CN108484922B - A kind of hydrophobic type polycaprolactone and preparation method thereof - Google Patents
A kind of hydrophobic type polycaprolactone and preparation method thereof Download PDFInfo
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- CN108484922B CN108484922B CN201810356614.1A CN201810356614A CN108484922B CN 108484922 B CN108484922 B CN 108484922B CN 201810356614 A CN201810356614 A CN 201810356614A CN 108484922 B CN108484922 B CN 108484922B
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Abstract
The invention discloses a kind of hydrophobic type polycaprolactones and preparation method thereof: pla-pcl being reacted with alkamine compound, prepares terminal hydroxy group polycaprolactone；By terminal hydroxy group pla-pcl and anhydride reaction, carboxyl end group polycaprolactone is prepared；Bromo acid glycol ester is reacted with containing fluoroalkyl, prepares terminal hydroxy group fluorine-contaninig polyacrylate；Carboxyl end group polycaprolactone is reacted with terminal hydroxy group fluorine-contaninig polyacrylate, prepares hydrophobic type polycaprolactone.Product hydrophobic segment molecular weight of the present invention is controllable, narrow molecular weight distribution, and fluorine content and hydrophobicity are controllable.When prepared by hydrophobic type polycaprolactone, fluoropolymer is activated by previously prepared end group, fluoropolymer product, the easily controllable degree of polymerization are obtained in homogeneous system.It solves the problems, such as that transformation occurs due to dissolubility, be difficult to directly in PCL end of the chain in-situ preparation fluoropolymer chain.Pendant carboxylic group PCL will be contained, and direct polycondensation prepares product under mild reaction conditions with organo-fluorine polymer containing activity hydroxy, avoids PCL degradation.
Description
Technical field
The present invention relates to a kind of macromolecule modified technologies, and in particular to a kind of hydrophobic type polycaprolactone and preparation method thereof.
Background technique
Polycaprolactone (poly-caprolactone, PCL) is by ω-caprolactone monomer in metallo-organic compound (such as four
Phenyltin) it is catalyzed a kind of linear aliphatic adoption ester that lower ring-opening polymerisation obtains, there is superior biological degradability, good biology
Compatibility, drug permeability and mechanical property, oneself obtain U.S. FDA certification, in film application field oneself have extensively research and
Using.Polycaprolactone (PCL) fusing point is 59~64 DEG C, and glass transition temperature is -60 DEG C.There are 5 non-poles on its structural repeat unit
Property methylene-CH2And a polar ester groups-COO-, i.e. ,-(COOCHCH2CH2CH2CH2CH2) Pn, such structure makes PCL
With good flexibility and processability, while this material has good biocompatibility.
Currently, polycaprolactone is the most extensive as the research that biomaterial is applied, especially repaired using it as tissue
Biomaterial scaffolds, the research for biomedicine fields such as medicament slow releases and the application report on multiplexing way emerge one after another.At this
In a little application fields, when polycaprolactone is used as the organization bracket that Artificial neural, artificial blood vessel etc. are contacted with human body fluid, due to
Inside pipe wall may adsorb active constituent in body fluid when contacting body fluid, this may cause tube wall adventitious deposit, even make sometimes
At vessel wall occlusion.Therefore, it has been proposed that carrying out hydrophobically modified to polycaprolactone.
However, lacking reactivity side group functional group on the macromolecular chain of polycaprolactone, it is difficult to be grafted by pendant chemical etc.
It is modified that hydrophobic material is provided.Therefore, the active end group of polycaprolactone is transformed into carbon bromine key (C-Br), then by atom transfer freedom
Base polymerize (ATRP) method and obtains block copolymer by the generation free radical polymerization of the unsaturated monomers such as acrylate, it is expected to realize poly-
The chemical modification of caprolactone.This method but has the following deficiencies: that (1) is influenced by macromolecular chain, gathers oneself in the course of the polymerization process
The lactone end of the chain carbon bromine key (C-Br) poor activity, it is difficult to effectively cause unsaturated monomer generation polymerization realization and be modified；(2) due to fluorine-containing
The modified polycaprolactone of monomer block is hydrophobic, and polarity is very low, it is difficult to be dissolved in conventional organosolv, in block polymerization initial reaction stage
It may be precipitated from conventional organic solvent system.Therefore cause the fluoropolymer block accessed when chemical modification short, it is modified
Effect is undesirable and poor controllability, is changed to be difficult to if using the solvent (such as organic fluorous solvent) that can dissolve block modified polycaprolactone
Dissolve atom transfer radical polymerization (ATRP) initiator.
In addition, fluoro-containing macromolecule material is difficult to degrade compared with PCL.For example, since carbon-fluorine bond (C-F) has in fluoroalkyl chain
Have the bond energy of 460kJ/mol, be about 4 times of carbon-carbon bond (C-C) bond energy, therefore carbon-fluorine bond is highly stable, is difficult to crack, also it is positive because
In this way, fluorochemical difficulty is decomposed, and there is cumulative bad and bio-toxicity.This chemical structure feature makes fluoro containing polymers difficult
Macromolecule is set to degrade in the form removed according to side group.In addition, fluorine material can assign polymer excellent liquid repellent performance
With low-surface-energy and low polarity, therefore it is unfavorable for biological adsorption and degrades.Exactly because these of fluoro-containing macromolecule material
Essential attribute is highly desirable to develop a kind of fluoro-containing macromolecule material with degradation capability.
Summary of the invention
It is that fluorine-containing alkyl polyacrylates are block modified the purpose of the present invention is to provide a kind of block modified polycaprolactone
Polycaprolactone.
To achieve the above object of the invention, the technical scheme adopted by the invention is that:
A kind of hydrophobic type polycaprolactone, chemical structural formula are as follows:
Wherein, Rf is containing fluoroalkyl；R is H or alkyl；M is 35~1300；N is 5~100；Asterisk is from raw material
Pla-pcl.
Preferably, described containing fluoroalkyl is nine fluorine amyl groups, ten trifluoro octyls, 17 fluorine decyls, hexafluoro butyl, ten difluoro heptan
Base or octafluoro amyl (- CH2(CF2)3CF3、-CH2(CF2)5CF3、-CH2(CF2)7CF3、-CF2CFHCF3、-CH2(CF2)4H、-
(CF2)6One of H)；The alkyl is methyl.
The invention also discloses the preparation methods of above-mentioned hydrophobic type polycaprolactone, include the following steps:
(1) pla-pcl is reacted with alkamine compound, prepares terminal hydroxy group polycaprolactone；
(2) by terminal hydroxy group pla-pcl and anhydride reaction, carboxyl end group polycaprolactone is prepared；
(3) bromo acid glycol ester is reacted with containing fluoroalkyl, prepares the fluorine-containing polyacrylic acid of terminal hydroxy group
Ester；
(4) carboxyl end group polycaprolactone is reacted with terminal hydroxy group fluorine-contaninig polyacrylate, prepares hydrophobic type polycaprolactone.
The invention also discloses a kind of preparation methods of hydrophobic type polycaprolactone film, include the following steps:
(1) pla-pcl is reacted with alkamine compound, prepares terminal hydroxy group polycaprolactone；
(2) by terminal hydroxy group pla-pcl and anhydride reaction, carboxyl end group polycaprolactone is prepared；
(3) bromo acid glycol ester is reacted with containing fluoroalkyl, prepares the fluorine-containing polyacrylic acid of terminal hydroxy group
Ester；
(4) carboxyl end group polycaprolactone is reacted with terminal hydroxy group fluorine-contaninig polyacrylate, prepares hydrophobic type polycaprolactone；
(5) at room temperature, hydrophobic type polycaprolactone is dissolved in organic solvent, is configured to solution；Then by solution room temperature
Lower natural drying film forming, prepares hydrophobic type polycaprolactone film.
The invention also discloses the preparation method of terminal hydroxy group fluorine-contaninig polyacrylate, include the following steps: bromo isobutyl
Sour glycol ester, pentamethyl-diethylenetriamine and cuprous bromide under a nitrogen 30~40 DEG C stirring 1~for 24 hours；Then it is added fluorine-containing
50~90 DEG C of alkyl acrylate reactions 1~for 24 hours, prepare terminal hydroxy group fluorine-contaninig polyacrylate.
In the present invention, the molecular weight of the pla-pcl is 4.56 ten thousand~14.82 ten thousand；Alkamine compound is 6- amino-
1- hexanol；Acid anhydrides is succinic anhydride；Containing fluoroalkyl be nine fluorine amyl group acrylate, ten trifluoro octyl acrylates,
Ten trifluoro octyl methyl acrylate, 17 fluorine decyl acrylate, 17 fluorine decyl methacrylates, hexafluoro butyl propyleneglycol
One of acid esters, hexafluoro butyl methyl acrylate, ten difluoro heptyl methacrylates or octafluoro acrylate.
In the present invention, the mass ratio of pla-pcl and alkamine compound is 1: 0.2~2；Terminal hydroxy group pla-pcl and acid
The mass ratio of acid anhydride is (1~200): (0.5~2)；Bromo acid glycol ester is with the mass ratio containing fluoroalkyl
(1 × 10-6~5 × 10-5): (0.5~5)；The mass ratio of carboxyl end group polycaprolactone and terminal hydroxy group fluorine-contaninig polyacrylate be (1~
4): (0.05~10).
In the present invention, the reaction of step (1) is to react at room temperature 1~24 hour under nitrogen protection；The reaction of step (2) is nitrogen
1~6h is reacted at room temperature under gas shielded；The reaction of step (3) be 50~90 DEG C reaction 1~for 24 hours；The reaction of step (4) is 30~65
DEG C reaction 1~8h.
In the present invention, the reaction of step (1) carries out in organic solvent；The reaction of step (2) in organic solvent, it is anhydrous
It is carried out in the presence of potassium carbonate and 4-dimethylaminopyridine；The reaction of step (3) in organic solvent, pentamethyl-diethylenetriamine and
It is carried out in the presence of cuprous bromide；The reaction of step (4) in organic solvent, N, carry out in the presence of N '-carbonyl dimidazoles.
In the present invention, in step (3), bromo acid glycol ester, pentamethyl-diethylenetriamine and cuprous bromide are existed
Under nitrogen 30~40 DEG C stirring 1~for 24 hours；Then be added containing 50~90 DEG C of fluoroalkyl reaction 1~for 24 hours, prepare end hydroxyl
Base fluorine-contaninig polyacrylate.
In the present invention, in step (4), carboxyl end group polycaprolactone and N, N '-carbonyl dimidazoles are reacted at room temperature 1 under a nitrogen
~24 hours；Then terminal hydroxy group fluorine-contaninig polyacrylate solution is added to prepare hydrophobic type in 30~65 DEG C of 1~8h of reaction and gather oneself
Lactone.
The present invention further discloses hydrophobic type polycaprolactones to prepare answering in hydrophobic material or biodegradation material
With；Terminal hydroxy group fluorine-contaninig polyacrylate is preparing the application in hydrophobic type polycaprolactone material.
In the present invention, above-mentioned reaction is completed to carry out purification processes, can carry out as follows:
After reaction, reaction solution is added in 10 ~ 300 parts of dehydrated alcohols for step (1), and solid is precipitated.Filtering, filter cake with
Dehydrated alcohol wash 1 ~ 2 part × 3 times, at 30 ~ 50 DEG C be dried in vacuo 1 ~ for 24 hours, obtain terminal hydroxy group polycaprolactone (PCL)-OH.
After reaction, 0.3 ~ 1.0 part of acetic acid is added in filtering, filtrate to step (2), and 20 ~ 500 parts of deionizations are added in solution
In water, solid is precipitated.Filtering, filter cake with dehydrated alcohol washing 2 ~ 10 parts × 3 times, at 30 ~ 50 DEG C be dried in vacuo 1 ~ for 24 hours, obtain
To carboxyl end group polycaprolactone (PCL)-COOH.
After reaction, 1 ~ 20 part of THF and 1 ~ 20 part of fluorine-containing organic solvent is added in step (3), crosses neutral alumina (200-
300 mesh) column, obtain faint yellow clear solution.Solution at 30 ~ 70 DEG C vacuum rotary steam remove solvent, then by crude product be added 5 ~
In 30 parts of anhydrous methanols, be precipitated solid, filtering, wash 1 ~ 3 part × 3 times with n-hexane, at 30 ~ 100 DEG C DEG C vacuum drying 1 ~
24 hours, obtain terminal hydroxy group fluorine-contaninig polyacrylate.
After reaction, reaction solution is poured into 5 ~ 200 parts of n-hexanes for step (4), and crude product, filtering, with anhydrous is precipitated
After ethanol washing 2 ~ 10 parts × 3 times, it is dried in vacuo 1 at 30 ~ 50 DEG C ~ ~ for 24 hours, it is block modified poly- to obtain fluorine-containing alkyl polymer
Caprolactone is hydrophobic type polycaprolactone.
Above-mentioned fluorine-containing organic solvent is trifluoromethylbenzene, and one or both of 1,3- bis- (trifluoromethyl) benzene are arbitrarily to compare
Example mixing.
The present invention is first by high molecular weight polycaprolactone terminal hydroxy group, carboxylated；It is controllable by ATRP method synthesized polymer degree again
Terminal hydroxy group fluorine-contaninig polyacrylate；Finally existed by carboxyl end group polycaprolactone and pre-synthesis terminal hydroxy group fluorine-contaninig polyacrylate
Under N, N '-carbonyl dimidazoles (CDI) activation, esterification is carried out under temperate condition, it is embedding to obtain fluorine-containing alkyl polyacrylates
The modified polycaprolactone of section, reaction structure formula are shown in attached drawing 1.
Compared with prior art, technical solution provided by the invention the beneficial effect is that:
(1) by high molecular weight PCL with carboxyl end group activation, N, N '-carbonyl dimidazoles (CDI) activation after, with contain activity hydroxy
Organo-fluorine polymer can be with direct polycondensation, the extent of reaction is high, and reaction condition is mild.
(2) fluoropolymer is activated by the previously prepared end group of ATRP, then accessed in PCL strand, due to being in homogeneous body
Fluoropolymer product is obtained in system, therefore is easy to control the degree of polymerization of fluoropolymer product and modified PCL, obtained product point
Son amount narrowly distributing.Meanwhile it also solving due to dissolubility generation transformation, being difficult to directly in PCL end of the chain in-situ preparation fluoropolymer
The problem of object chain.
(3) it by introducing degradable segment polycaprolactone (PCL) in fluoropolymer molecular structure, has obtained degradable
Fluoro-containing macromolecule material；The PCL molecular size range of control access obtains block polymer, and available degradation property is different
Fluoro-containing macromolecule material；Carboxyl end group PCL is reacted with organo-fluorine polymer containing activity hydroxy in mild under activator effect
Under the conditions of direct polycondensation prepare the block modified fluoropolymer of PCL, can to avoid PCL entirely preparation reaction process in occur heat
Degradation.
(4) the hydrophobic type polycaprolactone that block modified PCL produced according to the present invention can degrade to avoid PCL, therefore obtain
(PCL) molecular weight product is high, and preparation process is easy, raw material are easy to get, easy to industrialized production and popularization and application.
Detailed description of the invention
Fig. 1 is hydrophobic type polycaprolactone preparation reaction schematic diagram of the present invention；
Fig. 2 is the structural schematic diagram of 1 hydrophobic type polycaprolactone of embodiment；
Fig. 3 is the structural schematic diagram of 2 hydrophobic type polycaprolactone of embodiment；
Fig. 4 is the structural schematic diagram of 3 hydrophobic type polycaprolactone of embodiment；
Fig. 5 is the structural schematic diagram of 4 hydrophobic type polycaprolactone of embodiment；
Fig. 6 is the structural schematic diagram of 5 hydrophobic type polycaprolactone of embodiment；
Fig. 7 is the structural schematic diagram of 6 hydrophobic type polycaprolactone of embodiment；
Fig. 8 is the structural schematic diagram of 7 hydrophobic type polycaprolactone of embodiment；
Fig. 9 is the structural schematic diagram of 8 hydrophobic type polycaprolactone of embodiment；
Figure 10 is the structural schematic diagram of 9 hydrophobic type polycaprolactone of embodiment；
Figure 11 is the structural schematic diagram of 10 hydrophobic type polycaprolactone of embodiment；
Figure 12 is the structural schematic diagram of 1 hydrophobic type polycaprolactone of comparative example；
Figure 13 is connecing to water for the hydrophobic type polycaprolactone film of unmodified polycaprolactone (PCL) and preparation of the embodiment of the present invention
Feeler test chart.Wherein, PCL-PTFOA (2h) is hydrophobic type polycaprolactone film prepared by embodiment 1, and PCL-PTFOA (4h) is
Hydrophobic type polycaprolactone film prepared by embodiment 2, PCL-PTFOA (6h) are hydrophobic type polycaprolactone film prepared by embodiment 3,
PCL-PTFOA (8h) is hydrophobic type polycaprolactone film prepared by embodiment 4；
Figure 14 is the infrared absorption of the hydrophobic type polycaprolactone of unmodified polycaprolactone (PCL) and preparation of the embodiment of the present invention
Curve.Wherein, curve a is unmodified polycaprolactone, and curve b is hydrophobic type polycaprolactone prepared by embodiment 1, and curve c is real
The hydrophobic type polycaprolactone of the preparation of example 2 is applied, curve d is hydrophobic type polycaprolactone prepared by embodiment 3, and curve e is the system of embodiment 4
Standby hydrophobic type polycaprolactone；
Figure 15 is the nuclear magnetic resonance of the hydrophobic type polycaprolactone of unmodified polycaprolactone (PCL) and preparation of the embodiment of the present invention
Figure.Wherein, curve (1) is unmodified polycaprolactone, and curve (2) is hydrophobic type polycaprolactone prepared by embodiment 1, curve (3)
For hydrophobic type polycaprolactone prepared by embodiment 2, curve (4) is hydrophobic type polycaprolactone prepared by embodiment 3, and curve (5) is
Hydrophobic type polycaprolactone prepared by embodiment 4；
Figure 16 is the Polycaprolactone modified fluoropolymer-containing degradation process photo figure of the present invention；
Figure 17 is the degradation process SEM shape appearance figure of hydrophobic type polycaprolactone of the invention；
Figure 18 is the fluorine-containing polycaprolactone solution thereon of the present invention, wherein (a) solvent is methylene chloride, solution concentration is
2wt%；(b) solvent is tetrahydrofuran, solution concentration 3wt%；(c) solvent is methylene chloride, solution concentration 10wt%；
Figure 19 is the photo of the fluorine-containing polycaprolactone film of the present invention, wherein (a) solvent is methylene chloride, solution concentration is
3wt%；(b) solvent is tetrahydrofuran, solution concentration 10wt%.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and examples.
Embodiment 1
(1) polycaprolactone terminal hydroxy group
The 50.0g PCL that molecular weight is 80,000 is dissolved in 500g Isosorbide-5-Nitrae-dioxane at 37 DEG C, under nitrogen protection,
51g 6- amino -1- hexanol is added, reacts 8h.After reaction, reaction solution is slowly added to the anhydrous second of the 1000g being stirred continuously
In alcohol, solid is precipitated.Filtering, filter cake wash 100g × 3 time with dehydrated alcohol, are dried in vacuo for 24 hours at 37 DEG C, obtain product
39.6g, yield 79.2%.Measuring molecular weight of product is 69800.
(2) polycaprolactone carboxyl end group
500g 1,4- bis- is added in the terminal hydroxy group polycaprolactone 25.0g(PCL-OH of above-mentioned preparation) and 28.5g succinic anhydride
In six ring of oxygen.After stirring and dissolving, 9.85g Anhydrous potassium carbonate (K is sequentially added2CO3) and 8.70g 4-dimethylaminopyridine
(DMAP), 2h is reacted at room temperature under nitrogen protection.After reaction, it filters, 15g acetic acid is added in filtrate, and solution addition 1000g is gone
In ionized water, solid is precipitated.Filtering, filter cake wash 120g × 3 time with dehydrated alcohol, are dried in vacuo for 24 hours, obtain at 37 DEG C
Product 21.5g, yield 86.0%.Measuring molecular weight of product is 68500.
(3) it is poly- (ten trifluoro octyl acrylate of 1H, 1H, 2H, 2H-) to prepare terminal hydroxy group for ATRP method
420ug bromo acid glycol ester and 642ug pentamethyl-diethylenetriamine (PMDETA) are dissolved in 60g 2- fourth
In ketone, after dissolution, 0.4g cuprous bromide is added, is stirred to react 15min at 40 DEG C under nitrogen protection, obtains catalyst.It is added
Ten trifluoro octyl acrylate (TFOA) of 63.0g 1H, 1H, 2H, 2H- is heated to 80 DEG C, reacts 2 hours.After reaction, add
Enter 300gTHF and 100g benzotrifluoride, crosses neutral alumina (200-300 mesh) column, obtain faint yellow clear solution.Solution is 65
Vacuum rotary steam removes solvent at DEG C, and then crude product is added in 950g anhydrous methanol, and solid is precipitated, and filtering is washed with n-hexane
150g × 3 time are dried in vacuo 24 hours at 55 DEG C, obtain terminal hydroxy group fluorine-contaninig polyacrylate 57.1g, yield 90.6%.
(4) esterification prepares block polymer
7.0g carboxyl end group polycaprolactone (PCL-COOH) is dissolved in the anhydrous THF of 80g in three-necked flask at room temperature, is added
Enter 4.7g N, N '-carbonyl dimidazoles (CDI) react 2h at 30 DEG C under nitrogen protection.By 0.5g terminal hydroxy group it is poly- (1H, 1H,
Ten trifluoro octyl acrylate of 2H, 2H-) it is dissolved in 30g benzotrifluoride and is configured to solution, it is added in three-necked flask, reaction is mixed
It closes object and reacts 3h at 53 ~ 55 DEG C.After reaction, reaction solution is poured into 280g n-hexane, crude product is precipitated, filtered, with
After dehydrated alcohol washs 45g × 3 time, it is dried in vacuo 3h at 37 DEG C, obtains the i.e. fluorine-containing alkyl polymer of hydrophobic type polycaprolactone
Block modified polycaprolactone 6.5g, yield 86.7%.Measuring molecular weight of product is 72800.Product structure formula is as shown in Figure 2.
(5) hydrophobicity is tested
At room temperature, the block modified polycaprolactone of the fluorine-containing alkyl polymer of 0.5g is dissolved in 10g methylene chloride, is configured to
The solution that mass concentration is 5%.It pours this solution into surface plate, spontaneously dries film forming at room temperature.Using the U.S.
The full-automatic microscopic droplets wetability measuring instrument of 200 type of OCAH of dataphysics company carries out contact angle to polymer film
Test, judges the surface wettability of polymer.Water is chosen as test droplets, droplet size is 3 μ L, and testing five times must put down
Equal contact angle is 108.0 ± 0.8 ° (unmodified polycaprolactone is 96.8 ± 1.0 ° to water contact angle), referring to attached drawing 13.
Embodiment 2
(1) polycaprolactone terminal hydroxy group
The 50.0g PCL that molecular weight is 80,000 is dissolved in 520g Isosorbide-5-Nitrae-dioxane at 37 DEG C, under nitrogen protection,
49g 6- amino -1- hexanol is added, reacts 12h.After reaction, the 1050g for reaction solution being slowly added to be stirred continuously is anhydrous
In ethyl alcohol, solid is precipitated.Filtering, filter cake wash 100g × 3 time with dehydrated alcohol, are dried in vacuo for 24 hours, are produced at 37 DEG C
Object 37.9g, yield 75.8%.Measuring molecular weight of product is 67500.
(2) polycaprolactone carboxyl end group
510g 1,4- bis- is added in the terminal hydroxy group polycaprolactone 25.0g(PCL-OH of above-mentioned preparation) and 29.2g succinic anhydride
In six ring of oxygen.After stirring and dissolving, 9.88g Anhydrous potassium carbonate (K is sequentially added2CO3) and 8.75g 4-dimethylaminopyridine
(DMAP), 4h is reacted at room temperature under nitrogen protection.After reaction, it filters, 15g acetic acid is added in filtrate, and solution addition 990g is gone
In ionized water, solid is precipitated.Filtering, filter cake wash 120g × 3 time with dehydrated alcohol, are dried in vacuo for 24 hours, obtain at 37 DEG C
Product 21.1g, yield 84.4%.Measuring molecular weight of product is 67700.
(3) it is poly- (ten trifluoro octyl acrylate of 1H, 1H, 2H, 2H-) to prepare terminal hydroxy group for ATRP method
423ug bromo acid glycol ester and 645ug pentamethyl-diethylenetriamine (PMDETA) are dissolved in 65g 2- fourth
In ketone, after dissolution, 0.4g cuprous bromide is added, is stirred to react 15min at 40 DEG C under nitrogen protection, obtains catalyst.It is added
Ten trifluoro octyl acrylate (TFOA) of 63.5g 1H, 1H, 2H, 2H- is heated to 78 DEG C, reacts 4 hours.After reaction, add
Enter m- (bis trifluoromethyl) benzene of 310gTHF and 105g, cross neutral alumina (200-300 mesh) column, it is molten to obtain faint yellow clarification
Liquid.Solution vacuum rotary steam at 65 DEG C removes solvent, and then crude product is added in 960g anhydrous methanol, solid is precipitated, filters, uses
N-hexane washs 150g × 3 time, is dried in vacuo 24 hours at 55 DEG C, obtains terminal hydroxy group fluorine-contaninig polyacrylate 56.2g, receives
Rate is 88.5%.
(4) esterification prepares block polymer
7.1g carboxyl end group polycaprolactone (PCL-COOH) is dissolved in the anhydrous THF of 85g in three-necked flask at room temperature, is added
Enter 4.8g N, N '-carbonyl dimidazoles (CDI) react 2h at 30 DEG C under nitrogen protection.By 0.5g terminal hydroxy group it is poly- (1H, 1H,
Ten trifluoro octyl acrylate of 2H, 2H-) it is dissolved in m- (bis trifluoromethyl) benzene of 32g and is configured to solution, three-necked flask is added
In, reaction mixture reacts 6h at 50 ~ 55 DEG C.After reaction, reaction solution is poured into 310g n-hexane, thick produce is precipitated
Object, filtering are dried in vacuo 3h at 37 DEG C, obtain fluorine-containing alkyl polymer block and change after washing 45g × 3 time with dehydrated alcohol
Property polycaprolactone 6.8g, yield 89.5%.Measuring molecular weight of product is 77000.Product structure formula is as shown in Figure 3.
(5) hydrophobicity is tested
At room temperature, the block modified polycaprolactone of the fluorine-containing alkyl polymer of 0.5g is dissolved in 10g tetrahydrofuran (THF),
It is configured to the solution that mass concentration is 5%.It pours this solution into surface plate, spontaneously dries film forming at room temperature.Using the U.S.
The full-automatic microscopic droplets wetability measuring instrument of 200 type of OCAH of dataphysics company carries out contact angle to polymer film
Test, judges the surface wettability of polymer.Water is chosen as test droplets, droplet size is 3 μ L, and testing five times must put down
Equal contact angle is 116.0 ± 1.2 °, referring to attached drawing 13；After undergoing 72 hours enzymatic degradations, 87.9% degradation.
Embodiment 3
(1) polycaprolactone terminal hydroxy group and polycaprolactone carboxyl end group operating procedure are the same as embodiment 1.
(2) it is poly- (ten trifluoro octyl acrylate of 1H, 1H, 2H, 2H-) to prepare terminal hydroxy group for ATRP method
418ug bromo acid glycol ester and 620ug pentamethyl-diethylenetriamine (PMDETA) are dissolved in 60g 2- fourth
In ketone, after dissolution, 0.6g cuprous bromide is added, is stirred to react 15min at 40 DEG C under nitrogen protection, obtains catalyst.It is added
Ten trifluoro octyl acrylate (TFOA) of 65.6g 1H, 1H, 2H, 2H- is heated to 80 DEG C, reacts 6 hours.After reaction, add
Enter 360gTHF and 120g benzotrifluoride, crosses neutral alumina (200-300 mesh) column, obtain faint yellow clear solution.Solution is 65
Vacuum rotary steam removes solvent at DEG C, and then crude product is added in 1050g anhydrous methanol, and solid is precipitated, and filtering is washed with n-hexane
150g × 3 time are dried in vacuo 24 hours at 55 DEG C, obtain terminal hydroxy group fluorine-contaninig polyacrylate 55.3g, yield 84.3%.
(3) esterification prepares block polymer
7.0g carboxyl end group polycaprolactone (PCL-COOH) is dissolved in the anhydrous THF of 100g in three-necked flask at room temperature, is added
Enter 5.1g N, N '-carbonyl dimidazoles (CDI) react 2h at 30 DEG C under nitrogen protection.By 0.7g terminal hydroxy group it is poly- (1H, 1H,
Ten trifluoro octyl acrylate of 2H, 2H-) it is dissolved in 40g benzotrifluoride and is configured to solution, it is added in three-necked flask, reaction is mixed
It closes object and reacts 4h at 51 ~ 55 DEG C.After reaction, reaction solution is poured into 350g n-hexane, crude product is precipitated, filtered, with
After dehydrated alcohol washs 45g × 3 time, it is dried in vacuo 3h at 37 DEG C, obtains the block modified polycaprolactone of fluorine-containing alkyl polymer
7.1g, yield 92.2%.Measuring molecular weight of product is 78700.Product structure formula is as shown in Figure 4.
(4) hydrophobicity is tested
At room temperature, the block modified polycaprolactone of the fluorine-containing alkyl polymer of 0.5g is dissolved in 10g tetrahydrofuran, is configured to
The solution that mass concentration is 5%.It pours this solution into surface plate, spontaneously dries film forming at room temperature.Using the U.S.
The full-automatic microscopic droplets wetability measuring instrument of 200 type of OCAH of dataphysics company carries out contact angle to polymer film
Test, judges the surface wettability of polymer.Water is chosen as test droplets, droplet size is 3 μ L, and testing five times must put down
Equal contact angle is 128.4 ± 1.3 °, referring to attached drawing 13.
Embodiment 4
(1) polycaprolactone terminal hydroxy group and polycaprolactone carboxyl end group reaction step are the same as embodiment 2.
(2) it is poly- (ten trifluoro octyl acrylate of 1H, 1H, 2H, 2H-) to prepare terminal hydroxy group for ATRP method
490ug bromo acid glycol ester and 655ug pentamethyl-diethylenetriamine (PMDETA) are dissolved in 60g 2- fourth
In ketone, after dissolution, 0.5g cuprous bromide is added, is stirred to react 15min at 40 DEG C under nitrogen protection, obtains catalyst.It is added
Ten trifluoro octyl acrylate (TFOA) of 66.1g 1H, 1H, 2H, 2H- is heated to 80 DEG C, reacts 8 hours.After reaction, add
Enter bis- (trifluoromethyl) benzene of 380gTHF and 155g, crosses neutral alumina (200-300 mesh) column, obtain faint yellow clear solution.It is molten
Liquid at 65 DEG C vacuum rotary steam remove solvent, then will crude product be added 1050g anhydrous methanol in, be precipitated solid, filtering, use just oneself
Alkane washs 150g × 3 time, is dried in vacuo 24 hours at 55 DEG C, obtains terminal hydroxy group fluorine-contaninig polyacrylate 57.3g, yield is
86.7%。
(3) esterification prepares block polymer
7.2g carboxyl end group polycaprolactone (PCL-COOH) is dissolved in the anhydrous THF of 80g in three-necked flask at room temperature, is added
Enter 4.9g N, N '-carbonyl dimidazoles (CDI) react 2h at 30 DEG C under nitrogen protection.By 0.55g terminal hydroxy group it is poly- (1H, 1H,
Ten trifluoro octyl acrylate of 2H, 2H-) it is dissolved in bis- (trifluoromethyl) benzene of 30g and is configured to solution, it is added in three-necked flask,
Reaction mixture reacts 4h at 50 ~ 54 DEG C.After reaction, reaction solution is poured into 310g n-hexane, crude product, mistake is precipitated
Filter is dried in vacuo 3h at 37 DEG C after washing 45g × 3 time with dehydrated alcohol, and it is block modified poly- to obtain fluorine-containing alkyl polymer
Caprolactone 6.3g, yield 81.3%.Measuring molecular weight of product is 79900.Product structure formula is as shown in Figure 5.
(4) hydrophobicity is tested
At room temperature, the block modified polycaprolactone of the fluorine-containing alkyl polymer of 0.5g is dissolved in 10g methylene chloride, is configured to
The solution that mass concentration is 5%.It pours this solution into surface plate, spontaneously dries film forming at room temperature.Using the U.S.
The full-automatic microscopic droplets wetability measuring instrument of 200 type of OCAH of dataphysics company carries out contact angle to polymer film
Test, judges the surface wettability of polymer.Water is chosen as test droplets, droplet size is 3 μ L, and testing five times must put down
Equal contact angle is 127.3 ± 0.8 °, referring to attached drawing 13.
Embodiment 5
(1) polycaprolactone terminal hydroxy group
The 125.0g PCL that molecular weight is 50,000 is dissolved in 850g Isosorbide-5-Nitrae-dioxane at 37 DEG C, nitrogen protection
Under, 25g 6- amino -1- hexanol is added, reacts 12h.After reaction, by reaction solution be slowly added to the 650g being stirred continuously without
In water-ethanol, solid is precipitated.Filtering, filter cake wash 60g × 3 time with dehydrated alcohol, are dried in vacuo for 24 hours, are produced at 37 DEG C
Object 87.8g, yield 70.2%.Measuring molecular weight of product is 50500.
(2) polycaprolactone carboxyl end group
620g 1,4- bis- is added in the terminal hydroxy group polycaprolactone 62.5g(PCL-OH of above-mentioned preparation) and 29.5g succinic anhydride
In six ring of oxygen.After stirring and dissolving, 9.98g Anhydrous potassium carbonate (K is sequentially added2CO3) and 8.97g 4-dimethylaminopyridine
(DMAP), 4h is reacted at room temperature under nitrogen protection.After reaction, it filters, 15g acetic acid is added in filtrate, and solution addition 1020g is gone
In ionized water, solid is precipitated.Filtering, filter cake wash 120g × 3 time with dehydrated alcohol, are dried in vacuo for 24 hours, obtain at 37 DEG C
Product 48.8g, yield 78.0%.Measuring molecular weight of product is 49800.
(3) it is poly- (1H, 1H, 3H- hexafluoro butyl methyl acrylate) to prepare terminal hydroxy group for ATRP method
453ug bromo acid glycol ester and 662ug pentamethyl-diethylenetriamine (PMDETA) are dissolved in 65g 2- fourth
In ketone, after dissolution, 0.6g cuprous bromide is added, is stirred to react 15min at 40 DEG C under nitrogen protection, obtains catalyst.It is added
67.1g 1H, 1H, 3H- hexafluoro butyl methyl acrylate (HFBMA) is heated to 80 DEG C, reacts 12 hours.After reaction,
350gTHF and 115g trifluoromethylbenzene is added, crosses neutral alumina (200-300 mesh) column, obtains faint yellow clear solution.Solution
Vacuum rotary steam removes solvent at 55 DEG C, and then crude product is added in 1020g anhydrous methanol, and solid is precipitated, and n-hexane is used in filtering
150g × 3 time are washed, is dried in vacuo 24 hours at 55 DEG C, obtains poly- (1H, 1H, 3H- the hexafluoro butyl methyl propylene of terminal hydroxy group
Acid esters) 61.8g, yield 92.1%.
(4) esterification prepares block polymer
45.1g carboxyl end group polycaprolactone (PCL-COOH) is dissolved in the anhydrous THF of 255g in three-necked flask at room temperature,
5.1g N is added, N '-carbonyl dimidazoles (CDI) react 2h at 30 DEG C under nitrogen protection.By 0.6g terminal hydroxy group it is poly- (1H,
1H, 3H- hexafluoro butyl methyl acrylate) it is dissolved in 32g trifluoromethylbenzene and is configured to solution, it is added in three-necked flask, instead
Mixture is answered to react 6h at 50 ~ 55 DEG C.After reaction, reaction solution is poured into 330g n-hexane, crude product, mistake is precipitated
Filter is dried in vacuo 3h at 37 DEG C after washing 45g × 3 time with dehydrated alcohol, and it is block modified poly- to obtain fluorine-containing alkyl polymer
Caprolactone 42.0g, yield 92.0%.Measuring molecular weight of product is 59100.Product structure formula is as shown in Figure 6.
(5) hydrophobicity is tested
At room temperature, the block modified polycaprolactone of the fluorine-containing alkyl polymer of 0.5g is dissolved in 10g tetrahydrofuran (THF),
It is configured to the solution that mass concentration is 5%.It pours this solution into surface plate, spontaneously dries film forming at room temperature.Using the U.S.
The full-automatic microscopic droplets wetability measuring instrument of 200 type of OCAH of dataphysics company carries out contact angle to polymer film
Test, judges the surface wettability of polymer.Water is chosen as test droplets, droplet size is 3 μ L, and testing five times must put down
Equal contact angle is 109.0 ± 1.0 °.
Embodiment 6
(1) polycaprolactone terminal hydroxy group and polycaprolactone carboxyl end group are the same as embodiment 5.
(2) it is poly- (1H, 1H, 3H- hexafluoro butyl methyl acrylate) to prepare terminal hydroxy group for ATRP method
450ug bromo acid glycol ester and 666ug pentamethyl-diethylenetriamine (PMDETA) are dissolved in 65g 2- fourth
In ketone, after dissolution, 0.5g cuprous bromide is added, is stirred to react 15min at 40 DEG C under nitrogen protection, obtains catalyst.It is added
66.8g 1H, 1H, 3H- hexafluoro butyl methyl acrylate (HFBMA) is heated to 80 DEG C, reacts 5 hours.After reaction, add
Enter 345gTHF and 110g trifluoromethylbenzene, crosses neutral alumina (200-300 mesh) column, obtain faint yellow clear solution.Solution exists
Vacuum rotary steam removes solvent at 55 DEG C, and then crude product is added in 1010g anhydrous methanol, and solid is precipitated, and filtering is washed with n-hexane
150g × 3 time are washed, are dried in vacuo 24 hours at 55 DEG C, poly- (1H, 1H, 3H- the hexafluoro butyl methyl acrylic acid of terminal hydroxy group is obtained
Ester) 58.1g, yield 87.0%.
(3) esterification prepares block polymer
45.3g carboxyl end group polycaprolactone (PCL-COOH) is dissolved in the anhydrous THF of 285g in three-necked flask at room temperature,
5.2g N is added, N '-carbonyl dimidazoles (CDI) react 2h at 30 DEG C under nitrogen protection.By 0.4g terminal hydroxy group it is poly- (1H,
1H, 3H- hexafluoro butyl methyl acrylate) it is dissolved in 31g trifluoromethylbenzene and is configured to solution, it is added in three-necked flask, instead
Mixture is answered to react 6h at 52 ~ 55 DEG C.After reaction, reaction solution is poured into 320g n-hexane, crude product, mistake is precipitated
Filter is dried in vacuo 3h at 37 DEG C after washing 45g × 3 time with dehydrated alcohol, and it is block modified poly- to obtain fluorine-containing alkyl polymer
Caprolactone 41.4g, yield 90.5%.Measuring molecular weight of product is 49120.Product structure formula is as shown in Figure 7.
(4) hydrophobicity is tested
At room temperature, the block modified polycaprolactone of the fluorine-containing alkyl polymer of 0.5g is dissolved in 10g tetrahydrofuran (THF),
It is configured to the solution that mass concentration is 5%.It pours this solution into surface plate, spontaneously dries film forming at room temperature.Using the U.S.
The full-automatic microscopic droplets wetability measuring instrument of 200 type of OCAH of dataphysics company carries out contact angle to polymer film
Test, judges the surface wettability of polymer.Water is chosen as test droplets, droplet size is 3 μ L, and testing five times must put down
Equal contact angle is 106.0 ± 0.8 °；After undergoing 72 hours enzymatic degradations, 86.2% degradation.
Embodiment 7
(1) it is poly- (ten trifluoro octyl acrylate of 1H, 1H, 2H, 2H-) to prepare terminal hydroxy group for ATRP method
210ug bromo acid glycol ester and 320ug pentamethyl-diethylenetriamine (PMDETA) are dissolved in 30g 1,3-
In bis- (trifluoromethyl) benzene, after dissolution, 0.2g cuprous bromide is added, is stirred to react 15min at 40 DEG C under nitrogen protection, obtains
Catalyst.32.5g 1H, 1H, 2H is added, ten trifluoro octyl acrylate (TFOA) of 2H- is heated to 80 DEG C, reacts 24 hours.
After reaction, 250g1,3-(bis trifluoromethyl is added) benzene, neutral alumina (200-300 mesh) column is crossed, is obtained faint yellow clear
Clear solution.Solution vacuum rotary steam at 75 DEG C removes solvent, and then crude product is added in 510g anhydrous methanol, solid, mistake is precipitated
Filter, washs 60g × 3 time with n-hexane, is dried in vacuo 24 hours at 55 DEG C, obtains terminal hydroxy group fluorine-contaninig polyacrylate
29.6g, measuring product number-average molecular weight is 6030, yield 91.2%.
(2) polycaprolactone carboxyl end group
The 125.0g PCL that molecular weight is 4500 is dissolved in 850g Isosorbide-5-Nitrae-dioxane at 37 DEG C, nitrogen protection
Under, 25g 6- amino -1- hexanol is added, reacts 12h.After reaction, by reaction solution be slowly added to the 650g being stirred continuously without
In water-ethanol, solid is precipitated.Filtering, filter cake wash 60g × 3 time with dehydrated alcohol, are dried in vacuo for 24 hours, are produced at 37 DEG C
Object terminal hydroxy group polycaprolactone, yield 76.2%.Measuring molecular weight of product is 4000.
Terminal hydroxy group polycaprolactone (PCL) 25.0g(PCL-OH for being 4000 by molecular weight) and the addition of 0.7g succinic anhydride
In 110g 1,4- dioxane.After stirring and dissolving, 1.9g Anhydrous potassium carbonate (K is sequentially added2CO3) and 2.5g 4- dimethylamino
Pyridine (DMAP) reacts at room temperature 4h under nitrogen protection.After reaction, it filters, 4g acetic acid is added in filtrate, and 300g is added in solution
In deionized water, solid is precipitated.Filtering, filter cake wash 250g × 3 time with dehydrated alcohol, are dried in vacuo for 24 hours, obtain at 37 DEG C
To product 18.5g, yield 74.1%.Measuring molecular weight of product is 4520.
(3) esterification prepares block polymer
4.2g carboxyl end group polycaprolactone (PCL-COOH) is dissolved in the anhydrous THF of 45g in three-necked flask at room temperature, is added
Enter 0.3g N, N '-carbonyl dimidazoles (CDI) react 2h at 30 DEG C under nitrogen protection.By 5.9g terminal hydroxy group it is poly- (1H, 1H,
Ten trifluoro octyl acrylate of 2H, 2H-) it is dissolved in 65g 1,3-(bis trifluoromethyl) solution is configured in benzene, three mouthfuls of burnings are added
In bottle, reaction mixture reacts 6h at 50 ~ 55 DEG C.After reaction, reaction solution is poured into 350g n-hexane, thick produce is precipitated
Object, filtering are dried in vacuo 3h at 37 DEG C, obtain the block modified fluothane of polycaprolactone after washing 50g × 3 time with dehydrated alcohol
Based polyalcohol (PCL4000-PTFOA) 7.1g, yield 70.3%.Measuring molecular weight of product is 10080.Product structure formula such as Fig. 8 institute
Show.
(4) degradability is tested
The block modified fluothane based polyalcohol (PCL4000-PTFOA) of 2 g polycaprolactones is dissolved in 20mL tetrahydrofuran,
It is subsequently transferred in surface plate, is horizontally arranged in an oven, is dried for 24 hours at 40 DEG C.The circle that film is cut into diameter about 10mm is thin
Piece, weight about 0.04g.The disk cut is put and is cleaned in ethanol, the impurity of film surface is removed, finally uses thin discs
Deionized water cleaning, is placed in vacuum drying oven, dries at 37 DEG C and obtain clean thin discs for 24 hours, remains degradation and uses.
By the thin slice made, weighing is recorded and is put into numbered culture plate aperture again respectively, then uses pipette
Aspergillus oryzae lipase PBS (pH=7.2 ~ 7.4) solution of 8 U/mL of 3mL (0. 027 mg/mL) is pipetted, corresponding training is added
It supports in plate aperture.Each disk is completely immersed in enzyme solutions, and three samples are arranged in each degradation time point, accidental to reduce
Error.They are degraded respectively after 12 h, 24 h, 48 h and 72 h, and taking-up is cleaned with a large amount of deionized water, and remove surface can
Solubility impurity.Then, it is placed in vacuum drying oven, is dried for 24 hours at 37 DEG C, and record of weighing.
Weight-loss ratio calculation formula is as follows, and following embodiment and comparative example also use this formula:
Weight-loss ratio (%)=(W0-Wi)/(W0)
Wherein W0For the quality before the degradation of thin slice, Wi For the average quality of three samples after degradation.
Measure 12 hours, 24 hours, 48 hours and 72 hours weight-loss ratios of PCL4000-PTFOA sample be respectively 2.1%,
22.3%, 43.5% and 77.2%.The block modified fluoroalkyl polymeric articles of polycaprolactone after undergoing 72 hours enzymatic degradations,
77.2% degradation, it is 119.0 ± 1.1 ° that test five times, which obtain average contact angle,.
Embodiment 8
(1) ATRP method prepares terminal hydroxy group poly- (ten trifluoro octyl acrylate of 1H, 1H, 2H, 2H-) such as embodiment 2.
(2) polycaprolactone carboxyl end group
The 125.0g PCL that molecular weight is 7000 is dissolved in 850g Isosorbide-5-Nitrae-dioxane at 37 DEG C, nitrogen protection
Under, 25g 6- amino -1- hexanol is added, reacts 12h.After reaction, by reaction solution be slowly added to the 650g being stirred continuously without
In water-ethanol, solid is precipitated.Filtering, filter cake wash 60g × 3 time with dehydrated alcohol, are dried in vacuo for 24 hours, are produced at 37 DEG C
Object terminal hydroxy group polycaprolactone, yield 73.2%.Measuring molecular weight of product is 6100.
Terminal hydroxy group polycaprolactone (PCL) 38.0g(PCL-OH for being 6000 by molecular weight) and the addition of 0.8g succinic anhydride
In 150g 1,4- dioxane.After stirring and dissolving, 1.8g Anhydrous potassium carbonate (K is sequentially added2CO3) and 2.6g 4- dimethylamino
Pyridine (DMAP) reacts at room temperature 4h under nitrogen protection.After reaction, it filters, 5g acetic acid is added in filtrate, and 300g is added in solution
In deionized water, solid is precipitated.Filtering, filter cake wash 250g × 3 time with dehydrated alcohol, are dried in vacuo 12h at 37 DEG C, obtain
To product 30.4g, yield 80.2%.Measuring molecular weight of product is 6700.
(3) esterification prepares block polymer
6.5g carboxyl end group polycaprolactone (PCL-COOH) is dissolved in the anhydrous THF of 55g in three-necked flask at room temperature, is added
Enter 0.4g N, N '-carbonyl dimidazoles (CDI) react 2h at 30 DEG C under nitrogen protection.By 5.9g terminal hydroxy group it is poly- (1H, 1H,
Ten trifluoro octyl acrylate of 2H, 2H-) it is dissolved in 65g 1,3-(bis trifluoromethyl) solution is configured in benzene, three mouthfuls of burnings are added
In bottle, reaction mixture reacts 6h at 50 ~ 55 DEG C.After reaction, reaction solution is poured into 350g n-hexane, thick produce is precipitated
Object, filtering are dried in vacuo 10h at 37 DEG C, obtain the block modified fluorine of polycaprolactone after washing 50g × 3 time with dehydrated alcohol
Alkyl polymer (PCL6000-PTFOA) 9.1g, yield 73.4%.Measuring molecular weight of product is 12110.Product structure formula such as Fig. 9
It is shown.
(4) degradability is tested
The block modified fluothane based polyalcohol (PCL6000-PTFOA) of 2 g polycaprolactones is dissolved in 20mL tetrahydrofuran,
It is subsequently transferred in surface plate, is horizontally arranged in an oven, is dried for 24 hours at 40 DEG C.The circle that film is cut into diameter about 10mm is thin
Piece, weight about 0.04g.The disk cut is put and is cleaned in ethanol, the impurity of film surface is removed, finally uses thin discs
Deionized water cleaning, is placed in vacuum drying oven, dries at 37 DEG C and obtain clean thin discs for 24 hours, remains degradation and uses.
By the thin slice made, weighing is recorded and is put into numbered culture plate aperture again respectively, then uses pipette
Aspergillus oryzae lipase PBS (pH=7.2 ~ 7.4) solution of 8 U/mL of 3mL (0. 027 mg/mL) is pipetted, corresponding training is added
It supports in plate aperture.Each disk is completely immersed in enzyme solutions, and three samples are arranged in each degradation time point, accidental to reduce
Error.They are degraded respectively after 12 h, 24 h, 48 h and 72 h, and taking-up is cleaned with a large amount of deionized water, and remove surface can
Solubility impurity.Then, it is placed in vacuum drying oven, is dried for 24 hours at 37 DEG C, and record of weighing.
Measuring 12 hours, 24 hours, 48 hours and 72 hours weight-loss ratios of PCL6000-PTFOA sample is respectively
1.9%, 21.8%, 43.8% and 80.2%.The block modified fluoroalkyl polymeric articles of polycaprolactone are undergoing the drop of enzymatic in 72 hours
Xie Hou, 80.2% degradation, it is 123.2 ± 1.2 ° that test five times, which obtain average contact angle,.
Embodiment 9
(1) it is poly- (ten trifluoro octyl acrylate of 1H, 1H, 2H, 2H-) to prepare terminal hydroxy group for ATRP method
220ug bromo acid glycol ester and 300ug pentamethyl-diethylenetriamine (PMDETA) are dissolved in 35g 1,3-
In bis- (trifluoromethyl) benzene, after dissolution, 0.2g cuprous bromide is added, is stirred to react 15min at 40 DEG C under nitrogen protection, obtains
Catalyst.33.1g 1H, 1H, 2H is added, ten trifluoro octyl acrylate (TFOA) of 2H- is heated to 80 DEG C, reacts 28 hours.
After reaction, 265g1,3-(bis trifluoromethyl is added) benzene, neutral alumina (200-300 mesh) column is crossed, is obtained faint yellow clear
Clear solution.Solution vacuum rotary steam at 78 DEG C removes solvent, and then crude product is added in 500g anhydrous methanol, solid, mistake is precipitated
Filter, washs 60g × 3 time with n-hexane, is dried in vacuo 24 hours at 65 DEG C, obtains terminal hydroxy group fluorine-contaninig polyacrylate
22.1g measuring product number-average molecular weight is 6630, yield 66.7%.
(2) polycaprolactone carboxyl end group
The 125.0g PCL that molecular weight is 9800 is dissolved in 850g Isosorbide-5-Nitrae-dioxane at 37 DEG C, nitrogen protection
Under, 25g 6- amino -1- hexanol is added, reacts 12h.After reaction, by reaction solution be slowly added to the 650g being stirred continuously without
In water-ethanol, solid is precipitated.Filtering, filter cake wash 60g × 3 time with dehydrated alcohol, are dried in vacuo for 24 hours, are produced at 37 DEG C
Object terminal hydroxy group polycaprolactone, yield 72.2%.Measuring molecular weight of product is 8210.
Terminal hydroxy group polycaprolactone (PCL) 49.0g(PCL-OH for being 8000 by molecular weight) and the addition of 0.8g succinic anhydride
In 175g 1,4- dioxane.After stirring and dissolving, 1.9g Anhydrous potassium carbonate (K is sequentially added2CO3) and 2.5g 4- dimethylamino
Pyridine (DMAP) reacts at room temperature 4h under nitrogen protection.After reaction, it filters, 6g acetic acid is added in filtrate, and 300g is added in solution
In deionized water, solid is precipitated.Filtering, filter cake wash 250g × 3 time with dehydrated alcohol, are dried in vacuo for 24 hours, obtain at 37 DEG C
To product 37.0g, yield 75.6%.Measuring molecular weight of product is 8020.
(3) esterification prepares block polymer
8.4g carboxyl end group polycaprolactone (PCL-COOH) is dissolved in the bis- trifluoros of 75g1,3-(in three-necked flask at room temperature
Methyl) benzene, 0.5g N is added, N '-carbonyl dimidazoles (CDI) react 2h at 30 DEG C under nitrogen protection.By 5.8g terminal hydroxy group
Poly- (ten trifluoro octyl acrylate of 1H, 1H, 2H, 2H-) is dissolved in 70g 1,3-(bis trifluoromethyl) solution is configured in benzene, add
Enter in three-necked flask, reaction mixture reacts 6h at 50 ~ 55 DEG C.After reaction, reaction solution is poured into 350g n-hexane,
Crude product is precipitated, filtering is dried in vacuo 3h at 37 DEG C, obtains polycaprolactone block after washing 50g × 3 time with dehydrated alcohol
Modified fluothane based polyalcohol (PCL8000-PTFOA) 9.2g, yield 65.0%.Measuring molecular weight of product is 15090.Product structure
Formula is as shown in Figure 10.
(4) degradability is tested
The block modified fluothane based polyalcohol (PCL8000-PTFOA) of 2 g polycaprolactones is dissolved in 20mL tetrahydrofuran,
It is subsequently transferred in surface plate, is horizontally arranged in an oven, is dried for 24 hours at 40 DEG C.The circle that film is cut into diameter about 10mm is thin
Piece, weight about 0.04g.The disk cut is put and is cleaned in ethanol, the impurity of film surface is removed, finally uses thin discs
Deionized water cleaning, is placed in vacuum drying oven, dries at 37 DEG C and obtain clean thin discs for 24 hours, remains degradation and uses.
By the thin slice made, weighing is recorded and is put into numbered culture plate aperture again respectively, then uses pipette
Aspergillus oryzae lipase PBS (pH=7.2 ~ 7.4) solution of 8 U/mL of 3mL (0. 027 mg/mL) is pipetted, corresponding training is added
It supports in plate aperture.Each disk is completely immersed in enzyme solutions, and three samples are arranged in each degradation time point, accidental to reduce
Error.They are degraded respectively after 12 h, 24 h, 48 h and 72 h, and taking-up is cleaned with a large amount of deionized water, and remove surface can
Solubility impurity.Then, it is placed in vacuum drying oven, is dried for 24 hours at 37 DEG C, and record of weighing.
Measuring 12 hours, 24 hours, 48 hours and 72 hours weight-loss ratios of PCL8000-PTFOA sample is respectively
1.9%, 22.9%, 44.5% and 84.8%.The block modified fluoroalkyl polymeric articles of polycaprolactone are undergoing the drop of enzymatic in 72 hours
Xie Hou, 84.8% degradation.
Embodiment 10
(1) it is poly- (1H, 1H, 3H- hexafluoro butyl methyl acrylate) to prepare terminal hydroxy group for ATRP method
453ug bromo acid glycol ester and 662ug pentamethyl-diethylenetriamine (PMDETA) are dissolved in 65g 2- fourth
In ketone, after dissolution, 0.6g cuprous bromide is added, is stirred to react 15min at 40 DEG C under nitrogen protection, obtains catalyst.It is added
67.1g 1H, 1H, 3H- hexafluoro butyl methyl acrylate (HFBDA) is heated to 80 DEG C, reacts 28 hours.After reaction,
350gTHF and 115g benzotrifluoride is added, crosses neutral alumina (200-300 mesh) column, obtains faint yellow clear solution.Solution exists
Vacuum rotary steam removes solvent at 55 DEG C, and then crude product is added in 1020g anhydrous methanol, and solid is precipitated, and filtering is washed with n-hexane
150g × 3 time are washed, are dried in vacuo 24 hours at 55 DEG C, poly- (1H, 1H, 3H- the hexafluoro butyl methyl acrylic acid of terminal hydroxy group is obtained
Ester) 61.8g, molecular weight of product 3950, yield 92.1%.
(2) polycaprolactone carboxyl end group
Terminal hydroxy group polycaprolactone (prepared by PCL, the embodiment 5) 329.0g(PCL-OH for being 50500 by molecular weight) and 0.8g
Succinic anhydride is added in 152g 1,4- dioxane.After stirring and dissolving, 1.9g Anhydrous potassium carbonate (K is sequentially added2CO3) and
2.3g 4-dimethylaminopyridine (DMAP) reacts at room temperature 6h under nitrogen protection.After reaction, it filters, 4g second is added in filtrate
Solution is added in 300g deionized water acid, and solid is precipitated.Filtering, filter cake washs 250g × 3 time with dehydrated alcohol, in 37 DEG C
Lower vacuum drying for 24 hours, obtains product 245.5g, yield 74.6%.Measuring molecular weight of product is 49900.
(3) esterification prepares block polymer
The carboxyl end group polycaprolactone that 50.1g molecular weight is 49900 is dissolved in 550g1,3- in three-necked flask at room temperature
(bis trifluoromethyl) benzene, is added 0.5g N, and N '-carbonyl dimidazoles (CDI) react 2h at 30 DEG C under nitrogen protection.It will
5.8g terminal hydroxy group poly- (1H, 1H, 3H- hexafluoro butyl methyl acrylate), which is dissolved in 71g benzotrifluoride, is configured to solution, is added
In three-necked flask, reaction mixture reacts 6h at 50 ~ 55 DEG C.After reaction, reaction solution is poured into 860g n-hexane, is analysed
Crude product out, filtering are dried in vacuo 3h at 37 DEG C, obtain polycaprolactone block after washing 200g × 3 time with dehydrated alcohol
Modified fluothane based polyalcohol (PCL50000-PHFDA) 79.8g, yield 80.1%.Measuring molecular weight of product is 50230.Product knot
Structure formula is as shown in figure 11.
(4) degradability testing procedure is the same as embodiment 7
Measuring 12 hours, 24 hours, 48 hours and 72 hours weight-loss ratios of PCL50000-PHFDA sample is respectively
2.2%, 23.4%, 41.2% and 86.3%.The block modified fluoroalkyl polymeric articles of polycaprolactone are undergoing the drop of enzymatic in 72 hours
Xie Hou, 86.3% degradation.
Comparative example:
(1) ATRP method prepares terminal hydroxy group poly- (ten trifluoro octyl acrylate of 1H, 1H, 2H, 2H-) with embodiment 7.
(2) polycaprolactone carboxyl end group
The 125.0g PCL that molecular weight is 2300 is dissolved in 850g Isosorbide-5-Nitrae-dioxane at 37 DEG C, nitrogen protection
Under, 25g 6- amino -1- hexanol is added, reacts 12h.After reaction, by reaction solution be slowly added to the 650g being stirred continuously without
In water-ethanol, solid is precipitated.Filtering, filter cake wash 60g × 3 time with dehydrated alcohol, are dried in vacuo for 24 hours, are produced at 37 DEG C
Object terminal hydroxy group polycaprolactone, yield 75.6%.Measuring molecular weight of product is 2000.
Terminal hydroxy group polycaprolactone (PCL) 12.4g(PCL-OH for being 2000 by molecular weight) and 0.8g succinic anhydride addition 90g
In 1,4- dioxane.After stirring and dissolving, 1.6g Anhydrous potassium carbonate (K is sequentially added2CO3) and 2.1g 4-dimethylaminopyridine
(DMAP), 6h is reacted at room temperature under nitrogen protection.After reaction, filter, filtrate be added 3g acetic acid, by solution addition 200g go from
In sub- water, solid is precipitated.Filtering, filter cake wash 150g × 3 time with dehydrated alcohol, are dried in vacuo for 24 hours, are produced at 37 DEG C
Object 6.3g, yield 51.2%.Measuring molecular weight of product is 1920.
(3) esterification prepares block polymer
2.0g carboxyl end group polycaprolactone (PCL-COOH) is dissolved in the anhydrous THF of 35g in three-necked flask at room temperature, is added
Enter 0.3g N, N '-carbonyl dimidazoles (CDI) react 2h at 30 DEG C under nitrogen protection.By 5.5g terminal hydroxy group it is poly- (1H, 1H,
Ten trifluoro octyl acrylate of 2H, 2H-) it is dissolved in 65g 1,3-(bis trifluoromethyl) solution is configured in benzene, three mouthfuls of burnings are added
In bottle, reaction mixture reacts 6h at 50 ~ 55 DEG C.After reaction, reaction solution is poured into 290g n-hexane, thick produce is precipitated
Object, filtering are dried in vacuo 3h at 37 DEG C, obtain the block modified fluothane of polycaprolactone after washing 50g × 3 time with dehydrated alcohol
Based polyalcohol (PCL2000-PTFOA) 6.8g, yield 91.1%.Measuring molecular weight of product is 8150.Product structure formula such as Figure 12 institute
Show.
(4) degradability is tested
The block modified fluothane based polyalcohol (PCL2000-PTFOA) of 2 g polycaprolactones is dissolved in 20mL tetrahydrofuran,
It is subsequently transferred in surface plate, is horizontally arranged in an oven, is dried for 24 hours at 40 DEG C.The circle that film is cut into diameter about 10mm is thin
Piece, weight about 0.04g.The disk cut is put and is cleaned in ethanol, the impurity of film surface is removed, finally uses thin discs
Deionized water cleaning, is placed in vacuum drying oven, dries at 37 DEG C and obtain clean thin discs for 24 hours, remains degradation and uses.
By the thin slice made, weighing is recorded and is put into numbered culture plate aperture again respectively, then uses pipette
Aspergillus oryzae lipase PBS (pH=7.2 ~ 7.4) solution of 8 U/mL of 3mL (0. 027 mg/mL) is pipetted, corresponding training is added
It supports in plate aperture.Each disk is completely immersed in enzyme solutions, and three samples are arranged in each degradation time point, accidental to reduce
Error.They are degraded respectively after 12 h, 24 h, 48 h and 72 h, and taking-up is cleaned with a large amount of deionized water, and remove surface can
Solubility impurity.Then, it is placed in vacuum drying oven, is dried for 24 hours at 37 DEG C, and record of weighing.
Measuring 12 hours, 24 hours, 48 hours and 72 hours weight-loss ratios of PCL2000-PTFOA sample is respectively
1.5%, 5.2%, 8.0% and 12.1%, product is degraded very slow after enzyme catalysis 72 hours, and testing five times must be averaged
Contact angle is 98.5 ± 1.3 °.
Figure 14 is the infrared absorption of the hydrophobic type polycaprolactone of unmodified polycaprolactone (PCL) and preparation of the embodiment of the present invention
Curve.Wherein, curve a is unmodified polycaprolactone, and curve b is hydrophobic type polycaprolactone prepared by embodiment 1, and curve c is real
The hydrophobic type polycaprolactone of the preparation of example 2 is applied, curve d is hydrophobic type polycaprolactone prepared by embodiment 3, and curve e is the system of embodiment 4
Standby hydrophobic type polycaprolactone.In Figure 14,2950.4 cm-1With 2866.8 cm-1The absorption peak at place belong to the symmetrical of-CH and
Antisymmetric stretching vibration peak, 1728.0 cm-1 The stretching vibration absworption peak for belonging to C=O, in 1237.1 cm-1、1190.1
cm-1、1145.1 cm-1、1082.3 cm-1The peak at place belongs to the characteristic absorption peak of C-F, and in 1237.1 cm-1、1190.1
cm-1Locate the characteristic absorption overlap of peaks at peak and C=O.It is compared with unmodified PCL infrared absorption curve a, can be evident that, contain
In PCL infrared absorption curve after fluoropolymer is block modified, there is the characteristic absorption peak of C-F.
Figure 15 is the nuclear magnetic resonance of the hydrophobic type polycaprolactone of unmodified polycaprolactone (PCL) and preparation of the embodiment of the present invention
Figure.Wherein, curve (1) is unmodified polycaprolactone, and curve (2) is hydrophobic type polycaprolactone prepared by embodiment 1, curve (3)
For hydrophobic type polycaprolactone prepared by embodiment 2, curve (4) is hydrophobic type polycaprolactone prepared by embodiment 3, and curve (5) is
Hydrophobic type polycaprolactone prepared by embodiment 4.In Figure 15, the peak point of 4.05 ppm, 2.31 ppm, 1.65 ppm and 1.39 ppm
- C in PCL chain structural unit is not belonged toH 2Peak.In addition, in curve (2), (3), (4), (5), the peak e of 4.31 ppm
It is attributed to O=COCH 2Peak, the peak f of 2.42 ppm is-CH2C6F13Characteristic peak.
Figure 16 is the Polycaprolactone modified fluoropolymer-containing degradation process photo figure of the present invention；Wherein, comparative example gathers oneself
Lactone 2000(PCL2000) block modified fluoro-containing macromolecule material PCL2000-PTFOA degradation is slow；Embodiment 8 and implementation
The block modified fluoro-containing macromolecule material PCL6000-PTFOA and PCL8000-PTFOA of polycaprolactone prepared by example 9 is small through 72
When enzymatic treatment after, it is most of to degrade, and polycaprolactone 8000(PCL8000) block modified fluoro-containing macromolecule material residual
Less, it degrades more thorough.
Figure 17 is the degradation process SEM shape appearance figure of hydrophobic type polycaprolactone of the invention.Wherein, it 1,2,3,4 respectively indicates
Shape appearance figure before enzymatic degradation, after 12 h of degradation, 48 h of degradation, 72 h of degradation；A is to prepare according to embodiment 7
Shape appearance figure of the PCL4000-PTFOA before enzymatic degradation, after 12 h of degradation, 48 h of degradation, 72 h of degradation；B is according to implementation
The shape appearance figure of PCL6000-PTFOA prepared by example 8 before enzymatic degradation, after 12 h of degradation, 48 h of degradation, 72 h of degradation；C is
The pattern of PCL8000-PTFOA prepared by embodiment 9 before enzymatic degradation, after 12 h of degradation, 48 h of degradation, 72 h of degradation
Figure.
Figure 18 is the fluorine-containing polycaprolactone solution thereon of the present invention, wherein (a) solvent is methylene chloride, solution concentration is
2wt%；(b) solvent is tetrahydrofuran, solution concentration 3wt%；(c) solvent is methylene chloride, solution concentration 10wt%；Figure 19
For the photo of the fluorine-containing polycaprolactone film of the present invention, wherein (a) solvent is methylene chloride, solution concentration 3wt%；(b) solvent is four
Hydrogen furans, solution concentration 10wt%.Show that fluorine-containing polycaprolactone dissolubility of the invention is good, good film-forming property.
The preparation method of hydrophobic type polycaprolactone of the invention is synthesized using atom transfer radical polymerization (ATRP) method
Hydrophobic fluorine-containing alkyl polyacrylates, then be condensed mutually by macromolecule and directly prepare block polymer, belong to macromolecule conjunction
At field.Hydrophobic type polycaprolactone disclosed by the invention and preparation method thereof, due to using mildly anti-during the preparation process
Condition is answered, polycaprolactone is avoided and degrades, obtained modification PCL polymerizate structure-controllable and molecular weight is high, film forming
Good, processing performance is excellent.The fluorine-contaninig polyacrylate of structure-controllable, therefore modified product are introduced in modified polycaprolactone structure
Hydrophobicity it is controllable；Due to introducing the polycaprolactone of biodegradable and enzyme degradation in fluorine-contaninig polyacrylate structure, because
This modified product is degradable.
Claims (7)
1. a kind of hydrophobic type polycaprolactone, which is characterized in that the chemical structural formula of the hydrophobic type polycaprolactone is as follows:
Wherein, Rf is containing fluoroalkyl；R is H or alkyl；M is 35~1300；N is 5~100；The fluoroalkyl that contains is nine fluorine
One of amyl, ten trifluoro octyls, 17 fluorine decyls, hexafluoro butyl, ten difluoro heptyl or octafluoro amyl；The alkyl is first
Base.
2. hydrophobic type polycaprolactone as described in claim 1, which is characterized in that the preparation method packet of the hydrophobic type polycaprolactone
Include following steps:
(1) pla-pcl is reacted with alkamine compound, prepares terminal hydroxy group polycaprolactone；
(2) by terminal hydroxy group pla-pcl and anhydride reaction, carboxyl end group polycaprolactone is prepared；
(3) bromo acid glycol ester is reacted with containing fluoroalkyl, prepares terminal hydroxy group fluorine-contaninig polyacrylate；
(4) carboxyl end group polycaprolactone is reacted with terminal hydroxy group fluorine-contaninig polyacrylate, prepares hydrophobic type polycaprolactone；
The molecular weight of the pla-pcl is 4.56 ten thousand~14.82 ten thousand；Alkamine compound is 6- amino -1- hexanol；Acid anhydrides is
Succinic anhydride；It is nine fluorine amyl group acrylate, ten trifluoro octyl acrylates, ten trifluoro octyl methyls containing fluoroalkyl
Acrylate, 17 fluorine decyl acrylate, 17 fluorine decyl methacrylates, hexafluoro butyl propyleneglycol acid esters, hexafluoro butyl
One of methacrylate, ten difluoro heptyl methacrylates or octafluoro acrylate.
3. hydrophobic type polycaprolactone as claimed in claim 2, it is characterised in that: the mass ratio of pla-pcl and alkamine compound
It is 1: 0.2~2；The mass ratio of terminal hydroxy group pla-pcl and acid anhydrides is (1~200): (0.5~2)；Bromo acid glycol ester
It is (1 × 10 with the mass ratio containing fluoroalkyl-6~5 × 10-5): (0.5~5)；Carboxyl end group polycaprolactone and terminal hydroxy group
The mass ratio of fluorine-contaninig polyacrylate is (1~4): (0.05~10).
4. hydrophobic type polycaprolactone as claimed in claim 2, it is characterised in that: the reaction of step (1) is room temperature under nitrogen protection
Reaction 1~24 hour；The reaction of step (2) is that 1~6h is reacted at room temperature under nitrogen protection；The reaction of step (3) is 50~90 DEG C
Reaction 1~for 24 hours；The reaction of step (4) is 30~65 DEG C of 1~8h of reaction.
5. hydrophobic type polycaprolactone as claimed in claim 2, it is characterised in that: the reaction of step (1) carries out in organic solvent；
The reaction of step (2) carries out in organic solvent, in the presence of Anhydrous potassium carbonate and 4-dimethylaminopyridine；The reaction of step (3)
In organic solvent, it is carried out in the presence of pentamethyl-diethylenetriamine and cuprous bromide；The reaction of step (4) in organic solvent,
It is carried out in the presence of N, N '-carbonyl dimidazoles.
6. hydrophobic type polycaprolactone as claimed in claim 2, it is characterised in that: in step (4), by carboxyl end group polycaprolactone and N,
N '-carbonyl dimidazoles react at room temperature 1~24 hour under a nitrogen；Then terminal hydroxy group fluorine-contaninig polyacrylate solution is added, in 30
~65 DEG C of 1~8h of reaction, prepare hydrophobic type polycaprolactone.
7. hydrophobic type polycaprolactone described in claim 1 is preparing the application in hydrophobic material or biodegradation material.
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