratio of described first base propylene acid glycidyl ester ester ︰ n-butyl glycidyl ethers is preferably
The ︰ 2 of 2 ︰ 3~3, preferably 1 ︰ 1.
In the above method, the addition of described tert-butylhydroquinone is preferably to take the mole of succinic anhydride
2~8%, preferably take the 5% of the mole of succinic anhydride.
In the above method, the addition of described catalyst preferably takes the 2~8% of the mole of succinic anhydride, most
It is the 5% of the mole of taken succinic anhydride well.
In the above method, the preferred tetra-n-butyl ammonium bromide of described catalyst.
In the above method, the temperature of described ring opening copolymer reaction is preferably 100~120 DEG C, preferably 110 DEG C；It is described
Ring opening copolymer reaction time be preferably 5~10h, preferably 6~8h.
Unsaturated aliphatic polyester of the present invention, there is good biocompatibility and biodegradability, and
Contain unsaturated double-bond on side chain, its further functional modification or photocuring plastic biological can be dropped for preparing
The photocuring hydrogel of solution.
Above-mentioned photocuring hydrogel by unsaturated aliphatic polyester, hydrophily unsaturated monomer, soft unsaturated monomer and
Light trigger forms, wherein, the content of hydrophily unsaturated monomer is the 40~60% of unsaturated aliphatic polyester weight, soft
The content of unsaturated monomer is the 40~60% of unsaturated aliphatic polyester weight, and the content of light trigger is unsaturated aliphatic
The 0.5~1% of weight polyester；
Described hydrophily unsaturated monomer is hydroxypropyl acrylate, hydroxy propyl methacrylate, hydroxyethyl methacrylate second
Ester, hydroxy-ethyl acrylate and acrylic acid-N, more than one or two kinds of in TMSDMA N dimethylamine base ethyl ester；
Described soft unsaturated monomer is in butyl acrylate, acrylic acid-2-ethyl caproite and Isooctyl acrylate monomer
It is one or two kinds of；
Described light trigger be 4- (2- hydroxyl-oxethyls) phenyl-(2- hydroxyl -2- propyl group) ketone, 2- hydroxy-2-methyls -
1- phenylacetones, 2,4,6- trimethylbenzoy-diphenies phosphine oxide and one kind in thio propoxyl group thioxanthone or
It is two or more.
In above-mentioned photocuring hydrogel, the content of described hydrophily unsaturated monomer is preferably unsaturated aliphatic polyester
The 50% of weight.
In above-mentioned photocuring hydrogel, the content of described soft unsaturated monomer is preferably unsaturated aliphatic polyester weight
The 50% of amount.
Photocuring hydrogel of the present invention answers black out to preserve, in use, the light-initiated condition of photocuring hydrogel is
Ultraviolet light light intensity is 200~600 millijoules/square centimeter, and the Photoinitiated reactions time is 1~5min.
Tissue engineering bracket prepared by photocuring hydrogel of the present invention has preferable modulus of elasticity and swellability
Can, the advantages of cytotoxicity is low, good biocompatibility, and cellular affinity is high.
Embodiment
The preparation method and its effect of the present invention are described in further detail with specific embodiment below.
Embodiment 1
(1) preparation of unsaturated aliphatic polyester
Succinic anhydride 10g (100mmol), GMA 7.1g (50mmol), normal-butyl is taken to shrink sweet
Oily ether 6.5g (50mmol), tert-butylhydroquinone 0.83g (5mmol) and zinc Isoocatanoate 1.755g (5mmol), add
100mL ethyl acetate：Butyl acetate=1:The mixed solution dissolving of 1 volume ratio, under nitrogen protection, 110 DEG C of ring opening copolymers are anti-
8h is answered, solvent is removed and obtains unsaturated aliphatic polyester.
The weight average molecular weight for obtaining unsaturated aliphatic polyester and number-average molecular weight are used into Jasco Gulliver system
(PU-980, CO-965, RI-930, and UV-1570) gel permeation chromatograph is measured.It is equipped with Aquapak A-440 post
(Shodex col umns K804, K805, and J806), by the use of THF as eluant, eluent, polystyrene is as standard correction, and 30
Determined at DEG C, measurement result is：Mw=16432, Mn=11255, PDI=1.46.
(2) preparation of photocuring hydrogel and its performance
(a) formula of photocuring hydrogel
Unsaturated aliphatic polyester 5g, hydroxypropyl acrylate 1g, hydroxyethyl methacrylate 1g prepared by step 1, propylene
Acid butyl ester 1g, Isooctyl acrylate monomer 1g, 4- (2- hydroxyl-oxethyls) phenyl-(2- hydroxyl -2- propyl group) ketone 0.025g.
(b) preparation of photocuring hydrogel
Above-mentioned steps (a) raw material is well mixed, black out encapsulation, produces described photocuring hydrogel.
(c) photocuring hydrogel performance
To verify the performance of photocuring hydrogel of the present invention, above-mentioned photocuring hydrogel is filled into first transparent
In meniscus of knee joint mould, then by the meniscus of knee joint mould light intensity be 300 millijoules/square centimeter ultraviolet light
4min is irradiated, tissue engineering bracket meniscus of knee joint is obtained after the demoulding.
1. swelling behavior
Prepared meniscus of knee joint is placed in 60 DEG C of baking oven and dries 24h, it is fully dehydrated, determines it
The weight of stem organization's engineering rack, is then soaked in deionized water at room temperature, is treated that it reaches swelling equilibrium, is wiped with filter paper
The moisture that tissue engineering bracket surface is unnecessary is removed, the quality of tissue engineering bracket is determined again, finally calculates swelling ratio.
The swelling ratio of the tissue engineering bracket prepared according to above method detecting step 2 is 943%.
2. modulus of elasticity
By the universal testing machines of Zwick/Roell 2202 on prepared meniscus of knee joint (German Zwick companies)
Detected.
Detected as stated above, the modulus of elasticity of prepared tissue engineering bracket is 3.27MPa
3. cell experiment
3.1. cell is inoculated with
Prepared meniscus of knee joint is used into deionized water rinsing repeatedly, is then soaked 1 hour and rinsed with PBS, repeat 3
It is secondary.Support is transferred in 24 orifice plates, addition DMEM cell culture fluids, which are put into incubator, prewets.The people liver of culture is normally thin
Born of the same parents HL-7702 is inoculated with (2.0 × 10 on support6Cell/100uL/ supports), 37 DEG C, 5%CO2Culture 4 is small in incubator
When make cell preferably adherent.Then 1mL nutrient solution, 37 DEG C, 5%CO are added in each culture hole2Cultivated in incubator, 2d is more
Change nutrient solution once.
3.2. cell viability is evaluated
24 well culture plates are taken out in 1d, 3d, 7d respectively, 80uL MTT solution is added per hole, incubator is put into and is further continued for training
Support 4h.Nutrient solution is abandoned in suction, adds 750uL hydrochloric acid aqueous isopropanol (0.4mol/L) per hole, in being incubated 15min in incubator, is blown and beaten
Take 200uL to move into 96 well culture plates per hole after mixing, detect each hole absorbance value (OD at 540nm with full-automatic ELIASA
Value).
Cell viability %=((cell OD- blank OD to be measured)/(control cell OD- blank OD)) × 100
Detected as stated above, the cell viability of prepared tissue engineering bracket is as shown in table 1.
The cell viability of the tissue engineering bracket of table 1
| Time (my god) | 1 | 3 | 7 |
| Cell viability % | 102 | 117 | 106 |
By table 1 it is known that the tissue engineering bracket cytotoxicity prepared is small, cellular affinity is high, and cytoactive is influenceed
It is small.
3.3. cell adherence
The infiltration and adhesion of cell are by gross examination of skeletal muscle (MTT dyeing).People normal cell lines of human liver HL-7702 kinds plant on support
In vitro culture 3 days, suctions out nutrient solution, and PBS is rinsed 3 times, every time 10 minutes.80uL MTT solution is added per hole, is put into incubator
Continue to cultivate 4h.Nutrient solution is abandoned in suction, adds 750uL hydrochloric acid aqueous isopropanol (0.4mol/L) per hole, in being incubated in incubator
15min, piping and druming take 200uL to move into 96 well culture plates per hole, each Kong Guang are detected at 540nm with full-automatic ELIASA after mixing
Absorption value (OD values).
Cell adherence rate %=((cell OD- blank OD to be measured)/(control cell OD- blank OD)) × 100
Detected as stated above, the cell adherence rate of prepared tissue engineering bracket is 98%.By cell adherence
Rate is visible, and prepared tissue engineering bracket cell adhesion is good, and cellular affinity is high.
The above results show that prepared support cytotoxicity is low, and cell adhesion is good, and cellular affinity is high.
Embodiment 2
(1) preparation of unsaturated aliphatic polyester
Succinic anhydride (10g, 100mmol), GMA (50mmol, 7.1g), normal-butyl is taken to shrink
Glycerin ether (50mmol, 6.5g), tert-butylhydroquinone (0.33g, 2mmol) and TBAB (0.64g, 2mmol),
Add 100mL ethyl acetate：Butyl acetate=1:The mixed solution dissolving of 1 volume ratio, under nitrogen protection, 90 DEG C of ring opening copolymers
5h is reacted, solvent is removed and obtains unsaturated aliphatic polyester.
Gained unsaturated aliphatic polyester is detected by the methods described of embodiment 1, testing result is：Mw=6028, Mn
=4982, PDI=1.21.
(2) preparation of photocuring hydrogel and its performance
(a) formula of photocuring hydrogel
Unsaturated aliphatic polyester 5g prepared by step 1, hydroxy propyl methacrylate 0.5g, hydroxyethyl methacrylate
0.5g, hydroxy-ethyl acrylate 0.8g, acrylic acid-N, TMSDMA N dimethylamine base ethyl ester 1.2g, butyl acrylate 1g, acrylic acid-2-ethyl
Own ester 2g, 2,4,6- trimethylbenzoy-dipheny phosphine oxide 0.02g, thio propoxyl group thioxanthone 0.02g.
(b) preparation of photocuring hydrogel
Above-mentioned steps (a) raw material is well mixed, black out encapsulation, produces described photocuring hydrogel.
(c) photocuring hydrogel performance
To verify the performance of photocuring hydrogel of the present invention, above-mentioned photocuring hydrogel is filled into first transparent
In meniscus of knee joint mould, then by the meniscus of knee joint mould light intensity be 200 millijoules/square centimeter ultraviolet light
5min is irradiated, tissue engineering bracket meniscus of knee joint is obtained after the demoulding.
1. swelling behavior
Detected by the methods described of embodiment 1, the swelling ratio of prepared tissue engineering bracket is 864%.
2. modulus of elasticity
Detected by the methods described of embodiment 1, the modulus of elasticity of prepared tissue engineering bracket is 2.99MPa
3. cell experiment
Detected by the methods described of embodiment 1, the cell viability of prepared tissue engineering bracket is as shown in table 2.
The cell viability of the tissue engineering bracket of table 2
| Time (my god) | 1 | 3 | 7 |
| Cell viability % | 97 | 109 | 118 |
Detected by the methods described of embodiment 1, the cell adherence rate of prepared tissue engineering bracket is 105%.
The above results show that prepared support cytotoxicity is low, and cell adhesion is good, and cellular affinity is high.
Embodiment 3
(1) preparation of unsaturated aliphatic polyester
Succinic anhydride (10g, 100mmol), GMA (40mmol, 5.68g), normal-butyl is taken to shrink
Glycerin ether (60mmol, 7.8g), tert-butylhydroquinone (1.33g, 8mmol) and zinc acetate (0.98g, 8mmol), add
100mL ethyl acetate：Butyl acetate=1:The mixed solution dissolving of 1 volume ratio, under nitrogen protection, 120 DEG C of ring opening copolymers are anti-
12h is answered, solvent is removed and obtains unsaturated aliphatic polyester.
Resulting unsaturated aliphatic polyester is detected by the methods described of embodiment 1, testing result is：Mw=
21611,Mn=12006, PDI=1.80.
(2) preparation of photocuring hydrogel and its performance
(a) formula of photocuring hydrogel
Unsaturated aliphatic polyester 5g prepared by step 1, hydroxy propyl methacrylate 0.5g, hydroxyethyl methacrylate
0.5g, hydroxy-ethyl acrylate 0.8g, acrylic acid-N, TMSDMA N dimethylamine base ethyl ester 1.2g, butyl acrylate 1g, acrylic acid-2-ethyl
Own ester 2g, 4- (2- hydroxyl-oxethyls) phenyl-(2- hydroxyl -2- propyl group) ketone 0.025g, thio propoxyl group thioxanthone 0.025g.
(b) preparation of photocuring hydrogel
Above-mentioned steps (a) raw material is well mixed, black out encapsulation, produces described photocuring hydrogel.
(c) photocuring hydrogel performance
To verify the performance of photocuring hydrogel of the present invention, above-mentioned photocuring hydrogel is filled into first transparent
In meniscus of knee joint mould, then by the meniscus of knee joint mould light intensity be 600 millijoules/square centimeter ultraviolet light
1min is irradiated, tissue engineering bracket meniscus of knee joint is obtained after the demoulding.
1. swelling behavior
Detected by the methods described of embodiment 1, the swelling ratio of prepared tissue engineering bracket is 686%.
2. modulus of elasticity
Detected by the methods described of embodiment 1, the modulus of elasticity of prepared tissue engineering bracket is 3.48MPa
3. cell experiment
Detected by the methods described of embodiment 1, the cell viability of prepared tissue engineering bracket is as shown in table 3.
The cell viability of the tissue engineering bracket of table 3
| Time (my god) | 1d | 3d | 7d |
| Cell viability % | 112 | 98 | 108 |
Detected by the methods described of embodiment 1, the cell adherence rate of prepared tissue engineering bracket is 91%.
The above results show that prepared support cytotoxicity is low, and cell adhesion is good, and cellular affinity is high.
Embodiment 4
(1) preparation of unsaturated aliphatic polyester
Succinic anhydride (10g, 100mmol), GMA (60mmol, 8.52g), normal-butyl is taken to shrink
Glycerin ether (40mmol, 5.2g), tert-butylhydroquinone (1.0g, 6mmol) and cobalt iso-octoate (1.38g, 4mmol), add
100mL ethyl acetate：Butyl acetate=1:The mixed solution dissolving of 1 volume ratio, under nitrogen protection, 100 DEG C of ring opening copolymers are anti-
10h is answered, solvent is removed and obtains unsaturated aliphatic polyester.
Resulting unsaturated aliphatic polyester is detected by the methods described of embodiment 1, testing result is：Mw=
15902,Mn=9756, PDI=1.63.
(2) preparation of photocuring hydrogel and its performance
(a) formula of photocuring hydrogel
Unsaturated aliphatic polyester 5g, acrylic acid-N, TMSDMA N dimethylamine base ethyl ester 1.5g prepared by step 1, five polyethylene glycol
Methyl ether acetate 1.0g, acrylic acid-2-ethyl caproite 2.4g, 4- (2- hydroxyl-oxethyls) phenyl-(2- hydroxyl -2- propyl group) ketone
0.005g, 2- hydroxy-2-methyl -1- phenylacetones 0.015g, 2,4,6- trimethylbenzoy-dipheny phosphine oxides
0.015g。
(b) preparation of photocuring hydrogel
Above-mentioned steps (a) raw material is well mixed, black out encapsulation, produces described photocuring hydrogel.
(c) photocuring hydrogel performance
To verify the performance of photocuring hydrogel of the present invention, above-mentioned photocuring hydrogel is filled into first transparent
In meniscus of knee joint mould, then by the meniscus of knee joint mould light intensity be 300 millijoules/square centimeter ultraviolet light
3min is irradiated, tissue engineering bracket meniscus of knee joint is obtained after the demoulding.
1. swelling behavior
Detected by the methods described of embodiment 1, the swelling ratio of prepared tissue engineering bracket is 11228%.
2. modulus of elasticity
Detected by the methods described of embodiment 1, the modulus of elasticity of prepared tissue engineering bracket is 3.44MPa
3. cell experiment
Detected by the methods described of embodiment 1, the cell viability of prepared tissue engineering bracket is as shown in table 4.
The cell viability of the tissue engineering bracket of table 4
| Time (my god) | 1 | 3 | 7 |
| Cell viability % | 109 | 116 | 110 |
Detected by the methods described of embodiment 1, the cell adherence rate of prepared tissue engineering bracket is 98%.
The above results show that prepared support cytotoxicity is low, and cell adhesion is good, and cellular affinity is high.
Embodiment 5
(1) preparation of unsaturated aliphatic polyester
Succinic anhydride (10g, 100mmol), GMA (30mmol, 4.26g), normal-butyl is taken to shrink
Glycerin ether (70mmol, 9.1g), tert-butylhydroquinone (0.664g, 4mmol) and tetra-n-butyl ammonium bromide (0.966g,
3mmol), 100mL ethyl acetate is added：Butyl acetate=1:The mixed solution dissolving of 1 volume ratio, under nitrogen protection, 90 DEG C
Ring opening copolymer reacts 5h, removes solvent and obtains unsaturated aliphatic polyester.
Resulting unsaturated aliphatic polyester is detected by the methods described of embodiment 1, testing result is：Mw=
7451,Mn=5867, PDI=1.27.
(2) preparation of photocuring hydrogel and its performance
(a) formula of photocuring hydrogel
Unsaturated aliphatic polyester 5g prepared by step 1, hydroxy propyl methacrylate 2.2g, acrylic acid-2-ethyl caproite
2.8g, 4- (2- hydroxyl-oxethyls) phenyl-(2- hydroxyl -2- propyl group) ketone 0.01g, 2- hydroxy-2-methyl -1- phenylacetones
0.01g, 2,4,6- trimethylbenzoy-dipheny phosphine oxide 0.01g, thio propoxyl group thioxanthone 0.01g.
(b) preparation of photocuring hydrogel
Above-mentioned steps (a) raw material is well mixed, black out encapsulation, produces described photocuring hydrogel.
(c) photocuring hydrogel performance
To verify the performance of photocuring hydrogel of the present invention, above-mentioned photocuring hydrogel is filled into first transparent
In meniscus of knee joint mould, then by the meniscus of knee joint mould light intensity be 500 millijoules/square centimeter ultraviolet light
4min is irradiated, tissue engineering bracket meniscus of knee joint is obtained after the demoulding.
1. swelling behavior
Detected by the methods described of embodiment 1, the swelling ratio of prepared tissue engineering bracket is 1042%.
2. modulus of elasticity
Detected by the methods described of embodiment 1, the modulus of elasticity of prepared tissue engineering bracket is 2.86MPa
3. cell experiment
Detected by the methods described of embodiment 1, the cell viability of prepared tissue engineering bracket is as shown in table 5.
The cell viability of the tissue engineering bracket of table 5
| Time (my god) | 1 | 3 | 7 |
| Cell viability % | 114 | 98 | 110 |
Detected by the methods described of embodiment 1, the cell adherence rate of prepared tissue engineering bracket is 102%.
The above results show that prepared support cytotoxicity is low, and cell adhesion is good, and cellular affinity is high.
Embodiment 6
(1) preparation of unsaturated aliphatic polyester
Succinic anhydride (10g, 100mmol), GMA (70mmol, 9.94g), normal-butyl is taken to shrink
Glycerin ether (30mmol, 3.9g), tert-butylhydroquinone (0.664g, 4mmol) and tetra-n-butyl ammonium bromide (1.61g,
5mmol), 100mL ethyl acetate is added：Butyl acetate=1:The mixed solution dissolving of 1 volume ratio, under nitrogen protection, 105 DEG C
Ring opening copolymer reacts 7h, removes solvent and obtains unsaturated aliphatic polyester.
Resulting unsaturated aliphatic polyester is detected by the methods described of embodiment 1, testing result is：Mw=
10218,Mn=7683, PDI=1.33.
(2) preparation of photocuring hydrogel and its performance
(a) formula of photocuring hydrogel
Unsaturated aliphatic polyester 5g prepared by step 1, hydroxyethyl methacrylate 0.2g, hydroxy propyl methacrylate
0.8g, hydroxy-ethyl acrylate 1g, acrylic acid-N, TMSDMA N dimethylamine base ethyl ester 0.6g, acrylic acid-2-ethyl caproite 2.3g, 4- (2- hydroxyls
Base oxethyl) phenyl-(2- hydroxyl -2- propyl group) ketone 0.03g.
(b) preparation of photocuring hydrogel
Above-mentioned steps (a) raw material is well mixed, black out encapsulation, produces described photocuring hydrogel.
(c) photocuring hydrogel performance
To verify the performance of photocuring hydrogel of the present invention, above-mentioned photocuring hydrogel is filled into first transparent
In meniscus of knee joint mould, then by the meniscus of knee joint mould light intensity be 350 millijoules/square centimeter ultraviolet light
2.5min is irradiated, tissue engineering bracket meniscus of knee joint is obtained after the demoulding.
1. swelling behavior
Detected by the methods described of embodiment 1, the swelling ratio of prepared tissue engineering bracket is 985%.
2. modulus of elasticity
Detected by the methods described of embodiment 1, the modulus of elasticity of prepared tissue engineering bracket is 3.41MPa
3. cell experiment
Detected by the methods described of embodiment 1, the cell viability of prepared tissue engineering bracket is as shown in table 6.
The cell viability of the tissue engineering bracket of table 6
| Time (my god) | 1 | 3 | 7 |
| Cell viability % | 99 | 98 | 96 |
Detected by the methods described of embodiment 1, the cell adherence rate of prepared tissue engineering bracket is 91%.
The above results show that prepared support cytotoxicity is low, and cell adhesion is good, and cellular affinity is high.
Embodiment 7
(1) preparation of unsaturated aliphatic polyester
Succinic anhydride (10g, 100mmol), GMA (50mmol, 7.1g), normal-butyl is taken to shrink
Glycerin ether (50mmol, 6.5g), tert-butylhydroquinone (0.83g, 5mmol) and TBAB (0.83g, 5mmol),
Add 100mL ethyl acetate：Butyl acetate=1:The mixed solution dissolving of 1 volume ratio, under nitrogen protection, 115 DEG C of open loops are total to
Poly- reaction 6h, removes solvent and obtains unsaturated aliphatic polyester.
Resulting unsaturated aliphatic polyester is detected by the methods described of embodiment 1, testing result is：Mw=
15074,Mn=8764, PDI=1.72.
(2) preparation of photocuring hydrogel and its performance
(a) formula of photocuring hydrogel
Unsaturated aliphatic polyester 5g prepared by step 1, hydroxy propyl methacrylate 2.5g, acrylic acid-2-ethyl caproite
2.8g, 4- (2- hydroxyl-oxethyls) phenyl-(2- hydroxyl -2- propyl group) ketone 0.045g.
(b) preparation of photocuring hydrogel
Above-mentioned steps (a) raw material is well mixed, black out encapsulation, produces described photocuring hydrogel.
(c) photocuring hydrogel performance
To verify the performance of photocuring hydrogel of the present invention, above-mentioned photocuring hydrogel is filled into first transparent
In meniscus of knee joint mould, then by the meniscus of knee joint mould light intensity be 450 millijoules/square centimeter ultraviolet light
4min is irradiated, tissue engineering bracket meniscus of knee joint is obtained after the demoulding.
1. swelling behavior
Detected by the methods described of embodiment 1, the swelling ratio of prepared tissue engineering bracket is 869%.
2. modulus of elasticity
Detected by the methods described of embodiment 1, the modulus of elasticity of prepared tissue engineering bracket is 2.86MPa
3. cell experiment
Detected by the methods described of embodiment 1, the cell viability of prepared tissue engineering bracket is as shown in table 7.
The cell viability of the tissue engineering bracket of table 7
| Time (my god) | 1 | 3 | 7 |
| Cell viability % | 97 | 99 | 95 |
Detected by the methods described of embodiment 1, the cell adherence rate of prepared tissue engineering bracket is 91%.
The above results show that prepared support cytotoxicity is low, and cell adhesion is good, and cellular affinity is high.
Embodiment 8
(1) preparation of unsaturated aliphatic polyester
Succinic anhydride (10g, 100mmol), GMA (50mmol, 7.1g), normal-butyl is taken to shrink
Glycerin ether (50mmol, 6.5g), tert-butylhydroquinone (0.83g, 5mmol) and TBAB (0.83g, 5mmol),
Add 100mL ethyl acetate：Butyl acetate=1:The mixed solution dissolving of 1 volume ratio, under nitrogen protection, 100 DEG C of open loops are total to
Poly- reaction 8h, removes solvent and obtains unsaturated aliphatic polyester.
Resulting unsaturated aliphatic polyester is detected by the methods described of embodiment 1, testing result is：Mw=
11558,Mn=7362, PDI=1.57.
(2) preparation of photocuring hydrogel and its performance
(a) formula of photocuring hydrogel
Unsaturated aliphatic polyester 5g, hydroxy propyl methacrylate 2.6g, Isooctyl acrylate monomer 2.4g prepared by step 1,
4- (2- hydroxyl-oxethyls) phenyl-(2- hydroxyl -2- propyl group) ketone 0.015g, thio propoxyl group thioxanthone 0.025g.
(b) preparation of photocuring hydrogel
Above-mentioned steps (a) raw material is well mixed, black out encapsulation, produces described photocuring hydrogel.
(c) photocuring hydrogel performance
To verify the performance of photocuring hydrogel of the present invention, above-mentioned photocuring hydrogel is filled into first transparent
In meniscus of knee joint mould, then by the meniscus of knee joint mould light intensity be 600 millijoules/square centimeter ultraviolet light
1min is irradiated, tissue engineering bracket meniscus of knee joint is obtained after the demoulding.
1. swelling behavior
Detected by the methods described of embodiment 1, the swelling ratio of prepared tissue engineering bracket is 916%.
2. modulus of elasticity
The methods described of embodiment 1 is detected, and the modulus of elasticity of prepared tissue engineering bracket is 2.49MPa
3. cell experiment
Detected by the methods described of embodiment 1, the cell viability of prepared tissue engineering bracket is as shown in table 8.
The cell viability of the tissue engineering bracket of table 8
| Time (my god) | 1 | 3 | 7 |
| Cell viability % | 103 | 97 | 108 |
Detected by the methods described of embodiment 1, the cell adherence rate of prepared tissue engineering bracket is 97%.
The above results show that prepared support cytotoxicity is low, and cell adhesion is good, and cellular affinity is high.
Claims (7)
1. a kind of unsaturated aliphatic polyester, the polyester is shown in construction unit and chemical formula (II) shown in chemical formula (I)
Construction unit presses 3:7~7:The polyester of the 3 linear random arrangement of mol ratio, its number-average molecular weight are 5000~12000, dispersiveness
Index is 1.21~1.80,
Described unsaturated aliphatic polyester is by GMA, n-butyl glycidyl ether and succinic anhydride
Ring opening copolymer is carried out to obtain.
2. unsaturated aliphatic polyester according to claim 1, it is characterised in that the structure shown in the chemical formula (I)
The mol ratio of unit and the construction unit shown in chemical formula (II) is 2:3~3:2, number-average molecular weight is 5000~10000, is disperseed
Sex index preferably 1.21~1.60.
3. unsaturated aliphatic polyester according to claim 1 or 2, it is characterised in that the unsaturated aliphatic polyester by
Following methods are made：
Succinic anhydride is taken, GMA, n-butyl glycidyl ether, tert-butylhydroquinone is added and urges
Agent, it is dissolved into appropriate mixed solution, under nitrogen protection, 90~120 DEG C of ring opening copolymers react 5~12h, remove solvent
Obtain described unsaturated aliphatic polyester；Wherein,
Described GMA and the addition sum of n-butyl glycidyl ether, which are equal to, takes succinic anhydride
Mole, described first base propylene acid glycidyl ester ester ︰ n-butyl glycidyl ethers=︰ 3 of 3 ︰ 7~7 mol ratio；
The addition of described tert-butylhydroquinone is the 1~10% of the mole of taken succinic anhydride；
The addition of described catalyst is the 1~10% of the mole of taken succinic anhydride；
Described mixed solution is made up of the ethyl acetate and butyl acetate of isometric ratio；
Described catalyst is one kind in tetra-n-butyl ammonium bromide, zinc acetate, zinc Isoocatanoate and cobalt iso-octoate.
A kind of 4. unsaturated aliphatic polyester according to claim 3, it is characterised in that
The mol ratio of described first base propylene acid glycidyl ester ester ︰ n-butyl glycidyl ethers is the ︰ 2 of 2 ︰ 3~3；
The addition of described tert-butylhydroquinone is the 2~8% of the mole of taken succinic anhydride；
The addition of described catalyst is the 2~8% of the mole of taken succinic anhydride；
Described catalyst is tetra-n-butyl ammonium bromide；
The temperature of described ring opening copolymer reaction is 100~120 DEG C；
The time of described ring opening copolymer reaction is 5~10h.
5. a kind of photocuring hydrogel, the photocuring hydrogel is as the unsaturated aliphatic polyester described in claim 1 or 2, parent
Water-based unsaturated monomer, soft unsaturated monomer and light trigger composition, wherein, the content of hydrophily unsaturated monomer is insatiable hunger
With aliphatic polyester weight 40~60%, the content of soft unsaturated monomer for unsaturated aliphatic polyester weight 40~
60%, the content of light trigger is the 0.5~1% of unsaturated aliphatic polyester weight；
Described hydrophily unsaturated monomer is hydroxypropyl acrylate, hydroxy propyl methacrylate, hydroxyethyl methacrylate, third
Olefin(e) acid hydroxyl ethyl ester and acrylic acid-N, more than one or two kinds of in TMSDMA N dimethylamine base ethyl ester；
Described soft unsaturated monomer is one kind in butyl acrylate, acrylic acid-2-ethyl caproite and Isooctyl acrylate monomer
Or two kinds；
Described light trigger is 4- (2- hydroxyl-oxethyls) phenyl-(2- hydroxyl -2- propyl group) ketone, 2- hydroxy-2-methyl -1- benzene
It is one or two kinds of in benzylacetone, 2,4,6- trimethylbenzoy-diphenies phosphine oxide and thio propoxyl group thioxanthone
More than.
6. a kind of photocuring hydrogel according to claim 5, it is characterised in that described hydrophily unsaturated monomer
Content is the 50% of unsaturated aliphatic polyester weight, and the content of described soft unsaturated monomer is unsaturated aliphatic polyester
The 50% of weight.
7. application of the photocuring hydrogel in tissue engineering bracket is prepared described in claim 5 or 6.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746547A (en) * | 2019-10-31 | 2020-02-04 | 南方医科大学南方医院 | Photo-curing hydrogel for preparing cell scaffold |
| CN110776599A (en) * | 2019-10-31 | 2020-02-11 | 南方医科大学南方医院 | Antibacterial hydrogel |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372826A (en) * | 2010-08-12 | 2012-03-14 | 株式会社Lg化学 | Thermally curable resin composition for protective film |
| CN102736411A (en) * | 2011-04-08 | 2012-10-17 | 奇美实业股份有限公司 | Photosensitive resin composition, and color filter and liquid crystal display device using same |
| US20140171568A1 (en) * | 2012-12-18 | 2014-06-19 | Reichhold, Inc. | Vinyl-containing compounds with high heat distortion |
| CN103890659A (en) * | 2011-08-26 | 2014-06-25 | 罗门哈斯电子材料韩国有限公司 | Photopolymerizable unsaturated resin, photosensitive resin composition comprising the same, and light shielding spacer and liquid crystal display device formed therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372826A (en) * | 2010-08-12 | 2012-03-14 | 株式会社Lg化学 | Thermally curable resin composition for protective film |
| CN102736411A (en) * | 2011-04-08 | 2012-10-17 | 奇美实业股份有限公司 | Photosensitive resin composition, and color filter and liquid crystal display device using same |
| CN103890659A (en) * | 2011-08-26 | 2014-06-25 | 罗门哈斯电子材料韩国有限公司 | Photopolymerizable unsaturated resin, photosensitive resin composition comprising the same, and light shielding spacer and liquid crystal display device formed therefrom |
| US20140171568A1 (en) * | 2012-12-18 | 2014-06-19 | Reichhold, Inc. | Vinyl-containing compounds with high heat distortion |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746547A (en) * | 2019-10-31 | 2020-02-04 | 南方医科大学南方医院 | Photo-curing hydrogel for preparing cell scaffold |
| CN110776599A (en) * | 2019-10-31 | 2020-02-11 | 南方医科大学南方医院 | Antibacterial hydrogel |
| CN110776599B (en) * | 2019-10-31 | 2021-12-24 | 南方医科大学南方医院 | Antibacterial hydrogel |
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